Patent Publication Number: US-10759989-B2

Title: Temperature-stable paraffin inhibitor compositions

Description:
This application claims benefit of 62/275,339 filed Jan. 6, 2016. 
    
    
     FIELD OF THE INVENTION 
     The present invention generally relates to temperature stable paraffin inhibitor compositions. 
     BACKGROUND 
     Crude oil products are globally obtained from subterranean reservoirs using techniques such as drilling and hydraulic fracturing. Transportation of crude oil products from the subterranean reservoir, required to process, i.e. refine, the crude oil, is accomplished by moving the crude oil through pipes and into storage/transportation means such as rail cars, tanks, and the like. During the moving and/or storage, the crude is often subjected to ambient temperatures between −40° C. and 60° C. 
     Crude oil products include linear and branched alkanes having the general formula C n H 2n+2  wherein n is typically about 1-50, although minor amounts of longer hydrocarbon chains do occur. The higher molecular weight alkanes can be problematic in that their melting points tend to be greater than ambient temperatures in some cases. For example, nonadecane has a melting point of 33° C.; higher alkanes can have melting points in excess of 60° C. for example. 
     The high melting alkane fractions lead to formation of paraffinic residue that solidifies and deposits on the sides and bottoms of pipes, storage vessels, and transportation vessels (rail cars, ocean tankers, etc.). The solidified paraffinic residue, also known as “paraffin wax”, not only reduces the effective volume of the structure it&#39;s contained within but also represents a loss of a valuable component from the body of the crude oil. Excessive paraffin wax buildup reduces the efficiency of transporting crude oil and leads to increased costs related to added downtime for cleaning of the pipes and/or vessels as well as disposal of residues removed from the vessel which increase environmental burden. While the pipelines and vessels can be cleaned to remove the paraffinic residue, the process generates hazardous waste, takes the vessel out of service during the cleaning period, and is expensive. 
     The formation of paraffin wax can be reduced by additives, called “paraffin inhibitors” (PI) which interfere with the crystallization process of wax and/or suspend wax crystals in the oil. The addition of PI to the crude oil is effective in dispersing the paraffinic residue, thereby reducing the formation of residues in the pipelines and vessels to the benefit of the oil and gas industry. The PI effectively reduce the formation of paraffinic residues during storage and transportation of the crude oil products, mitigating economic loss and decreasing environmental impact. 
     Typical paraffin inhibitor polymers include, e.g. ethylene polymers and copolymers thereof with vinyl acetate, acrylonitrile, or α-olefins such as octene, butene, propylene, and the like; comb polymers with alkyl side chains such as methacrylate ester copolymers, maleic-olefinic ester copolymers, and maleic-olefinic amide copolymers; and branched copolymers having alkyl side chains such as alkylphenol-formaldehyde copolymers and polyethyleneimines. 
     Nonaqueous formulations including such paraffin inhibitors as concentrate (PIC) must also be transported to, and stored at the field locations where crude oil is recovered so that it can be applied as needed to pipes, vessels, and the like. Providing PIC in a fluid format—i.e. in solution or dispersion—is highly advantageous for applying PI in the field because pumping equipment suitable to meter the desired amount of PI into a pipe or vessel is readily available. However, severe dispensing and usage problems are associated with the use of nonaqueous paraffin inhibitor concentrates (PIC) in areas where the winter temperature goes well below 0° C. In some field locations, for example, a winter temperature of −10° C. or less, −20° C. or less, −30° C. or less, or even −40° C. or less is not unusual. In such temperatures, PIC tend to form a gel or a solid with decreasing temperature, leading to the aforementioned severe dispensing and usage problems. 
     Previous solutions to the problem of PIC solidification include the addition of low-boiling solvents, such as methanol, to the PIC compositions. However, use of such solvents pose a different problem: at higher temperatures they can have a substantial vapor pressure. While cold temperatures are of concern to crude oil field operations, temperatures of up to about 60° C. are also encountered—often at the same field locations, depending on the seasonal weather patterns. It would be advantageous to provide additives for PIC that reduce the formation of solids therein from −40° C. to 60° C., thereby allowing the pumping of the PIC in the field within this temperature range and without buildup of high vapor pressure at the upper end of the range. 
     SUMMARY OF THE INVENTION 
     A paraffin inhibitor concentrate composition is provided for reducing paraffin or wax deposition in a crude oil storage or transportation vessel upon dilution. The paraffin inhibitor concentrate (PIC) composition comprises, consists essentially of, or consists at least of one paraffin inhibitor (PI) and at least one non-polymeric ester compound. The ester compound includes at least one ester group and in some embodiments two or more ester groups, wherein the ester compound is non-polymeric. In embodiments, the PIC compositions are nonaqueous compositions. In embodiments, the compositions flow at a temperature between about 0° C. and −40° C. 
     In some embodiments, the ester compound is a liquid at 20° C. at atmospheric pressure and has a boiling point greater than 100° C., or greater than 200° C. at atmospheric pressure. In some embodiments, the nonpolymeric ester compound comprises a glycol ester, a glycol ether ester, an esterified hydroxycarboxylic acid, an esterified mono-, di-, or tri-carboxylic acid, an esterified aromatic dicarboxylic acid, or a mixture of two or more thereof. In some embodiments, the ester compound comprises a glycol ether alkanoate, a glycol alkanoate, a glycol dialkanoate, a glycerol alkanoate, a glycerol dialkanoate, a glycerol trialkanoate, a citrate alkanoate, a citrate dialkanoate, a citrate trialkanoate, an alkyl 2-alkanoylcitrate, a dialkyl 2-alkanoylcitrate, a trialkyl 2-alkanoylcitrate, a maleate diester, an adipate diester, a terephthalate diester, a benzoate ester, a sebacate diester, a trimellitate triester, or a mixture of two or more thereof. In some embodiments, the glycol ether alkanoate is a glycol ether acetate or a blend of two or more thereof. In some embodiments, the glycol dialkanoate is a glycol diacetate or a blend of two or more thereof. In some embodiments, the glycerol trialkanoate is triacetin. In some embodiments, the ester compound is selected from propylene glycol diacetate, triethyl 2-acetyl citrate, tributyl 2-acetyl citrate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, ethylene glycol butyl ether acetate, diethylene glycol butyl ether acetate, triacetin, dipropylene glycol dibenzoate, diethyl succinate, or a combination of two or more thereof. 
     In some embodiments, the composition comprises about 1 wt % to 99 wt % of the ester compound or mixture thereof. In some embodiments, the composition comprises about 5 wt % to 75 wt % of the ester compound or mixture thereof. In some embodiments, the composition further comprises a refined petroleum solvent. In some embodiments, the composition further comprises a surfactant. In some embodiments, the composition comprises about 1 wt % to 5 wt % of the surfactant. In some embodiments, the surfactant comprises an alcohol alkoxylate, the alcohol comprising a linear, branched, aromatic, or alkaromatic hydrocarbyl group having about 8 to 30 carbons and the alkoxylate comprising about 3 to 70 alkoxylate repeat units. In some embodiments, the alkoxylate is selected from ethoxylate, propoxylate, or a combination thereof. 
     In some embodiments, the composition comprises about 1 wt % to 20 wt % of a paraffin inhibiting polymer. In some embodiments, the paraffin inhibiting polymer comprises a copolymer comprising the residues of one or more alpha olefin monomers and a maleic anhydride monomer, the one or more alpha olefin monomers having the formula (I): 
                         
wherein R 1 , R 2 , R 3 , and R 4  are independently selected from hydrogen and C 5 -C 60  alkyl, with the proviso that at least two thereof are hydrogen; the alkyl maleic anhydride monomer having the formula (II):
 
                         
wherein R 5  and R 6  are independently selected from hydrogen or C 1 -C 30  alkyl. In some embodiments, the maleic anhydride residue is further reacted with about 0.01 to 2.0 equivalents of a C 12 -C 60  alkanol or amine per equivalent of anhydride. In some embodiments, the paraffin inhibiting polymer comprises an ethylene-vinyl acetate copolymer. In some embodiments, the paraffin inhibiting polymer comprises an alkylphenol-formaldehyde copolymer. In some embodiments, the paraffin inhibiting polymer comprises an acrylate and/or methacrylate (co)polymer.
 
     A composition is provided comprising, consisting essentially of, or consisting of a crude oil source and a nonaqueous liquid composition comprising a paraffin inhibiting polymer and a nonpolymeric ester compound, wherein the paraffin inhibiting polymer is present in the crude oil source at about 50 ppm to 10,000 ppm (parts by weight). 
     A method is provided comprising, consisting essentially of, or consisting of forming a nonaqueous liquid composition comprising a paraffin inhibiting polymer and a nonpolymeric ester compound; storing the composition in an enclosed container at a first temperature between about −40° C. and 60° C.; removing the composition from the container at a second temperature between about −40° C. and 60° C.; and applying the composition to a crude oil source, wherein the removing and the applying are accomplished using a mechanical pump. In some such embodiments, the first temperature, the second temperature, or both are between about −40° C. and −20° C. 
     Other objects and features will be in part apparent and in part pointed out hereinafter. 
    
    
     DETAILED DESCRIPTION 
     Although the present disclosure provides references to preferred embodiments, persons skilled in the art will recognize that changes may be made in form and detail without departing from the spirit and scope of the invention. Various embodiments will be described in detail with reference to the drawings, wherein like reference numerals represent like parts and assemblies throughout the several views. Reference to various embodiments does not limit the scope of the claims attached hereto. Additionally, any examples set forth in this specification are not intended to be limiting and merely set forth some of the many possible embodiments for the appended claims. 
     Definitions 
     Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In case of conflict, the present document, including definitions, will control. Preferred methods and materials are described below, although methods and materials similar or equivalent to those described herein can be used in practice or testing of the present invention. All publications, patent applications, patents and other references mentioned herein are incorporated by reference in their entirety. The materials, methods, and examples disclosed herein are illustrative only and not intended to be limiting. 
     As used herein, the term “ester compound” means a non-polymeric compound having at least one ester moiety, for example in some embodiments one ester moiety, in other embodiments two ester moieties, in still other embodiments three ester moieties, and in still other embodiments more than three ester moieties. 
     As used herein, the term “non-polymeric” refers to a compound characterized as having 0 to about 4 covalently bonded repeating units and a molecular weight of less than 1000. 
     As used herein, the term “PIC additive” means an ester compound or a mixture of two or more ester compounds. 
     As used herein, the term “nonaqueous” means substantially excluding water. 
     As used herein, the term “liquid”, “flows”, or “flow” referring to a composition of the invention means that 10 mL of the composition vertically at rest on a substantially horizontal surface in a cylindrical container having dimensions of radius 1 inch and height 2 inches flows observably within about 10 seconds when tipped to a substantially horizontal position. In some embodiments, “liquid”, “flows”, or “flow” referring to a composition of the invention means a composition that has a Brookfield viscosity at 10 s −1  of about 5 cP to 1000 cP. 
     As used herein, the term “crude oil” or “crude oil source” or “crude oil product” means the hydrocarbon product of a subterranean reservoir, wherein the product is a liquid or a solid at 20° C. under a pressure of 1 atm, the product including at least linear and branched alkanes having the general formula C 1 H 2n+2  wherein n is typically about 1-50, and can be greater than 50. 
     As used herein, the terms “comprise(s),” “include(s),” “having,” “has,” “can,” “contain(s),” and variants thereof, are intended to be open-ended transitional phrases, terms, or words that do not preclude the possibility of additional acts or structures. The singular forms “a,” “and” and “the” include plural references unless the context clearly dictates otherwise. The present disclosure also contemplates other embodiments “comprising,” “consisting of” and “consisting essentially of,” the embodiments or elements presented herein, whether explicitly set forth or not. 
     As used herein, the term “optional” or “optionally” means that the subsequently described event or circumstance may but need not occur, and that the description includes instances where the event or circumstance occurs and instances in which it does not. 
     As used herein, the term “about” modifying, for example, the quantity of an ingredient in a composition, concentration, volume, process temperature, process time, yield, flow rate, pressure, and like values, and ranges thereof, employed in describing the embodiments of the disclosure, refers to variation in the numerical quantity that can occur, for example, through typical measuring and handling procedures used for making compounds, compositions, concentrates or use formulations; through inadvertent error in these procedures; through differences in the manufacture, source, or purity of starting materials or ingredients used to carry out the methods, and like proximate considerations. The term “about” also encompasses amounts that differ due to aging of a formulation with a particular initial concentration or mixture, and amounts that differ due to mixing or processing a formulation with a particular initial concentration or mixture. Where modified by the term “about” the claims appended hereto include equivalents to these quantities. Further, where “about” is employed to describe a range of values, for example “about 1 to 5” the recitation means “1 to 5” and “about 1 to about 5” and “1 to about 5” and “about 1 to 5” unless specifically limited by context. 
     As used herein, the word “substantially” modifying, for example, the type or quantity of an ingredient in a composition, a property, a measurable quantity, a method, a position, a value, or a range, employed in describing the embodiments of the disclosure, refers to a variation that does not affect the overall recited composition, property, quantity, method, position, value, or range thereof in a manner that negates an intended composition, property, quantity, method, position, value, or range. Examples of intended properties include, solely by way of nonlimiting examples thereof, flexibility, partition coefficient, rate, solubility, temperature, and the like; intended values include thickness, yield, weight, concentration, and the like. The effect on methods that are modified by “substantially” include the effects caused by variations in type or amount of materials used in a process, variability in machine settings, the effects of ambient conditions on a process, and the like wherein the manner or degree of the effect does not negate one or more intended properties or results; and like proximate considerations. Where modified by the term “substantially” the claims appended hereto include equivalents to these types and amounts of materials. 
     Discussion 
     Paraffin Inhibitor Concentrate (PIC) Additive Compounds 
     It has been discovered that non-polymeric ester compounds are useful as additives to nonaqueous PIC compositions to reduce or eliminate the solidification of the PI (paraffin inhibitor) at low temperatures. Ester compounds having melting points of less than about 20° C., boiling points greater than 100° C., and low vapor pressure at 60° C. are especially useful as additives to PIC compositions to reduce or eliminate the solidification of the PI temperatures between about 0° C. to −40° C. (−40° F.), for example about −10° C. to −40° C., or about −20° C. to −40° C., or −30° C. to −40° C., or even below −40° C. while providing compositional stability to temperatures up to 60° C. (158° F.). 
     The PIC additives include one or more such non-polymeric ester compounds. Exemplary classes of ester compounds include aromatic esters, alkanoate esters, esterified glycol ethers, esterified glycols, and esterified glycerols. 
     Exemplary ester compounds include esters of benzoic acid with aromatic, linear, or branched alkanols including but not limited to methanol, ethanol, n-propanol, iso-propanol, phenol, 2-ethylhexanol, diisononanol, n-butanol, iso-butanol, t-butanol, n-hexanol, isodecanol, n-octanol, iso-octanol, and blends of two or more such esters. In some embodiments, mixtures of two or more such aromatic ester(s) as well as mixtures of one or more such aromatic ester(s) with one or more of the other ester compounds listed elsewhere herein are employed as the PIC additive. 
     Exemplary ester compounds further include dialkyl diesters of benzene dicarboxylic acids such as terephthalate (benzene-1,4-dicarboxylate) or isophthalate (benzene-1,3-dicarboxylate) diesters of aromatic, linear, or branched alkanols including but not limited to the alkanols listed above, and mixtures of two such alkanols functionalizing a single phthalate ester compound. In some embodiments, mixtures of two or more such aromatic ester(s) as well as mixtures of one or more such aromatic ester(s) with one or more of the other ester compounds listed elsewhere herein are employed as the PIC additive. 
     Exemplary ester compounds further include trimellitate triesters and isomers thereof including triesters of alkanols including but not limited to the alkanols listed above, and mixtures of two or three such alkanols functionalizing a single trimellitate ester compound. In some embodiments, mixtures of two or more such aromatic ester(s) as well as mixtures of one or more such aromatic ester(s) with one or more of the other ester compounds listed elsewhere herein are employed as the PIC additive. 
     Exemplary ester compounds further include esters of hydroxycarboxylic acids including but not limited to esters of the alkanols listed above, and hydroxycarboxylic acids esterified with mixtures of two or three such alkanols. Suitable esters of hydroxycarboxylic acids include 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate. In some embodiments, there are mixtures of two or more such ester(s) as well as mixtures of one or more such ester(s) with one or more of the other ester compounds listed elsewhere herein are employed as the PIC additive. 
     Exemplary ester compounds further include adipate, sebacate, succinate, and maleate diesters, citrate triesters, and isomers of any thereof wherein the alkanoate esters are diesters or triesters of alkanols including but not limited to the alkanols listed above, and mixtures of two such alkanols functionalizing a single alkanoate diester compound or even three such alkanols functionalizing a single citrate ester compound. In some embodiments, mixtures of two or more such alkanoate diester(s) or triester(s) as well as mixtures of one or more such alkanoate diester(s) and/or triester(s) with one or more of the other ester functional PIC additives listed elsewhere herein are employed as the PIC additive. In some embodiments where the alkanoate ester is a citrate, the citrate hydroxyl moiety not associated with a carboxylate is also functionalized, for example with an acetate or an alkyl ether moiety employing an alkanol or alkanoate as described above. 
     Exemplary ester compounds further include esterified glycol ethers, or glycol ether alkanoates having ester (alkanoate) groups corresponding to C2-C10 carboxylic acids, or C2-C8, or C2-C6, or C2-C4 carboxylic acids (where C2 carboxylic acid is acetic acid). Suitable esterified glycol ethers include ethylene glycol methyl ether acetate, ethylene glycol methyl ether butyrate, ethylene glycol methyl ether 2-ethylhexanoate, ethylene glycol ethyl ether acetate, ethylene glycol propyl ether acetate, ethylene glycol butyl ether acetate, ethylene glycol pentyl ether acetate, ethylene glycol hexyl ether acetate, diethylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, diethylene glycol propyl ether acetate, diethylene glycol butyl ether acetate, diethylene glycol pentyl ether acetate, diethylene glycol hexyl ether acetate, triethylene glycol methyl ether acetate, triethylene glycol ethyl ether acetate, triethylene glycol propyl ether acetate, triethylene glycol butyl ether acetate, triethylene glycol pentyl ether acetate, triethylene glycol hexyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, propylene glycol pentyl ether acetate, propylene glycol hexyl ether acetate, dipropylene glycol methyl ether acetate, dipropylene glycol ethyl ether acetate, dipropylene glycol propyl ether acetate, dipropylene glycol butyl ether acetate, dipropylene glycol pentyl ether acetate, dipropylene glycol hexyl ether acetate, tripropylene glycol methyl ether acetate, tripropylene glycol ethyl ether acetate, tripropylene glycol propyl ether acetate, tripropylene glycol butyl ether acetate, tripropylene glycol pentyl ether acetate, tripropylene glycol hexyl ether acetate, ethylene glycol phenyl ether acetate, diethylene glycol phenyl ether acetate, triethylene glycol phenyl ether acetate, propylene glycol phenyl ether acetate, dipropylene glycol phenyl ether acetate, and tripropylene glycol phenyl ether. In some embodiments, mixtures of two or more such esterified glycol ethers as well as mixtures of one or more such esterified glycol ethers with one or more of the other ester compounds listed elsewhere herein are employed as the PIC additive. 
     Exemplary ester compounds further include esterified glycols including alkanoate esters of dialkanols such as ethylene glycol, propylene glycol, and the like, wherein the ester (alkanoate) groups thereof correspond to C2-C10 carboxylic acids, or C2-C8, or C2-C6, or C2-C4 carboxylic acids. Suitable examples include propylene glycol diacetate (propylene diacetate), ethylene glycol diacetate (ethylene diacetate), ethylene glycol dipropanoate (ethylene propionate), diethylene glycol diacetate, butylene glycol diacetate (butylene diacetate), propylene glycol dibutyrate (propylene dibutyrate), and mixed esters such as ethylene acetate butyrate, propylene butyrate propanoate, and the like. In some embodiments, mixtures of two or more such esterified glycols as well as mixtures of one or more such esterified glycols with one or more of the other ester compounds listed elsewhere herein are employed as the PIC additive. 
     Exemplary ester compounds further include esterified glycerols including alkanoate esters of glycerol wherein the alkanoate groups correspond to C2-C10 carboxylic acids, or C2-C8, or C2-C6, or C2-C4 carboxylic acids, wherein the alkanoate esters include mono-, di-, and triglycerides (mono-, di-, or triesters). Suitable alkanoate esters of glycerol include olive oil, triacetin, glycerol monobutanoate, and glycerol dibutanoate. In some embodiments, mixtures of two or more such esterified glycerols as well as mixtures of one or more such esterified glycerols with one or more of the other ester compounds listed elsewhere herein are employed as the PIC additive. 
     In some embodiments the PIC additive comprises, consists essentially of, or consists of a glycol ether alkanoate, a glycol dialkanoate, a citrate trialkanoate, a maleate diester, an adipate diester, a terephthalate diester, a benzoate ester, a sebacate diester, a trimellitate triester, or a mixture of two or more thereof. In some embodiments one or more of the alkanoate groups is the residue of a C2-C10 carboxylic acid. In some embodiments one or more of the alkanoate groups is acetate, that is, the residue of acetic acid (C2 carboxylic acid). In some embodiments the glycol alkanoate is a glycol acetate or a glycol diacetate, or a blend of two or more thereof. In some embodiments one or more of the ester groups comprises the residue of a C2-C10 alkanol. 
     In some embodiments, the ester compounds are characterized as having log P (that is, partition coefficient when octanol and water are tested) of about −3 to 1, for example about −2 to 0. Log P is the logarithm of the ratio of the concentrations of an un-ionized solute in two solvents; when one of the solvents is water and the other is a non-polar solvent, then the log P value is also known as a measure of lipophilicity. When the non-polar solvent is octanol, Log P is the partition coefficient. 
     Solubility of the ester compounds in aqueous or oil-based systems can be predicted several ways, including HLB (hydrophilic-lipophilic balance) and OHLB (organic hydrophilic-lipophilic balance) values. HLB is most useful for predicting a solvent&#39;s solubility in water, and OHLB is most useful for predicting oil/water partitioning of solvents. The two scales run counter each other with respect to hydrophilicity. In some embodiments, the ester compounds have HLB of about 5 to 10, such as about 5 to 9, or about 6 to 10, or about 7 to 10, or about 7 to 9. In some embodiments, the ester compounds have an OHLB of about 10 to 21, such as about 11 to 21, or about 10 to 20, or about 10 to 19, or about 10 to 18, or about 10 to 17, or about 10 to 16, or about 11 to 16. 
     The HLB scale was derived initially for surfactants and provides a means of comparing the relative hydrophilicity of amphiphilic molecules. HLB values are also relevant for solvents with pseudo-surfactant qualities, such as glycol ethers. Complete water solubility occurs at HLB of about 7.3. Solvents with HLB values above this mark are completely miscible with water, while those below this value are only partially soluble in water. In some embodiments, the ester compounds or the PIC additives of the invention are soluble in water to at least 0.1 wt % at 20° C. and up to completely miscible in water at 20° C. (that is, any ratio of an ester compound or PIC additive and water form a solution). In some embodiments the ester compounds or PIC additives are soluble in water at between about 1 wt % and 30 wt % at 20° C., for example about 5 wt % to 25 wt %, or about 5 wt % to 20 wt %, or about 10 wt % to 30 wt %, or about 15 wt % to 30 wt %, or about 20 wt % to 30 wt % soluble in water at 20° C. 
     The ester compounds useful in the PIC of the invention are characterized as liquids at 20° C., and as having boiling points in excess of 100° C. at atmospheric pressure. The melting points of the ester compounds are generally 20° C. or less at atmospheric pressure, for example about 20° C. to −50° C., or about 5° C. to −50° C., or about 10° C. to −30° C. at atmospheric pressure. The boiling points of the ester compounds are greater than 100° C. at atmospheric pressure, for example about 100° C. to 300° C. at atmospheric pressure, or about 100° C. to 280° C., or about 100° C. to 250° C., or about 120° C. to 300° C., or about 150° C. to 300° C. at atmospheric pressure. The ester compounds are further characterized as having low vapor pressure at temperatures of about 60° C. or less. 
     In some embodiments, useful PIC additives comprise, consist essentially of, or consist of propylene glycol methyl ether acetate, propylene glycol diacetate, triethyl 2-acetyl citrate, tributyl 2-acetyl citrate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, ethylene glycol butyl ether acetate, diethylene glycol butyl ether acetate, triacetin (triacetyl glycerol), dipropylene glycol dibenzoate, or diethyl succinate, or a combination of two or more thereof. 
     The foregoing listed ester compounds have the following properties, wherein all properties are measured at ambient pressure unless otherwise specified. All are liquids at 20° C. 
     propylene glycol diacetate: bp=191° C. 
     propylene glycol methyl ether acetate, bp=146° C.; vapor pressure=0.37 kPa at 20° C. 
     triethyl 2-acetyl citrate: bp=228-229° C. 
     tributyl 2-acetyl citrate: bp=172° C.-174° C. at 0.1 kPa; mp=—80° C.; vapor pressure=1.79 kPa at 20° C.; vapor pressure=5.5 kPa at 55° C. 
     dipropylene glycol methyl ether acetate: bp=208.9° C.; mp=−25.2° C.; vapor pressure=0.90 kPa at 25° C. 
     propylene glycol methyl ether acetate: bp=145° C.=146° C.; vapor pressure=0.49 kPa at 25° C. 
     ethylene glycol butyl ether acetate: bp=186° C.; vapor pressure=0.04 kPa at 20° C.; 
     vapor pressure=0.77 kPa at 55° C. 
     diethylene glycol butyl ether acetate: bp=245° C. 
     triacetin: bp=259° C.; mp=3° C. 
     dipropylene glycol dibenzoate: bp=232° C. at 0.67 kPa 
     diethyl succinate: bp=217° C.; mp=−21° C.; vapor pressure=0.133 kPa at 55° C. 
     Paraffin Inhibitor Concentrates (PIC) 
     Disclosed herein are temperature stable paraffin inhibitor concentrate (PIC) compositions and methods for inhibiting solidification in paraffin inhibitor concentrates at temperatures encountered during storage and/or transportation thereof, e.g. about −40° C. to 60° C. The temperature stable paraffin inhibitor compositions flow, and thus are pourable or pumpable, at temperatures as low as −40° C., or about 0° C. to −40° C., or about −5° C. to −40° C., or about −10° C. to −40° C., or about −15° C. to −40° C., or about −20° C. to −40° C., or about −25° C. to −40° C., or about −30° C. to −40° C. and do not undergo observable phase separation at such temperatures. In some embodiments, the compositions further do not phase separate or solidify upon subsequent warming to 20° C., or as high as 60° C. In some embodiments the warmed compositions remain stable in a single phase. In some embodiments the compositions have a homogeneously dispersed or emulsified phase substantially over the temperature range of −40° C. to 60° C. 
     In some embodiments, the PIC compositions of the invention are nonaqueous. In other embodiments, the PIC compositions include up to about 10 wt % water, or up to about 9% water, or up to about 8% water, or up to about 7% water, or up to about 6% water, or up to about 5% water, or up to about 4% water, or up to about 3% water. In embodiments, the PIC compositions are characterized as having a substantially transparent, homogeneous appearance at least at one selected temperature between about 0° C. and 20° C., for example at 0° C., 1° C., 2° C., 3° C., 4° C., 5° C., 6° C., 7° C., 8° C., 9° C., 10° C., 11° C., 12° C., 13° C., 14° C., 15° C., 16° C., 17° C., 18° C., 19° C., or 20° C. 
     Conventional paraffin inhibitor concentrates (PIC) comprise, consist essentially of, or consist of a paraffin inhibitor (PI) and one or more petroleum-based solvents, optionally including a low-boiling cosolvent such as methanol, or a surfactant, or both. Typically, the PI is a polymer such as a branched or comb-like polymer. Suitable PI include, e.g. ethylene polymers and copolymers thereof with vinyl acetate, acrylonitrile, or α-olefins such as octene, butene, propylene, and the like; comb polymers with alkyl side chains such as methacrylate ester copolymers, maleic-olefinic ester copolymers, and maleic-olefinic amide copolymers; and branched copolymers having alkyl side chains such as alkylphenol-formaldehyde copolymers and polyethyleneimines. In some embodiments, the PI comprises a copolymer comprising the residues of (i) an alpha olefin monomer and a maleic anhydride monomer or (ii) a maleic anhydride monomer and styrene. The alpha olefin monomer has the formula (I): 
                         
wherein R 1 , R 2 , R 3 , and R 4  are independently selected from hydrogen and C 5 -C 60  alkyl, with the proviso that at least two thereof are hydrogen; a blend of two or more such alpha olefin monomers having formula (I) are suitably included in the copolymer. In some embodiments R 1 , R 2 , R 3 , and R 4  are independently hydrogen or C 12 -C 60 . The maleic anhydride monomer has the formula (II):
 
                         
wherein R 5  and R 6  are independently hydrogen or C 1 -C 60  alkyl. In some embodiments R 5  and R 6  are independently hydrogen or C 12 -C 30 .
 
     In some embodiments, the copolymer of (I) and (II) is further reacted via the maleic anhydride residue with one or more alkanol or amine compounds to form the corresponding carboxylate or amide functionalities. In some such embodiments, the maleic anhydride residue is reacted with about 0.5 to 2.0 equivalents of the alkanol or amine per equivalent of anhydride. The alkanol or amine compounds are linear, branched, aromatic, or alkaromatic compounds having about 12 to 60 carbons. 
     In some embodiments, polymers that are paraffin inhibitors for crude oil also have additional utility as asphaltene dispersants, pour point depressants, flow improvers, and may provide other crude oil benefits known to one skilled in the art. Therefore, in some embodiments the PIC provides a benefit to crude oil as not only paraffin inhibitor but also as an asphaltene dispersant, pour point depressant, and flow improver and may also provide other crude oil benefits known to one skilled in the art. 
     Conventionally, the PI is present in the PIC typically at about 1 wt % to 5 wt %, or example about 2 wt % to 3 wt % and is diluted in the field to about 50 ppm to 10,000 ppm PI (paraffin inhibitor) by adding the PIC into a crude oil source, often along with one or more additional additives to accomplish e.g. biocidal activity, corrosion resistance, and the like. Petroleum-based solvents that conventionally provide the balance of PIC compositions comprise, consist essentially of, or consist of a refined petroleum solvent. Refined petroleum solvents comprise, consist essentially of, or consist of aromatic compounds such as benzene, toluene, xylene, light aromatic naphtha, heavy aromatic naphtha, kerosene, or diesel; and/or aliphatic compounds such as pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, or any of their cyclic or branched isomers or a mixture thereof. Naphtha is a petrochemical industry term describing boiling point fractions of petroleum distillate collected at different points on a distillation column. Naphtha fractions may include linear or branched or cyclic alkanes or alkenes, aromatic hydrocarbons, or fused ring aromatic compounds or mixtures of these materials. Light naphtha is lower boiling material collected near the top portion of the distillation column; medium naphtha higher boiling material from near the middle. Heavy naphtha is an even higher boiling material from near the bottom portion of the column. PI solubility, particularly at temperatures below 20° C., limits the amount of polymer that can be delivered in such concentrates. 
     In some embodiments, the PIC compositions of the invention are nonaqueous compositions; that is, they are characterized by the substantial absence of water and are formed by substantially excluding water. The PIC compositions of the invention are liquids between about −40° C. and 60° C., or about −30° C. to 60° C., or about −20° C. to 60° C., or about −10° C. to 60° C., or about 0° C. to 60° C. By “liquid” it is meant that the PIC compositions of the invention flow. 
     In embodiments, the PIC compositions of the invention comprise up to 20 wt % PI, since the solubility of the PI in the PIC at temperatures below 20° C. is increased by the addition of the PIC additives of the invention. Thus, in embodiments, the PIC compositions of the invention comprise, consist essentially of, or consist of about 1 wt % to 20 wt % PI, or about 3 wt % to 20 wt %, or about 5 wt % to 20 wt %, or about 7 wt % to 20 wt %, or about 10 wt % to 20 wt % PI. In embodiments, the PIC of the invention comprise about 1 wt % to 99 wt % PIC additive including any of the ester functional compounds described above or a mixture of two or more thereof. For example, the PIC of the invention comprise about 3 wt % to 99 wt %, or about 5 wt % to 99 wt %, or about 10 wt % to 99 wt %, or about 15 wt % to 99 wt %, or about 20 wt % to 99 wt %, or about 25 wt % to 99 wt %, or about 30 wt % to 99 wt %, or about 35 wt % to 99 wt %, or about 40 wt % to 99 wt %, or about 45 wt % to 99 wt %, or about 50 wt % to 99 wt %, or about 55 wt % to 99 wt %, or about 60 wt % to 99 wt %, or about 65 wt % to 99 wt %, or about 70 wt % to 99 wt %, or about 75 wt % to 99 wt %, or about 80 wt % to 99 wt %, or about 85 wt % to 99 wt %, or about 1 wt % to 95 wt %, or about 1 wt % to 90 wt %, or about 1 wt % to 80 wt %, or about 1 wt % to 70 wt %, or about 1 wt % to 60 wt %, or about 1 wt % to 50 wt %, or about 5 wt % to 90 wt %, or about 5 wt % to 75 wt %, or about 10 wt % to 75 wt %, or about 25 wt % to 75 wt % of the PIC additive. In some embodiments, the balance of the PIC is a petroleum-based solvent such as benzene, toluene, xylene, or HAN. In some embodiments, the PIC is characterized by the substantial absence of a petroleum-based solvent. In some embodiments, the PIC includes one or more additional components such as surfactants, biocides, preservatives, stabilizers, and the like without limitation. 
     Optionally, the PIC of the invention, that is, a PIC including a PIC additive, further comprises a surfactant. In an embodiment, the surfactant is a nonionic or amphoteric surfactant. The PIC in such embodiments comprises about 0 wt % to 10 wt % of a nonionic or amphoteric surfactant, or about 0.5 wt % to 10 wt %, or about 1 wt % to 10 wt %, or about 2 wt % to 10 wt %, or about 3 wt % to 10 wt %, or about 4 wt % to 10 wt %, or about 5 wt % to 10 wt %, or about 0.5 wt % to 9 wt %, or about 0.5 wt % to 8 wt %, or about 0.5 wt % to 7 wt %, or about 0.5 wt % to 6 wt %, or about 0.5 wt % to 5 wt %, or about 0.5 wt % to 4 wt %, or about 0.5 wt % to 3 wt %, or about 0.5 wt % to 2 wt %, or about 0.5 wt % to 1 wt %, or about 1 wt % to 8 wt %, or about 1 wt % to 5 wt % nonionic or amphoteric surfactant. Nonionic surfactants useful in the PIC include but are not limited to alkoxylated alcohols, such as copolymers of ethylene oxide and/or propylene oxide and/or butylene oxide and epoxylated, propoxylated, and epoxylated-propoxylated compounds comprising C 6 -C 40  alkanols or C 8 -C 30  alkanols. Suitable alkanols include linear, branched, aromatic, or alkaromatic alkanols. In some embodiments, the alkoxylated alcohols comprise about 3 to 100 alkoxylate repeat units, or about 3 to 90, or about 3 to 80, or about 3 to 70, or about 3 to 60, or about 3 to 50, or about 3 to 40, or about 3 to 30 alkoxylate repeat units. In some embodiments the alkoxylate repeat units are selected from ethoxylate, propoxylate, or a combination thereof in random or block configuration. In many embodiments, a blend of two or more alkoxylated alcohol surfactants are employed in the PIC. Other nonionic surfactants are similarly useful in the PIC of the invention and are not particularly limited. Some examples of suitable nonionic surfactants include alkylphenol alkoxylates, block copolymers of ethylene, propylene and butylene oxides, alkyl polyglucosides, polyalkoxylated glycerides, sorbitan esters and polyalkoxylated sorbitan esters, and alkoyl polyethylene glycol esters and diesters. Some examples of suitable amphoteric surfactants include alkyl dimethyl amine oxides, alkyl-bis(2-hydroxyethyl) amine oxides, alkyl amidopropyl dimethyl amine oxides, alkylamidopropyl-bis(2-hydroxyethyl) amine oxides, betaines, sultaines, alkyl amphoacetates and amphodiacetates, alkyl amphopropionates and amphodipropionates, and alkyliminodipropionate. Blends of nonionic and/or amphoteric surfactants, including blends of any of the above recited surfactants, are also usefully employed in the PIC of the invention. 
     We have unexpectedly found that PIC compositions of the invention flow at temperatures as low as −40° C. Stated differently, an aliquot of a PIC composition will observably flow at least at one temperature between 0° C. and −40° C. when a vessel containing the PIC composition is tipped on its side. This is an unexpected result, since concentrates of paraffin inhibiting polymers tend to become solidified, or precipitate from dispersions or solutions, at temperatures of about 0° C. and less, as is familiar to one skilled in the art of petroleum collecting, refining, transporting, storing during the winter months in certain geographic locations in the world. To address this problem, conventionally manufacturers use more low-boiling solvents, such as methanol, in an effort to maintain homogeneity of the concentrates at low temperatures so that the PIC can be poured or pumped in the field. Use of more solvent necessitates shipping more product, and adding a larger volume thereof to the targeted petroleum product, in order to obtain an effective concentration of PI polymer in the petroleum product and thereby avoid paraffin deposition. 
     Further, the use of low boiling solvents such a methanol can present safety issues due to flammability and low flash point of some such solvents. This is particularly true during the summer months in the field. Vapor pressure can build up in enclosed containers inside which temperatures may reach up to 60° C. Manufacturers may address this issue by formulating two different PICs, one for use at e.g. temperatures below 0° C., and one for use at temperatures above 0° C. However, this is impractical at best. 
     Applicant has discovered an approach to obviate all of the above problems. The PIC additives of the invention are not flammable and have boiling points above 100° C., which confers good solution/dispersion stability at temperatures up to 60° C. Since the PIC additives have boiling points of greater than 100° C., and in many embodiments greater than 200° C., the PIC additives provide minimal contribution to hazardous conditions caused by buildup of pressure within a storage container or other sealed vessel when exposed to temperatures up to 60° C. Yet, the PIC additives still prevent solidification at temperatures as low as −40° C. or even lower, for example −40° C. to −60° C. We have found that concentrates from 1 wt % to as much as 20 wt % solids are still flowable at temperatures of about 0° C. to −40° C., or even between −40° C. and −60° C. Advantageously, the PICs of the invention deliver high PI concentration and also stability at temperatures as high as 60° C. 
     The PIC additive may be present in the PIC compositions of the invention in an amount of about 1 wt % to about 99 wt % of the PIC, or about 1 wt % to about 95 wt %, or about 5 wt % to about 75%, or about 10 wt % to about 50 wt %, or about 1 wt % to 90 wt %, or about 1 wt % to 80 wt %, or about 1 wt % to 70 wt %, or about 1 wt % to 60 wt %, or about 1 wt % to 50 wt %, or about 1 wt % to 40 wt %, or about 1 wt % to 30 wt %, or about 1 wt % to 20 wt %, or about 1 wt % to 10 wt %, or about 2 wt % to about 10 wt %, or about 2 wt % to about 5 wt %, or about 5 wt % to 90 wt %, or about 5 wt % to 75 wt %, or about 10 wt % to 75 wt %, or about 25 wt % to 75 wt %, or about 30 wt % to 70 wt %, or about 33 wt % to 67 wt %, or about 25 wt % to 40 wt %, or about 55 wt % to 70 wt %, or about 40 wt % to 60 wt %, or about 65 wt % to 90 wt %, or about 70 wt % to 90 wt % of the PIC composition. 
     In some embodiments, the PIC compositions of the invention are characterized as having Brookfield viscosity of about 5 cP to 1000 cP at −40° C., when measured at a shear rate of 10 s −1  using a Brookfield viscometer equipped with a cup and bob, DIN spindle size 21 (viscometer equipment obtained from the Brookfield Engineering Laboratories of Middleboro, Mass.). For example, in some embodiments, the PIC compositions of the invention are characterized as having Brookfield viscosity at −40° C. and 10 s −1  of about 5 cP to 900 cP, or about 5 cP to 800 cP, or about 5 cP to 700 cP, or about 5 cP to 600 cP, or about 5 cP to 500 cP, or about 5 cP to 400 cP, or about 5 cP to 300 cP, or about 5 cP to 200 cP, or about 5 cP to 100 cP, or about 10 cP to 1000 cP, or about 15 cP to 1000 cP, or about 20 cP to 1000 cP, or about 25 cP to 1000 cP, or about 30 cP to 1000 cP, or about 40 cP to 1000 cP, or about 50 cP to 1000 cP, or about 60 cP to 1000 cP, or about 70 cP to 1000 cP, or about 80 cP to 1000 cP, or about 90 cP to 1000 cP, or about 100 cP to 1000 cP, or about 10 cP to 500 cP, or about 20 cP to 500 cP, or about 10 cP to 250 cP, or about 20 cP to 250 cP, or about 10 cP to 200 cP, or about 20 cP to 200 cP, or about 10 cP to 100 cP, or about 20 cP to 100 cP. 
     Methods of Using the PIC Compositions 
     The PIC compositions are usefully added to a source of crude oil or another unrefined petroleum source at a concentration typically targeting about 100 ppm to 1000 ppm of the PI. Examples of unrefined petroleum sources may include transfer piping, storage tanks, and transport vessels. Unrefined petroleum is crude oil which has not yet been broken down into its component parts at an oil refinery. In this respect, the PIC behaves as intended and with the same beneficial effect as conventional PIC. However, in some embodiments, since the PIC additives usefully enable a higher PI concentration than is possible for conventional PIC, a lower rate of pumping, pouring, dripping, spraying etc. of the PIC is employed to achieve the target PI concentration in the petroleum source. That is, a lower dosing of the pipeline or other system to transport or store crude oil is required. 
     A principal benefit of the PIC additives is their ability to flow at temperatures as low as −40° C. to facilitate pouring or pumping of the PIC from a storage container or vessel into contact with a crude oil source requiring paraffin inhibition. Thus, in embodiments, a method of the invention includes forming a nonaqueous liquid composition comprising, consisting essentially of, or consisting of a PI and a PIC additive; storing the composition in an enclosed container at a first temperature between about −40° C. and 60° C.; removing the composition from the container at a second temperature between about −40° C. and 60° C.; and applying the composition to a crude oil (unrefined petroleum) source. In embodiments, the removing and the applying are accomplished using a mechanical pump. In embodiments, the first temperature, the second temperature, or both are between about −40° C. and 0° C., or about −40° C. to −10° C., or about −40° to −20° C., or about −40° C. to −30° C. It will be understood that storing and removing are carried out over a variable range of temperatures, and in particular storage temperatures often vary during the storage period. Thus, the first temperature of the method is suitably measured at any point during storage, wherein the temperature during at least some period of storage is within the stated range. In some embodiments the applying is sufficient to contact the crude petroleum source with about 100 ppm to 1000 ppm of the PI. 
     The method of applying the PIC to the crude oil source is not particularly limited. One of skill will appreciate that crude oil additives such as paraffin inhibitors are conventionally added by using available equipment including e.g. pipes, mixers, pumps, tanks, injection ports, and the like. Aside from the increased concentration of PI in the PIC of the invention, addition of the PIC to a petroleum source is usefully accomplished using conventional equipment and the same equipment with which an operator in the field is acquainted; that is, no special steps or other procedures are required to use the PIC of the invention. In some embodiments, the PIC is applied to one or more subterranean hydrocarbon recovery (oil well) locations, such as downhole or on the backside, using capillary string, gas lift, slip stream or other methods, at the wellhead, or at any other point downstream of the reservoir. 
     Experimental 
     General Procedure 
     Formulations of PIC with various ester compounds were blended. The following paraffin inhibitor polymers were employed in the blends. In each case, the indicated amount of polymer added is the amount of the polymer as supplied in a solution or dispersion (and not the actual weight of the dry polymer (actives)): 
     Polymer 1: A 70 wt % mixture in xylene of a copolymer of an α-olefin with about 13 wt % maleic anhydride, wherein the maleic anhydride functionality is esterified with C18+ alcohols at a ratio of about 0.9 moles alcohol to 1 mole maleic anhydride 
     Polymer 2: An 82 wt % mixture in xylene of a copolymer of an α-olefin with about 8 wt % maleic anhydride, wherein the maleic anhydride functionality is esterified with C20+ alcohols at a ratio of about 2.03 moles alcohol to 1 mole maleic anhydride 
     Polymer 3: A 70 wt % mixture in xylene of a copolymer of an α-olefin with about 14 wt % maleic anhydride, wherein the maleic anhydride functionality is esterified with C16+ alcohols at a ratio of about 0.9 moles alcohol to 1 mole maleic anhydride 
     Polymer 4: a 69 wt % mixture in HAN of a copolymer of an α-olefin with about 8 wt % maleic anhydride, wherein the maleic anhydride functionality is esterified with a mixture of C20+ alcohols at a ratio of about 1.21 moles alcohol to 1 mole maleic anhydride. 
     Polymer 5: an alkylated phenol-formaldehyde resin, 50 wt % in xylene. 
     Polymer 6: an 80 wt % mixture in xylene of a copolymer of an α-olefin with about 10 wt % maleic anhydride, wherein the maleic anhydride functionality is esterified with C18+ alcohols at a ratio of about 0.9 moles alcohol to 1 mole maleic anhydride. 
     After mixing the components, a 10 mL aliquot of each compositions was added to a 20 mL bottle having radius 1 inch and height 2 inches. The bottles were capped and warmed to between about 25° C. and 65° C. for up to about 30 minutes, as needed to complete mixing of the components. After allowing the contents of the bottles to cool to ambient laboratory temperature, the contents were observed and initial observations recorded (Initial Observations in the tables below). Then the bottles were placed in a freezer set to a temperature of −40° C. for between 12 and 18 hours. The bottles were removed from the freezer and observed (At −40° C. or −45° C. observations in the tables below); the bottles were further tipped onto their side in order to observe flow of the contents. 
     The compositions tested herein are said to “flow” at the indicated temperature when 10 mL of the composition vertically at rest on a substantially horizontal surface the cylindrical container (radius 1 inch, height 2 inches) flows observably within about 10 seconds when tipped to a substantially horizontal position. This amount of flow is known to be sufficient to indicate that the composition is pourable or pumpable for use in the field, where such concentrates are applied to one or more crude oil transportation or storage systems. 
     Finally, the bottles were allowed to warm to ambient laboratory temperature and the contents observed (RT After −40° C. observations in the tables below). In some cases, observations of the Example compositions were made after 48 hours or 1 week after allowing to warm to ambient laboratory temperature. 
     In some cases, one or more cooling and heating cycles is additionally carried out on the example compositions. In such cases the bottles are placed in a −40° C. freezer for about 72 hours, followed by observation then the bottles are allowed to warm to ambient laboratory temperature for about 2 hours, followed by observation; then the bottles are placed in an oven set to 60° C. for about 18 hours, followed by observation; then the bottles are allowed to cool to ambient laboratory temperature for about 2 hours, followed by observation; then the bottles may be subjected one or more additional cooling and heating cycles wherein the cycles are alternated. 
     Examples 1-45 
     Employing HAN (heavy aromatic naphtha) or a blend of HAN and toluene as solvent, 1.45 g of the Polymer 1 dispersion, and 0.3 g of C11-C15 alcohol ethoxylate (as surfactant), the ester compounds shown in Table 1 were combined therewith and tested according to the General Procedure set forth above. Results are shown in Table 1. 
     
       
         
           
               
             
               
                 TABLE 1 
               
             
            
               
                   
               
               
                 Compositions and observed results for Examples 1-45. 
               
            
           
           
               
               
               
            
               
                   
                 Component, g 
                 Observations 
               
               
                   
               
            
           
           
               
               
               
               
               
               
            
               
                 Example 
                 HAN 
                 none 
                 Initial 
                 At −40° C. 
                 RT After −40° C. 
               
               
                   
               
               
                 1 
                 8.25 
                 n/a 
                 Clear liquid 
                 Clear solid/gel 
                 Clear liquid 
               
               
                   
               
               
                   
                   
                 Toluene 
               
               
                   
               
               
                 2 
                 6.19 
                 2.06 
                 Clear liquid 
                 Clear solid/gel 
                 Clear liquid 
               
               
                 3 
                 4.13 
                 4.13 
                 Clear liquid 
                 Clear solid/gel 
                 Clear liquid 
               
               
                 4 
                 2.06 
                 6.19 
                 Clear liquid 
                 Clear solid/gel 
                 Clear liquid 
               
               
                 5 
                 0 
                 8.25 
                 Clear liquid 
                 Clear solid/gel 
                 Clear liquid 
               
               
                   
               
               
                   
                   
                 Diethylene glycol 
                   
                   
                   
               
               
                   
                   
                 butyl ether 
               
               
                   
               
               
                 6 
                 6.19 
                 2.06 
                 Clear liquid 
                 Clear solid/gel 
                 Clear liquid 
               
               
                 7 
                 4.13 
                 4.13 
                 Clear liquid 
                 Clear solid/gel 
                 Clear liquid 
               
               
                 8 
                 2.06 
                 6.19 
                 Clear liquid 
                 Liquid 
                 Hazy liquid 
               
               
                 9 
                 0 
                 8.25 
                 Hazy liquid 
                 Opaque solid 
                 Cloudy liquid 
               
               
                   
               
               
                   
                   
                 2,2,4-Trimethyl- 
                   
                   
                   
               
               
                   
                   
                 1,3-pentanediol 
                   
                   
                   
               
               
                   
                   
                 isobutyrate 
               
               
                   
               
               
                 10 
                 6.19 
                 2.06 
                 Clear liquid 
                 Clear solid/gel 
                 Clear liquid 
               
               
                 11 
                 4.13 
                 4.13 
                 Clear liquid 
                 Clear solid/gel 
                 Clear liquid 
               
               
                 12 
                 2.06 
                 6.19 
                 Clear liquid 
                 Opaque solid 
                 Slightly hazy liquid 
               
               
                 13 
                 0 
                 8.25 
                 Clear liquid 
                 Slush 
                 Cloudy liquid 
               
               
                   
               
               
                   
                   
                 Propylene Glycol 
                   
                   
                   
               
               
                   
                   
                 Diacetate 
               
               
                   
               
               
                 14 
                 6.19 
                 2.06 
                 Clear liquid 
                 Clear solid/gel 
                 Clear liquid 
               
               
                 15 
                 4.13 
                 4.13 
                 Clear liquid 
                 Liquid 
                 Hazy liquid 
               
               
                 16 
                 2.06 
                 6.19 
                 Hazy liquid 
                 Solid layer 
                 Solid layer over 
               
               
                   
                   
                   
                   
                 over liquid 
                 liquid 
               
               
                 17 
                 0 
                 8.25 
                 Hazy liquid 
                 Solid layer 
                 Solid layer over 
               
               
                   
                   
                   
                   
                 over liquid 
                 liquid 
               
               
                   
               
               
                   
                   
                 Triacetin 
               
               
                   
               
               
                 18 
                 6.19 
                 2.06 
                 Clear liquid 
                 Clear solid/gel 
                 Clear liquid 
               
               
                 19 
                 4.13 
                 4.13 
                 Hazy liquid 
                 Solid layer 
                 Separated hazy 
               
               
                   
                   
                   
                   
                 over liquid 
                 liquid 
               
               
                 20 
                 2.06 
                 6.19 
                 Hazy liquid 
                 Solid layer 
                 Solid layer over 
               
               
                   
                   
                   
                   
                 over liquid 
                 liquid 
               
               
                 21 
                 0 
                 8.25 
                 Hazy liquid 
                 Solid layer 
                   
               
               
                   
                   
                   
                   
                 over liquid 
               
               
                   
               
               
                   
                   
                 Triethyl 2- 
                   
                   
                   
               
               
                   
                   
                 Acetylcitrate 
               
               
                   
               
               
                 22 
                 6.19 
                 2.06 
                 Clear liquid 
                 Clear solid/gel 
                 Clear liquid 
               
               
                 23 
                 4.13 
                 4.13 
                 Clear liquid 
                 Liquid 
                 Hazy liquid 
               
               
                 24 
                 2.06 
                 6.19 
                 Hazy liquid 
                 Separated 
                 Solid layer over 
               
               
                   
                   
                   
                   
                 solid 
                 liquid 
               
               
                 25 
                 0 
                 8.25 
                 Hazy liquid 
                 Separated 
                 Solid layer over 
               
               
                   
                   
                   
                   
                 solid 
                 liquid 
               
               
                   
               
               
                   
                   
                 Dipropylene 
                   
                   
                   
               
               
                   
                   
                 Glycol Methyl 
                   
                   
                   
               
               
                   
                   
                 Ether Acetate 
               
               
                   
               
               
                 26 
                 6.19 
                 2.06 
                 Clear liquid 
                 Clear solid/gel 
                 Clear liquid 
               
               
                 27 
                 4.13 
                 4.13 
                 Clear liquid 
                 Opaque solid 
                 Clear liquid 
               
               
                 28 
                 2.06 
                 6.19 
                 Clear liquid 
                 Liquid 
                 Hazy liquid 
               
               
                 29 
                 0 
                 8.25 
                 Hazy liquid 
                 Liquid 
                 Cloudy liquid 
               
               
                   
               
               
                   
                   
                 Propylene Glycol 
                   
                   
                   
               
               
                   
                   
                 Methyl Ether 
                   
                   
                   
               
               
                   
                   
                 Acetate 
               
               
                   
               
               
                 30 
                 6.19 
                 2.06 
                 Clear liquid 
                 Clear solid/gel 
                 Clear liquid 
               
               
                 31 
                 4.13 
                 4.13 
                 Clear liquid 
                 Opaque solid 
                 Clear liquid 
               
               
                 32 
                 2.06 
                 6.19 
                 Clear liquid 
                 Liquid 
                 Hazy liquid 
               
               
                 33 
                 0 
                 8.25 
                 Cloudy liquid 
                 Liquid 
                 Cloudy liquid 
               
               
                   
               
               
                   
                   
                 Diethylene glycol 
                   
                   
                   
               
               
                   
                   
                 butyl ether acetate 
               
               
                   
               
               
                 34 
                 6.19 
                 2.06 
                 Clear liquid 
                 Clear solid/gel 
                 Clear liquid 
               
               
                 35 
                 4.13 
                 4.13 
                 Clear liquid 
                 Opaque solid 
                 Clear liquid 
               
               
                 36 
                 2.06 
                 6.19 
                 Clear liquid 
                 Liquid 
                 Very hazy liquid 
               
               
                 37 
                 0 
                 8.25 
                 Slightly Hazy 
                 Liquid 
                 Cloudy liquid 
               
               
                   
                   
                   
                 liquid 
               
               
                   
               
               
                   
                   
                 Ethylene glycol 
                   
                   
                   
               
               
                   
                   
                 butyl ether 
               
               
                   
               
               
                 38 
                 6.19 
                 2.06 
                 Clear liquid 
                 Clear solid/gel 
                 Clear liquid 
               
               
                 39 
                 4.13 
                 4.13 
                 Clear liquid 
                 Opaque solid 
                 Clear liquid 
               
               
                 40 
                 2.06 
                 6.19 
                 Clear liquid 
                 Slush 
                 Hazy liquid 
               
               
                 41 
                 0 
                 8.25 
                 Clear liquid 
                 Liquid 
                 Cloudy liquid 
               
               
                   
               
               
                   
                   
                 Diisononyl 
                   
                   
                   
               
               
                   
                   
                 Adipate 
               
               
                   
               
               
                 42 
                 6.19 
                 2.06 
                 Clear liquid 
                 Clear solid/gel 
                 Clear liquid 
               
               
                 43 
                 4.13 
                 4.13 
                 Clear liquid 
                 Clear solid/gel 
                 Clear liquid 
               
               
                 44 
                 2.06 
                 6.19 
                 Clear liquid 
                 Clear solid/gel 
                 Hazy liquid 
               
               
                 45 
                 0 
                 8.25 
                 Clear liquid 
                 Clear solid/gel 
                 Cloudy liquid 
               
               
                   
               
            
           
         
       
     
     The composition of Example 15 was found to have a Brookfield viscosity of about 45 cP at −40° C. and 10 s −1 . 
     Examples 46-86 
     The procedure of Examples 1-45 was repeated, except that toluene was used as solvent instead of HAN and observations at ambient temperature (RT) after storage at −40° C. were not recorded. Results are shown in Table 2. 
     
       
         
           
               
             
               
                 TABLE 2 
               
             
            
               
                   
               
               
                 Compositions and observed results for Examples 46-86. 
               
            
           
           
               
               
               
            
               
                   
                 Component, g 
                 Observations 
               
               
                   
               
            
           
           
               
               
               
               
               
            
               
                   
                   
                 Diethylene glycol butyl 
                   
                   
               
               
                 Example 
                 Toluene 
                 ether 
                 Initial 
                 At −40° C. 
               
               
                   
               
               
                 46 
                 8.25 
                 0   
                 Clear liquid 
                 Clear gel/solid 
               
               
                 47 
                 6.19 
                 2.06 
                 Clear liquid 
                 Clear gel/solid 
               
               
                 48 
                 4.13 
                 4.13 
                 Clear liquid 
                 Clear liquid 
               
               
                 49 
                 2.06 
                 6.19 
                 Clear liquid 
                 Clear gel/solid 
               
               
                 50 
                 0 
                 8.25 
                 Hazy liquid 
                 Opaque solid 
               
               
                   
               
               
                   
                   
                 2,2,4-Trimethyl-1,3- 
                   
                   
               
               
                   
                   
                 pentanediol 
                   
                   
               
               
                   
                   
                 monoisobutyrate 
               
               
                   
               
               
                 51 
                 6.19 
                 2.06 
                 Clear liquid 
                 Clear gel/solid 
               
               
                 52 
                 4.13 
                 4.13 
                 Clear liquid 
                 Clear gel/solid 
               
               
                 53 
                 2.06 
                 6.19 
                 Clear liquid 
                 Opaque solid 
               
               
                 54 
                 0 
                 8.25 
                 Clear liquid 
                 Opaque slush 
               
               
                   
               
               
                   
                   
                 Propylene Glycol 
                   
                   
               
               
                   
                   
                 Diacetate 
               
               
                   
               
               
                 55 
                 6.19 
                 2.06 
                 Clear liquid 
                 Clear gel/solid 
               
               
                 56 
                 4.13 
                 4.13 
                 Clear liquid 
                 Clear liquid 
               
               
                 57 
                 2.06 
                 6.19 
                 Hazy liquid 
                 Opaque solid 
               
               
                   
                   
                   
                   
                 over clear liquid 
               
               
                 58 
                 0 
                 8.25 
                 Hazy separated 
                 Opaque liquid 
               
               
                   
                   
                   
                 solid/gel 
                 with solid disk 
               
               
                   
               
               
                   
                   
                 Triacetin 
               
               
                   
               
               
                 59 
                 6.19 
                 2.06 
                 Clear liquid 
                 Clear liquid 
               
               
                 60 
                 4.13 
                 4.13 
                 Hazy liquid 
                 Opaque solid 
               
               
                   
                   
                   
                   
                 over clear liquid 
               
               
                 61 
                 2.06 
                 6.19 
                 Hazy liquid 
                 Opaque solid 
               
               
                   
                   
                   
                   
                 over clear liquid 
               
               
                 62 
                 0 
                 8.25 
                 Hazy separated 
                 Opaque solid 
               
               
                   
                   
                   
                 solid/gel 
                 over clear liquid 
               
               
                   
               
               
                   
                   
                 Triethyl 2-Acetylcitrate 
               
               
                   
               
               
                 63 
                 6.19 
                 2.06 
                 Clear liquid 
                 Clear slush 
               
               
                 64 
                 4.13 
                 4.13 
                 Hazy liquid 
                 Opaque solid 
               
               
                   
                   
                   
                   
                 over clear liquid 
               
               
                 65 
                 2.06 
                 6.19 
                 Hazy liquid 
                 Opaque solid 
               
               
                   
                   
                   
                   
                 over clear liquid 
               
               
                 66 
                 0 
                 8.25 
                 Hazy liquid with 
                 Clear slow 
               
               
                   
                   
                   
                 opaque gel chunks 
                 flowing gel with 
               
               
                   
                   
                   
                   
                 opaque solid 
               
               
                   
                   
                   
                   
                 chunks 
               
               
                   
               
               
                   
                   
                 Dipropylene Glycol 
                   
                   
               
               
                   
                   
                 Methyl Ether Acetate 
               
               
                   
               
               
                 67 
                 6.19 
                 2.06 
                 Clear liquid 
                 Clear gel/solid 
               
               
                 68 
                 4.13 
                 4.13 
                 Clear liquid 
                 Opaque slush 
               
               
                 69 
                 2.06 
                 6.19 
                 Clear liquid 
                 Opaque liquid 
               
               
                 70 
                 0 
                 8.25 
                 Hazy liquid 
                 Clear liquid with 
               
               
                   
                   
                   
                   
                 opaque solids 
               
               
                   
                   
                   
                   
                 lining vial walls 
               
               
                   
               
               
                   
                   
                 Propylene Glycol Methyl 
                   
                   
               
               
                   
                   
                 Ether Acetate 
               
               
                   
               
               
                 71 
                 6.19 
                 2.06 
                 Clear liquid 
                 Clear gel/solid 
               
               
                 72 
                 4.13 
                 4.13 
                 Clear liquid 
                 Opaque liquid 
               
               
                 73 
                 2.06 
                 6.19 
                 Clear liquid 
                 Opaque liquid 
               
               
                 74 
                 0 
                 8.25 
                 Cloudy liquid 
                 Clear liquid with 
               
               
                   
                   
                   
                   
                 opaque solids 
               
               
                   
                   
                   
                   
                 lining vial walls 
               
               
                   
               
               
                   
                   
                 Diethylene glycol butyl 
                   
                   
               
               
                   
                   
                 ether Acetate 
               
               
                   
               
               
                 75 
                 6.19 
                 2.06 
                 Clear liquid 
                 Clear gel/solid 
               
               
                 76 
                 4.13 
                 4.13 
                 Clear liquid 
                 Opaque liquid 
               
               
                 77 
                 2.06 
                 6.19 
                 Clear liquid 
                 Opaque liquid 
               
               
                 78 
                 0 
                 8.25 
                 Hazy liquid 
                 Opaque liquid 
               
               
                   
               
               
                   
                   
                 Ethylene glycol butyl ether 
                   
                   
               
               
                   
                   
                 acetate 
               
               
                   
               
               
                 79 
                 6.19 
                 2.06 
                 Clear liquid 
                 Clear gel/solid 
               
               
                 80 
                 4.13 
                 4.13 
                 Clear liquid 
                 Opaque slush 
               
               
                 81 
                 2.06 
                 6.19 
                 Clear liquid 
                 Opaque liquid 
               
               
                 82 
                 0 
                 8.25 
                 Clear liquid 
                 Opaque liquid 
               
               
                   
               
               
                   
                   
                 Diisononyl Adipate 
               
               
                   
               
               
                 83 
                 6.19 
                 2.06 
                 Clear liquid 
                 Clear gel/solid 
               
               
                 84 
                 4.13 
                 4.13 
                 Clear liquid 
                 Clear gel/solid 
               
               
                 85 
                 2.06 
                 6.19 
                 Clear liquid 
                 Opaque solid 
               
               
                 86 
                 0 
                 8.25 
                 Clear liquid 
                 Opaque solid 
               
               
                   
               
            
           
         
       
     
     Examples 87-106 
     The procedure of Examples 1-45 was repeated, except using 0.3 g of a C12-C15 alcohol ethoxylate in place of the 0.3 g of C11-C15 alcohol ethoxylate as surfactant. Results are shown in Table 3. 
     
       
         
           
               
             
               
                 TABLE 3 
               
             
            
               
                   
               
               
                 Compositions and observed results for Examples 87-106. 
               
            
           
           
               
               
               
            
               
                 Example 
                 Component, g 
                 Observations 
               
               
                   
               
            
           
           
               
               
               
               
               
               
            
               
                   
                   
                 Tributyl 2- 
                   
                   
                   
               
               
                   
                 HAN 
                 Acetylcitrate 
                 Initial 
                 At −40° C. 
                 RT After −40° C. 
               
               
                   
               
               
                 87 
                 8.25 
                 0   
                 Barely hazy 
                 Clear gel/solid 
                 Clear liquid 
               
               
                   
                   
                   
                 liquid 
                   
                   
               
               
                 88 
                 6.19 
                 2.06 
                 Barely hazy 
                 Clear gel/solid 
                 Clear liquid 
               
               
                   
                   
                   
                 liquid 
                   
                   
               
               
                 89 
                 4.13 
                 4.13 
                 Clear liquid 
                 Clear liquid 
                 Barely hazy liquid 
               
               
                 90 
                 2.06 
                 6.19 
                 Clear liquid 
                 Clear liquid 
                 Opaque liquid 
               
               
                 91 
                 0 
                 8.25 
                 Cloudy liquid 
                 Fast melting 
                 Opaque milky 
               
               
                   
                   
                   
                   
                 opaque solid 
                 liquid 
               
               
                   
               
               
                   
                   
                 Ethyl L- 
                   
                   
                   
               
               
                   
                   
                 Lactate 
               
               
                   
               
               
                 91 
                 6.19 
                 2.06 
                 Clear liquid 
                 Clear gel/solid 
                 Clear liquid 
               
               
                 92 
                 4.13 
                 4.13 
                 Clear liquid 
                 Clear gel/solid 
                 Clear liquid 
               
               
                 93 
                 2.06 
                 6.19 
                 Cloudy liquid 
                 Opaque solid 
                 Opaque fluffy stuff 
               
               
                   
                   
                   
                   
                 over clear 
                 over clear liquid 
               
               
                   
                   
                   
                   
                 liquid 
                   
               
               
                 94 
                 0 
                 8.25 
                 Cloudy liquid 
                 Cloudy liquid 
                 Opaque fluffy stuff 
               
               
                   
                   
                   
                 with solid ring 
                 with opaque 
                 over clear liquid 
               
               
                   
                   
                   
                   
                 ring 
                 with solid ring 
               
               
                   
               
               
                   
                   
                 Dipropylene 
                   
                   
                   
               
               
                   
                   
                 Glycol 
                   
                   
                   
               
               
                   
                   
                 Dibenzoate 
               
               
                   
               
               
                 95 
                 6.19 
                 2.06 
                 Barely hazy 
                 Clear gel/solid 
                 Slightly hazy liquid 
               
               
                   
                   
                   
                 liquid 
                   
                   
               
               
                 96 
                 4.13 
                 4.13 
                 Barely hazy 
                 Clear liquid 
                 Slightly hazy liquid 
               
               
                   
                   
                   
                 liquid 
                   
                   
               
               
                 97 
                 2.06 
                 6.19 
                 Cloudy liquid 
                 Clear slush 
                 Cloudy liquid 
               
               
                 98 
                 0 
                 8.25 
                 Cloudy flowing 
                 Clear gel/solid 
                 Cloudy liquid 
               
               
                   
                   
                   
                 gel 
               
               
                   
               
               
                   
                   
                 Dibutyl 
                   
                   
                   
               
               
                   
                   
                 Adipate 
               
               
                   
               
               
                 99 
                 6.19 
                 2.06 
                 Clear liquid 
                 Clear gel/solid 
                 Clear liquid 
               
               
                 100 
                 4.13 
                 4.13 
                 Clear liquid 
                 Clear gel/solid 
                 Clear liquid 
               
               
                 101 
                 2.06 
                 6.19 
                 Clear liquid 
                 Opaque slush 
                 Cloudy liquid 
               
               
                 102 
                 0 
                 8.25 
                 Clear liquid 
                 Opaque liquid 
                 Opaque milky 
               
               
                   
                   
                   
                   
                   
                 liquid 
               
               
                   
               
               
                   
                   
                 Diethyl 
                   
                   
                   
               
               
                   
                   
                 Succinate 
               
               
                   
               
               
                 103 
                 6.19 
                 2.06 
                 Clear liquid 
                 Clear gel/solid 
                 Clear liquid 
               
               
                 104 
                 4.13 
                 4.13 
                 Clear liquid 
                 Clear liquid 
                 Slightly hazy liquid 
               
               
                 105 
                 2.06 
                 6.19 
                 Cloudy liquid 
                 Cloudy liquid 
                 Opaque liquid 
               
               
                   
                   
                   
                   
                 with opaque ring 
                   
               
               
                 106 
                 0 
                 8.25 
                 Cloudy liquid 
                 Separated 
                 Chunky opaque 
               
               
                   
                   
                   
                 with solid ring 
                 opaque solid 
                 liquid 
               
               
                   
               
            
           
         
       
     
     Examples 107-115 
     Using the General Procedure, Polymer 2 and a C11-C15 alcohol ethoxylate as surfactant were employed in combination with various blends of ester compounds as the PIC additive, further wherein HAN, toluene, or a blend thereof was employed as solvent. Compositions that were pourable at −40° C. are shown in Table 4 along with observed appearance initially and at −40° C. 
     
       
         
           
               
             
               
                 TABLE 4 
               
             
            
               
                   
               
               
                 Observations for various PIC additives and solvents/solvent 
               
               
                 ratios employed in PIC compositions of Examples 107-115. 
               
            
           
           
               
               
            
               
                 Component, g 
                   
               
            
           
           
               
               
               
            
               
                   
                 Diethylene 
                   
               
            
           
           
               
               
               
               
               
               
            
               
                   
                 glycol 
                   
                 C11C15 
                   
                 Observations 
               
            
           
           
               
               
               
               
               
               
               
            
               
                   
                 Benzyl 
                 butyl 
                   
                 Alcohol 
                   
                 RT 
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                 Ex. 
                 Benzoate 
                 acetate 
                 Toluene 
                 Ethoxylate 
                 Polymer 2 
                 Initial 
                 At −40° C. 
                 After −40° C. 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                 107 
                  0.88 
                 3.59 
                  4.29 
                 0 
                 1.24 
                 Clear 
                 Flowing 
                 n/a 
               
               
                   
                   
                   
                   
                   
                   
                 liquid 
                 gel 
               
               
                   
               
               
                   
                   
                 Acetyl 
               
               
                   
                   
                 Triethyl 
               
               
                   
                 HAN 
                 Citrate 
                 Toluene 
               
               
                   
               
               
                 108 
                 52.30 
                 32.30 
                 0   
                 3 
                 12.4 
                 Clear 
                 Clear 
                 Cloudy 
               
               
                   
                   
                   
                   
                   
                   
                 liquid 
                 liquid 
                 liquid 
               
               
                   
               
               
                   
                 HAN 
                 Triacetin 
                 Toluene 
               
               
                   
               
               
                 109 
                 39.23 
                 24.23 
                 21.15 
                 3 
                 12.4 
                 Clear 
                 Clear 
                 Cloudy 
               
               
                   
                   
                   
                   
                   
                   
                 liquid 
                 liquid 
                 liquid 
               
               
                   
               
               
                   
                   
                   
                 Diethylene 
               
               
                   
                   
                 Propylene 
                 Glycol 
               
               
                   
                   
                 Glycol 
                 Butyl 
               
               
                   
                 HAN 
                 Diacetate 
                 Ether 
               
               
                   
               
               
                 110 
                 39.23 
                 24.23 
                 21.15 
                 3 
                 12.4 
                 Clear 
                 Clear 
                 Opaque 
               
               
                   
                   
                   
                   
                   
                   
                 liquid 
                 liquid 
                 liquid 
               
               
                   
               
               
                   
                   
                 Acetyl 
               
               
                   
                   
                 Triethyl 
               
               
                   
                 HAN 
                 Citrate 
                 Toluene 
               
               
                   
               
               
                 111 
                 32.48 
                 30.98 
                 21.15 
                 3 
                 12.4 
                 Clear 
                 Clear 
                 Cloudy 
               
               
                   
                   
                   
                   
                   
                   
                 liquid 
                 liquid 
                 liquid 
               
               
                   
               
               
                   
                 HAN 
                 Triacetin 
                 Toluene 
               
               
                   
               
               
                 112 
                 32.48 
                 30.98 
                 21.15 
                 3 
                 12.4 
                 Clear 
                 Clear 
                 Cloudy 
               
               
                   
                   
                   
                   
                   
                   
                 liquid 
                 liquid 
                 liquid 
               
               
                   
               
               
                   
                   
                 Propylene 
               
               
                   
                   
                 Glycol 
               
               
                   
                 HAN 
                 Diacetate 
                 Toluene 
               
               
                   
               
               
                 113 
                 43.30 
                 41.30 
                 0   
                 3 
                 12.4 
                 Cloudy 
                 Cloudy 
                 Opaque 
               
               
                   
                   
                   
                   
                   
                   
                 liquid 
                 liquid 
                 liquid 
               
               
                 114 
                 32.48 
                 30.98 
                 21.15 
                 3 
                 12.4 
                 Cloudy 
                 Cloudy 
                 Opaque 
               
               
                   
                   
                   
                   
                   
                   
                 liquid 
                 liquid 
                 liquid 
               
               
                   
               
               
                   
                   
                 Propylene 
               
               
                   
                   
                 Glycol 
               
               
                   
                 HAN 
                 Diacetate 
                 Toluene 
               
               
                   
               
               
                 115 
                 32.48 
                 30.98 
                 21.15 
                 3 
                 12.4 
                 Clear 
                 Clear 
                 Cloudy 
               
               
                   
                   
                   
                   
                   
                   
                 liquid 
                 liquid 
                 liquid 
               
               
                   
               
            
           
         
       
     
     Examples 116-145 
     Using the General Procedure, solvent blends and ratios of solvents in such blends was varied for 12.4 g Polymer 2 and 3.0 g of Tergitol 15-S-3 (secondary alcohol ethoxylate, available from the DOW® Chemical Company of Midland, Mich.) in the presence of various ester compounds. “Solvent 150” is SOLVESSO® 150 (obtained from the ExxonMobil Chemical Co. of Irving, Tex.); “Solvent 195” is SOLVESSO® 195 (obtained from ExxonMobil). Observations were made initially and after 12-18 hours storage at −40° C. Results are shown in Table 5. 
     
       
         
           
               
             
               
                 TABLE 5 
               
             
            
               
                   
               
               
                 Compositions and observations for Examples 116-145. 
               
            
           
           
               
               
               
            
               
                   
                 Component, g 
                 Observations 
               
               
                   
               
            
           
           
               
               
               
               
               
               
            
               
                   
                   
                 Acetyl 
                   
                   
                   
               
               
                   
                   
                 Triethyl 
                   
                   
                   
               
               
                 Example 
                 HAN 
                 Citrate 
                 Toluene 
                 Initial 
                 At −40° C. 
               
               
                   
               
               
                 116 
                 52.30 
                 32.30 
                  0.00 
                 Clear 
                 Clear liquid 
               
               
                   
                   
                   
                   
                 liquid 
                   
               
               
                 117 
                 32.48 
                 30.98 
                 21.15 
                 Clear 
                 Clear liquid 
               
               
                   
                   
                   
                   
                 liquid 
               
               
                   
               
               
                   
                 HAN 
                 Triacetin 
                 Toluene 
               
               
                   
               
               
                 118 
                 39.23 
                 24.23 
                 21.15 
                 Clear 
                 Clear liquid 
               
               
                   
                   
                   
                   
                 liquid 
                   
               
               
                 119 
                 32.48 
                 30.98 
                 21.15 
                 Hazy 
                 Clear liquid with 
               
               
                   
                   
                   
                   
                 liquid 
                 solid disk 
               
               
                   
               
               
                   
                   
                 Propylene 
                   
                   
                   
               
               
                   
                   
                 Glycol 
                   
                   
                   
               
               
                   
                 HAN 
                 Diacetate 
                 Toluene 
               
               
                   
               
               
                 120 
                 32.48 
                 30.98 
                 21.15 
                 Clear 
                 Clear fast 
               
               
                   
                   
                   
                   
                 liquid 
                 melting slush 
               
               
                   
               
               
                   
                   
                 Acetyl 
                   
                   
                   
               
               
                   
                   
                 Triethyl 
                 Solvent 
                   
                   
               
               
                   
                 HAN 
                 Citrate 
                 150 
               
               
                   
               
               
                 121 
                 52.30 
                 32.30 
                 0   
                 Clear 
                 Clear liquid 
               
               
                   
                   
                   
                   
                 liquid 
                   
               
               
                 122 
                 32.48 
                 30.98 
                 21.15 
                 Clear 
                 Clear fast 
               
               
                   
                   
                   
                   
                 liquid 
                 melting slush 
               
               
                   
               
               
                   
                   
                   
                 Solvent 
                   
                   
               
               
                   
                 HAN 
                 Triacetin 
                 150 
               
               
                   
               
               
                 123 
                 39.23 
                 24.23 
                 21.15 
                 Clear 
                 Clear liquid 
               
               
                   
                   
                   
                   
                 liquid 
                   
               
               
                 124 
                 32.48 
                 30.98 
                 21.15 
                 Hazy 
                 Clear liquid with 
               
               
                   
                   
                   
                   
                 liquid 
                 solid disk 
               
               
                   
               
               
                   
                   
                 Propylene 
                   
                   
                   
               
               
                   
                   
                 Glycol 
                 Solvent 
                   
                   
               
               
                   
                 HAN 
                 Diacetate 
                 150 
               
               
                   
               
               
                 125 
                 32.48 
                 30.98 
                 21.15 
                 Clear 
                 Clear fast 
               
               
                   
                   
                   
                   
                 liquid 
                 melting slush 
               
               
                   
               
               
                   
                   
                 Acetyl 
                   
                   
                   
               
               
                   
                   
                 Triethyl 
                 Solvent 
                   
                   
               
               
                   
                 HAN 
                 Citrate 
                 195 
               
               
                   
               
               
                 126 
                 52.30 
                 32.30 
                  0.00 
                 Clear 
                 Clear slush 
               
               
                   
                   
                   
                   
                 liquid 
                   
               
               
                 127 
                 32.48 
                 30.98 
                 21.15 
                 Clear 
                 Clear slush 
               
               
                   
                   
                   
                   
                 liquid 
               
               
                   
               
               
                   
                   
                   
                 Solvent 
                   
                   
               
               
                   
                 HAN 
                 Triacetin 
                 195 
               
               
                   
               
               
                 128 
                 39.23 
                 24.23 
                 21.15 
                 Clear 
                 Clear liquid with 
               
               
                   
                   
                   
                   
                 liquid 
                 solid ring 
               
               
                 129 
                 32.48 
                 30.98 
                 21.15 
                 Hazy 
                 Separated cloudy 
               
               
                   
                   
                   
                   
                 liquid 
                 solid 
               
               
                   
               
               
                   
                   
                 Propylene 
                   
                   
                   
               
               
                   
                   
                 Glycol 
                 Solvent 
                   
                   
               
               
                   
                 HAN 
                 Diacetate 
                 195 
               
               
                   
               
               
                 130 
                 32.48 
                 30.98 
                 21.15 
                 Clear 
                 Clear slush 
               
               
                   
                   
                   
                   
                 liquid 
               
               
                   
               
               
                   
                   
                 Acetyl 
                   
                   
                   
               
               
                   
                   
                 Triethyl 
                   
                   
                   
               
               
                   
                 HAN 
                 Citrate 
                 Toluene 
               
               
                   
               
               
                 131 
                 0   
                 32.30 
                 52.30 
                 Clear 
                 Clear slush 
               
               
                   
                   
                   
                   
                 liquid 
                   
               
               
                 132 
                 0   
                 30.98 
                 53.63 
                 Clear 
                 Clear slush 
               
               
                   
                   
                   
                   
                 liquid 
               
               
                   
               
               
                   
                 HAN 
                 Triacetin 
                 Toluene 
               
               
                   
               
               
                 133 
                 0   
                 24.23 
                 60.38 
                 Clear 
                 Clear liquid 
               
               
                   
                   
                   
                   
                 liquid 
                   
               
               
                 134 
                 0   
                 30.98 
                 53.63 
                 Hazy 
                 Separated cloudy 
               
               
                   
                   
                   
                   
                 liquid 
                 solid 
               
               
                   
               
               
                   
                   
                 Propylene 
                   
                   
                   
               
               
                   
                   
                 Glycol 
                   
                   
                   
               
               
                   
                 HAN 
                 Diacetate 
                 Toluene 
               
               
                   
               
               
                 135 
                 0   
                 30.98 
                 53.63 
                 Clear 
                 Clear liquid 
               
               
                   
                   
                   
                   
                 liquid 
               
               
                   
               
               
                   
                   
                 Acetyl 
                   
                   
                   
               
               
                   
                   
                 Triethyl 
                   
                   
                   
               
               
                   
                 HAN 
                 Citrate 
                 Toluene 
               
               
                   
               
               
                 136 
                 52.30 
                 32.30 
                  0.00 
                 Clear 
                 Clear liquid 
               
               
                   
                   
                   
                   
                 liquid 
                   
               
               
                 137 
                 32.48 
                 30.98 
                 21.15 
                 Clear 
                 Clear liquid 
               
               
                   
                   
                   
                   
                 liquid 
               
               
                   
               
               
                   
                 HAN 
                 Triacetin 
                 Toluene 
               
               
                   
               
               
                 138 
                 39.23 
                 24.23 
                 21.15 
                 Clear 
                 Clear liquid 
               
               
                   
                   
                   
                   
                 liquid 
                   
               
               
                 139 
                 32.48 
                 30.98 
                 21.15 
                 Hazy 
                 Opaque solid 
               
               
                   
                   
                   
                   
                 liquid 
                 over cloudy 
               
               
                   
                   
                   
                   
                   
                 liquid 
               
               
                   
               
               
                   
                   
                 Propylene 
                   
                   
                   
               
               
                   
                   
                 Glycol 
                   
                   
                   
               
               
                   
                 HAN 
                 Diacetate 
                 Toluene 
               
               
                   
               
               
                 140 
                 32.48 
                 30.98 
                 21.15 
                 Clear 
                 Clear slush 
               
               
                   
                   
                   
                   
                 liquid 
               
               
                   
               
               
                   
                   
                 Acetyl 
                   
                   
                   
               
               
                   
                 Solvent 
                 Triethyl 
                   
                   
                   
               
               
                   
                 195 
                 Citrate 
                 Toluene 
               
               
                   
               
               
                 141 
                 52.30 
                 32.30 
                  0.00 
                 Clear 
                 Clear liquid 
               
               
                   
                   
                   
                   
                 liquid 
                   
               
               
                 142 
                 32.48 
                 30.98 
                 21.15 
                 Clear 
                 Clear slush 
               
               
                   
                   
                   
                   
                 liquid 
               
               
                   
               
               
                   
                 Solvent 
                   
                   
                   
                   
               
               
                   
                 195 
                 Triacetin 
                 Toluene 
               
               
                   
               
               
                 143 
                 39.23 
                 24.23 
                 21.15 
                 Clear 
                 Clear liquid 
               
               
                   
                   
                   
                   
                 liquid 
                   
               
               
                 144 
                 32.48 
                 30.98 
                 21.15 
                 Hazy 
                 Opaque solid 
               
               
                   
                   
                   
                   
                 liquid 
                 over cloudy 
               
               
                   
                   
                   
                   
                   
                 liquid 
               
               
                   
               
               
                   
                   
                 Propylene 
                   
                   
                   
               
               
                   
                 Solvent 
                 Glycol 
                   
                   
                   
               
               
                   
                 195 
                 Diacetate 
                 Toluene 
               
               
                   
               
               
                 145 
                 32.48 
                 30.98 
                 21.15 
                 Clear 
                 Opaque slush 
               
               
                   
                   
                   
                   
                 liquid 
               
               
                   
               
            
           
         
       
     
     Example 146-152 
     Using the General Procedure, 12.4 g of Polymer 2 was tested with and without Tergitol 15-S-3 (obtained from the DOW® Chemical Company of Midland, Mich.), a mixture of C11-C15 secondary alcohol ethoxylates with an average of 3 ethylene oxide units; and with and without toluene in the presence of various ester compounds. Compositions and results are shown in Table 6. 
     
       
         
           
               
             
               
                 TABLE 6 
               
             
            
               
                   
               
               
                 Compositions and observed results for Examples 146-152. 
               
            
           
           
               
               
               
            
               
                   
                 Components, g 
                   
               
            
           
           
               
               
               
               
            
               
                   
                 Acetyl 
                   
                 Observations 
               
            
           
           
               
               
               
               
               
               
            
               
                   
                 Triethyl 
                   
                 Tergitol 
                   
                 RT 
               
            
           
           
               
               
               
               
               
               
               
               
            
               
                 Example 
                 HAN 
                 Citrate 
                 Toluene 
                 15-S-3 
                 Initial 
                 At −40° C. 
                 After −40° C. 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
            
               
                 146 
                 53.80 
                 33.80 
                 0 
                 0 
                 Clear 
                 Clear 
                 Cloudy 
               
               
                   
                   
                   
                   
                   
                 liquid 
                 liquid 
                 liquid 
               
               
                 147 
                 33.48 
                 31.98 
                 22.15 
                 0 
                 Clear 
                 Clear 
                 Cloudy 
               
               
                   
                   
                   
                   
                   
                 liquid 
                 liquid 
                 liquid 
               
               
                   
               
               
                   
                   
                 Triacetin 
               
               
                   
               
               
                 148 
                 37.23 
                 25.23 
                 22.15 
                 0 
                 Clear 
                 Clear 
                 Cloudy 
               
               
                   
                   
                   
                   
                   
                 liquid 
                 liquid 
                 liquid 
               
               
                 149 
                 33.48 
                 31.98 
                 22.15 
                 0 
                 Slightly 
                 Clear 
                 Chunky 
               
               
                   
                   
                   
                   
                   
                 hazy 
                 solid over 
                 cloudy 
               
               
                   
                   
                   
                   
                   
                 liquid 
                 clear 
                 liquid 
               
               
                   
                   
                   
                   
                   
                   
                 liquid 
               
               
                   
               
               
                   
                   
                 Propylene 
               
               
                   
                   
                 Glycol 
               
               
                   
                   
                 Diacetate 
               
               
                   
               
               
                 150 
                 43.30 
                 41.30 
                 0 
                 3 
                 Hazy 
                 Cloudy 
                 Opaque 
               
               
                   
                   
                   
                   
                   
                 liquid 
                 liquid 
                 liquid 
               
               
                 151 
                 44.80 
                 42.80 
                 0 
                 0 
                 Hazy 
                 Cloudy 
                 Opaque 
               
               
                   
                   
                   
                   
                   
                 liquid 
                 liquid 
                 liquid 
               
               
                 152 
                 33.48 
                 31.98 
                 22.15 
                 0 
                 Clear 
                 Clear 
                 Cloudy 
               
               
                   
                   
                   
                   
                   
                 liquid 
                 liquid 
                 liquid 
               
               
                   
               
            
           
         
       
     
     Examples 153-156 
     Using the General Procedure, ester compounds and solvent blends were varied with a blend of Polymer 1 and Polymer 2. The −40° C. flowability of a PIC compositions prepared from a physical blend of these two polymers were found to vary by ratio of the polymers, chemical structure of the ester compound, and the ratio of ester compound to solvent. Further, the presence of surfactant was found, in some embodiments, to stabilize the PIC composition during warming after exposure to −40° C., for example by preventing phase separation of liquids and solids during warming. 
     Results for PIC compositions exhibiting flow characteristics at −40° C. are shown in Table 7. 
     
       
         
           
               
             
               
                 TABLE 7 
               
             
            
               
                   
               
               
                 Compositions and observed results for Examples 153-156. 
               
            
           
           
               
               
               
            
               
                   
                 Component, g 
                   
               
            
           
           
               
               
               
               
            
               
                   
                 Triethyl 
                   
                 Observations 
               
            
           
           
               
               
               
               
            
               
                   
                 Acetyl 
                   
                 RT 
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                 Ex. 
                 HAN 
                 Citrate 
                   
                 Polymer 1 
                 Polymer 2 
                 Initial 
                 −40° C. 
                 After −40° C. 
               
               
                   
               
               
                 153 
                 64.62 
                 21.54 
                   
                 10.71 
                 3.13 
                 Barely 
                 Clear 
                 Barely 
               
               
                   
                   
                   
                   
                   
                   
                 hazy 
                 flowing 
                 hazy 
               
               
                   
                   
                   
                   
                   
                   
                 liquid 
                 gel 
                 liquid 
               
               
                   
               
               
                   
                   
                 Dimethyl 
               
               
                   
                 HAN 
                 Glutarate 
                   
                 Polymer 1 
                 Polymer 2 
               
               
                   
               
               
                 154 
                 43.08 
                 43.08 
                   
                 10.71 
                 3.13 
                 Hazy 
                 Cloudy 
                 Cloudy 
               
               
                   
                   
                   
                   
                   
                   
                 liquid 
                 liquid 
                 liquid 
               
               
                   
               
               
                   
                   
                 Propylene 
               
               
                   
                   
                 Glycol 
                 Tergitol 
               
               
                   
                 HAN 
                 Diacetate 
                 15-S-3 
                 Polymer 1 
                 Polymer 2 
               
               
                   
               
               
                 155 
                 41.58 
                 41.58 
                 3 
                 10.71 
                 3.13 
                 Clear 
                 Cloudy 
                 Cloudy 
               
               
                   
                   
                   
                   
                   
                   
                 liquid 
                 liquid 
                 liquid 
               
               
                   
               
               
                   
                   
                 Propylene 
               
               
                   
                   
                 Glycol 
               
               
                   
                   
                 Methyl 
               
               
                   
                   
                 Ether 
               
               
                   
                 HAN 
                 Acetate 
                   
                 Polymer 1 
                 Polymer 6 
               
               
                   
               
               
                 156 
                 43.30 
                 43.30 
                 0 
                  7.14 
                 6.25 
                 Clear 
                 Opaque 
                 Opaque 
               
               
                   
                   
                   
                   
                   
                   
                 liquid 
                 liquid 
                 liquid 
               
               
                   
               
            
           
         
       
     
     Example 157-275 
     Using the General Procedure, 1.45 g of Polymer 4 was blended with the components and in the amounts shown in Table 8. Results of testing are shown in Table 8. 
     
       
         
           
               
             
               
                 TABLE 8 
               
             
            
               
                   
               
               
                 Compositions and observations for Examples 157-275. 
               
            
           
           
               
               
            
               
                   
                 Observations 
               
            
           
           
               
               
               
               
               
               
            
               
                   
                 Component, g 
                   
                 RT 
                 RT 48 Hours 
                 RT 1 Week 
               
            
           
           
               
               
               
               
               
               
               
               
            
               
                 Ex. 
                 HAN 
                 Toluene 
                 Initial 
                 At −40° C. 
                 After −40° C. 
                 After −40° C. 
                 After −40° C. 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
            
               
                 157 
                 8.55 
                 0   
                 Clear liquid 
                 Cloudy Solid 
                 Hazy Liquid 
                 Hazy liquid 
                 Hazy liquid 
               
               
                 158 
                 6.41 
                 2.14 
                 Clear liquid 
                 Cloudy Solid 
                 Hazy Liquid 
                 Hazy liquid 
                 Hazy liquid 
               
               
                 159 
                 4.28 
                 4.28 
                 Clear liquid 
                 Cloudy Solid 
                 Hazy Liquid 
                 Hazy liquid 
                 Hazy liquid 
               
               
                 160 
                 2.14 
                 6.41 
                 Clear liquid 
                 Cloudy Solid 
                 Clear Liquid 
                 Clear Liquid 
                 Hazy liquid 
               
               
                 161 
                 0   
                 8.55 
                 Clear liquid 
                 Cloudy Solid 
                 Clear Liquid 
                 Clear Liquid 
                 Clear Liquid 
               
               
                   
               
               
                   
                   
                 Butyl 
               
               
                   
                 HAN 
                 Carbitol 
               
               
                   
               
               
                 162 
                 6.41 
                 2.14 
                 Clear liquid 
                 Cloudy Solid 
                 Hazy Liquid 
                 Hazy Liquid 
                 Hazy Liquid 
               
               
                 163 
                 4.28 
                 4.28 
                 Hazy liquid 
                 Cloudy Solid 
                 Cloudy Gel 
                 Cloudy solid 
                 Cloudy solid 
               
               
                 164 
                 2.14 
                 6.41 
                 Cloudy Liquid- 
                 Cloudy Slush- 
                 Cloudy Liquid- 
                 Clear liquid- 
                 Clear liquid- 
               
               
                   
                   
                   
                 Homogeneous 
                 Homogeneous 
                 Homogeneous 
                 top, Cloudy 
                 top, Cloudy 
               
               
                   
                   
                   
                   
                   
                   
                 gel-bottom 
                 gel-bottom 
               
               
                 165 
                 0   
                 8.55 
                 Cloudy Liquid- 
                 Cloudy Liquid- 
                 Cloudy Liquid- 
                 Clear liquid- 
                 Clear liquid- 
               
               
                   
                   
                   
                 Homogeneous 
                 Homogeneous 
                 Homogeneous 
                 top, cloudy 
                 top, cloudy 
               
               
                   
                   
                   
                   
                   
                   
                 liquid-bottom 
                 liquid-bottom 
               
               
                   
               
               
                   
                   
                 2,2,4- 
               
               
                   
                   
                 Trimethyl- 
               
               
                   
                   
                 1,3- 
               
               
                   
                 HAN 
                 pentanediol 
               
               
                   
               
               
                 166 
                 6.41 
                 2.14 
                 Clear liquid 
                 Cloudy Solid 
                 Hazy Liquid 
                 Hazy liquid- 
                 Hazy liquid- 
               
               
                   
                   
                   
                   
                   
                   
                 slight 
                 slight 
               
               
                   
                   
                   
                   
                   
                   
                 precipitate at 
                 precipitate at 
               
               
                   
                   
                   
                   
                   
                   
                 bottom 
                 bottom 
               
               
                 167 
                 4.28 
                 4.28 
                 Clear liquid 
                 Cloudy Solid 
                 Cloudy Liquid- 
                 Hazy liquid- 
                 Hazy liquid- 
               
               
                   
                   
                   
                   
                   
                 Homogeneous 
                 slight cloudy 
                 slight cloudy 
               
               
                   
                   
                   
                   
                   
                   
                 gel at bottom 
                 gel at bottom 
               
               
                 168 
                 2.14 
                 6.41 
                 Cloudy Liquid- 
                 Cloudy Solid 
                 Cloudy Gel 
                 Cloudy solid 
                 Cloudy solid 
               
               
                   
                   
                   
                 Homogeneous 
               
               
                 169 
                 0   
                 8.55 
                 Cloudy Liquid- 
                 Cloudy Solid 
                 Cloudy Liquid- 
                 Cloudy Liquid- 
                 Cloudy liquid- 
               
               
                   
                   
                   
                 Homogeneous 
                   
                 Homogeneous 
                 Homogeneous 
                 slight 
               
               
                   
                   
                   
                   
                   
                   
                   
                 separation 
               
               
                   
               
               
                   
                   
                 Propylene 
               
               
                   
                   
                 Glycol 
               
               
                   
                 HAN 
                 Diacetate 
               
               
                   
               
               
                 170 
                 6.41 
                 2.14 
                 Clear liquid 
                 Cloudy Solid 
                 Hazy Liquid 
                 Hazy liquid- 
                 Hazy liquid- 
               
               
                   
                   
                   
                   
                   
                   
                 slight 
                 slight 
               
               
                   
                   
                   
                   
                   
                   
                 precipitate at 
                 precipitate at 
               
               
                   
                   
                   
                   
                   
                   
                 bottom 
                 bottom 
               
               
                 171 
                 4.28 
                 4.28 
                 Cloudy Liquid- 
                 Cloudy Liquid- 
                 Cloudy Liquid- 
                 Cloudy liquid- 
                 Cloudy liquid- 
               
               
                   
                   
                   
                 Homogeneous 
                 Homogeneous 
                 Homogeneous 
                 Homogeneous 
                 slight 
               
               
                   
                   
                   
                   
                   
                   
                   
                 separation 
               
               
                 172 
                 2.14 
                 6.41 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 Multiple 
                 Cloudy liquid- 
                 Cloudy liquid- 
               
               
                   
                   
                   
                 solid top layer 
                 solid top layer 
                 layers- 
                 top, clear 
                 top, clear 
               
               
                   
                   
                   
                   
                   
                 cloudy/clear 
                 liquid-bottom 
                 liquid-bottom 
               
               
                 173 
                 0   
                 8.55 
                 Cloudy liquid- 
                 Cloudy Liquid- 
                 Multiple 
                 Cloudy liquid- 
                 Cloudy liquid- 
               
               
                   
                   
                   
                 solid top layer 
                 solid top layer 
                 layers- 
                 top, clear 
                 top, clear 
               
               
                   
                   
                   
                   
                   
                 cloudy/clear 
                 liquid-bottom 
                 liquid-bottom 
               
               
                   
               
               
                   
                 HAN 
                 Triacetin 
               
               
                   
               
               
                 174 
                 6.41 
                 2.14 
                 Clear liquid 
                 Cloudy Solid 
                 Multiple 
                 Cloudy liquid- 
                 Cloudy liquid- 
               
               
                   
                   
                   
                   
                   
                 layers- 
                 top, clear 
                 top, clear 
               
               
                   
                   
                   
                   
                   
                 cloudy/clear 
                 liquid-bottom 
                 liquid-bottom 
               
               
                 175 
                 4.28 
                 4.28 
                 Clear liquid- 
                 Cloudy Solid 
                 Multiple 
                 Cloudy liquid- 
                 Cloudy liquid- 
               
               
                   
                   
                   
                 two layers 
                   
                 layers- 
                 top, clear 
                 top, clear 
               
               
                   
                   
                   
                   
                   
                 cloudy/clear 
                 liquid-bottom 
                 liquid-bottom 
               
               
                 176 
                 2.14 
                 6.41 
                 Clear liquid- 
                 Cloudy Solid 
                 Multiple 
                 Cloudy solid- 
                 Cloudy solid- 
               
               
                   
                   
                   
                 solid top layer 
                   
                 layers- 
                 top, clear 
                 top, clear 
               
               
                   
                   
                   
                   
                   
                 cloudy/clear 
                 liquid-bottom 
                 liquid-bottom 
               
               
                 177 
                 0   
                 8.55 
                 Cloudy liquid- 
                 Cloudy Solid 
                 Multiple 
                 Cloudy solid- 
                 Cloudy solid- 
               
               
                   
                   
                   
                 two layers 
                   
                 layers- 
                 top, clear 
                 top, clear 
               
               
                   
                   
                   
                   
                   
                 cloudy/clear 
                 liquid-bottom 
                 liquid-bottom 
               
               
                   
               
               
                   
                   
                 Triethyl 2- 
               
               
                   
                 HAN 
                 Acetylcitrate 
               
               
                   
               
               
                 178 
                 6.41 
                 2.14 
                 Clear liquid 
                 Cloudy Solid 
                 Cloudy liquid 
                 Hazy liquid- 
                 Hazy liquid- 
               
               
                   
                   
                   
                   
                   
                   
                 slight 
                 slight 
               
               
                   
                   
                   
                   
                   
                   
                 precipitate at 
                 precipitate at 
               
               
                   
                   
                   
                   
                   
                   
                 bottom 
                 bottom 
               
               
                 179 
                 4.28 
                 4.28 
                 Hazy liquid- 
                 Solid-two 
                 Cloudy liquid 
                 Clear liquid 
                 Clear liquid 
               
               
                   
                   
                   
                 two layers 
                 layers 
                 top layer- 
                 bottom-cloudy 
                 bottom-cloudy 
               
               
                   
                   
                   
                   
                   
                 Clear liquid 
                 liquid top 
                 liquid top 
               
               
                   
                   
                   
                   
                   
                 bottom layer 
               
               
                 180 
                 2.14 
                 6.41 
                 Cloudy liquid- 
                 Solid-two 
                 Cloudy liquid 
                 Clear liquid 
                 Clear liquid 
               
               
                   
                   
                   
                 solid top layer 
                 layers 
                 top layer- 
                 bottom-cloudy 
                 bottom-cloudy 
               
               
                   
                   
                   
                   
                   
                 Clear liquid 
                 liquid top 
                 liquid top 
               
               
                   
                   
                   
                   
                   
                 bottom layer 
               
               
                 181 
                 0   
                 8.55 
                 Cloudy liquid- 
                 Solid-two 
                 Cloudy liquid 
                 Clear liquid 
                 Clear liquid 
               
               
                   
                   
                   
                 solid top layer 
                 layers 
                 top layer- 
                 bottom-cloudy 
                 bottom-cloudy 
               
               
                   
                   
                   
                   
                   
                 Clear liquid 
                 liquid top 
                 liquid top 
               
               
                   
                   
                   
                   
                   
                 bottom layer 
               
               
                   
               
               
                   
                   
                 Dipropylene 
               
               
                   
                   
                 Glycol 
               
               
                   
                   
                 Methyl 
               
               
                   
                   
                 Ether 
               
               
                   
                 HAN 
                 Acetate 
               
               
                   
               
               
                 182 
                 6.41 
                 2.14 
                 Clear liquid 
                 Cloudy Solid 
                 Hazy Liquid 
                 Hazy liquid- 
                 Hazy liquid- 
               
               
                   
                   
                   
                   
                   
                   
                 slight 
                 slight 
               
               
                   
                   
                   
                   
                   
                   
                 precipitate at 
                 precipitate at 
               
               
                   
                   
                   
                   
                   
                   
                 bottom 
                 bottom 
               
               
                 183 
                 4.28 
                 4.28 
                 Clear liquid 
                 Cloudy Solid 
                 Cloudy liquid 
                 Cloudy solid 
                 Cloudy solid 
               
               
                 184 
                 2.14 
                 6.41 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 Cloudy liquid 
                 Cloudy liquid- 
                 Cloudy liquid- 
               
               
                   
                   
                   
                 Homogeneous 
                 Homogeneous 
                   
                 two phase 
                 two phase 
               
               
                 185 
                 0   
                 8.55 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 Cloudy liquid- 
               
               
                   
                   
                   
                 Homogeneous 
                 Homogeneous 
                 Homogeneous 
                 Homogeneous 
                 Homogeneous 
               
               
                   
               
               
                   
                   
                 Propylene 
               
               
                   
                   
                 Glycol 
               
               
                   
                   
                 Methyl 
               
               
                   
                   
                 Ether 
               
               
                   
                 HAN 
                 Acetate 
               
               
                   
               
               
                 186 
                 6.41 
                 2.14 
                 Clear liquid 
                 Cloudy Solid 
                 Hazy Liquid 
                 Hazy liquid- 
                 Hazy liquid- 
               
               
                   
                   
                   
                   
                   
                   
                 slight 
                 slight 
               
               
                   
                   
                   
                   
                   
                   
                 precipitate at 
                 precipitate at 
               
               
                   
                   
                   
                   
                   
                   
                 bottom 
                 bottom 
               
               
                 187 
                 4.28 
                 4.28 
                 Clear liquid 
                 Cloudy Solid 
                 Cloudy liquid- 
                 Cloudy solid 
                 Cloudy solid 
               
               
                   
                   
                   
                   
                   
                 Homogeneous 
               
               
                 188 
                 2.14 
                 6.41 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 Cloudy liquid- 
               
               
                   
                   
                   
                 Homogeneous 
                 Homogeneous 
                 Homogeneous 
                 two phase 
                 two phase 
               
               
                 189 
                 0   
                 8.55 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 Cloudy liquid- 
               
               
                   
                   
                   
                 Homogeneous 
                 Homogeneous 
                 Homogeneous 
                 Homogeneous 
                 two phase 
               
               
                   
               
               
                   
                   
                 Butyl 
               
               
                   
                   
                 Carbitol 
               
               
                   
                 HAN 
                 Acetate 
               
               
                   
               
               
                 190 
                 6.41 
                 2.14 
                 Clear liquid 
                 Cloudy Solid 
                 Cloudy liquid- 
                 Hazy liquid- 
                 Hazy liquid- 
               
               
                   
                   
                   
                   
                   
                 Homogeneous 
                 slight 
                 slight 
               
               
                   
                   
                   
                   
                   
                   
                 precipitate at 
                 precipitate at 
               
               
                   
                   
                   
                   
                   
                   
                 bottom 
                 bottom 
               
               
                 191 
                 4.28 
                 4.28 
                 Clear liquid 
                 Cloudy Solid 
                 Cloudy liquid- 
                 Cloudy solid 
                 Cloudy solid 
               
               
                   
                   
                   
                   
                   
                 Homogeneous 
               
               
                 192 
                 2.14 
                 6.41 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 Cloudy liquid- 
               
               
                   
                   
                   
                 Homogeneous 
                 Homogeneous 
                 Homogeneous 
                 two phase 
                 two phase 
               
               
                 193 
                 0   
                 8.55 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 Cloudy liquid- 
               
               
                   
                   
                   
                 Homogeneous 
                 Homogeneous 
                 Homogeneous 
                 Homogeneous 
                 Homogeneous 
               
               
                   
               
               
                   
                   
                 Butyl 
               
               
                   
                   
                 Cellosolve 
               
               
                   
                 HAN 
                 Acetate 
               
               
                   
               
               
                 194 
                 6.41 
                 2.14 
                 Clear liquid 
                 Cloudy Solid 
                 Cloudy liquid- 
                 Hazy liquid- 
                 Cloudy liquid- 
               
               
                   
                   
                   
                   
                   
                 Homogeneous 
                 slight 
                 two phase 
               
               
                   
                   
                   
                   
                   
                   
                 precipitate at 
               
               
                   
                   
                   
                   
                   
                   
                 bottom 
               
               
                 195 
                 4.28 
                 4.28 
                 Clear liquid 
                 Cloudy Solid 
                 Cloudy liquid- 
                 Cloudy Solid 
                 Cloudy Solid 
               
               
                   
                   
                   
                   
                   
                 Homogeneous 
               
               
                 196 
                 2.14 
                 6.41 
                 Hazy liquid 
                 Cloudy Solid 
                 Cloudy liquid- 
                 Cloudy Solid 
                 Cloudy Solid 
               
               
                   
                   
                   
                   
                   
                 Homogeneous 
               
               
                 197 
                 0   
                 8.55 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 Cloudy liquid- 
               
               
                   
                   
                   
                 Homogeneous 
                 Homogeneous 
                 Homogeneous 
                 Homogeneous 
                 two phase 
               
               
                   
               
               
                   
                   
                 Diisononyl 
               
               
                   
                 HAN 
                 Adipate 
               
               
                   
               
               
                 198 
                 6.41 
                 2.14 
                 Clear liquid 
                 Cloudy Solid 
                 Cloudy liquid- 
                 Hazy liquid- 
                 Hazy liquid- 
               
               
                   
                   
                   
                   
                   
                 Homogeneous 
                 slight 
                 slight 
               
               
                   
                   
                   
                   
                   
                   
                 precipitate at 
                 precipitate at 
               
               
                   
                   
                   
                   
                   
                   
                 bottom 
                 bottom 
               
               
                 199 
                 4.28 
                 4.28 
                 Clear liquid 
                 Cloudy Solid 
                 Cloudy liquid- 
                 Cloudy Solid 
                 Cloudy Solid 
               
               
                   
                   
                   
                   
                   
                 Homogeneous 
               
               
                 200 
                 2.14 
                 6.41 
                 Clear liquid 
                 Cloudy Solid 
                 Cloudy liquid- 
                 Cloudy Solid 
                 Cloudy Solid 
               
               
                   
                   
                   
                   
                   
                 Homogeneous 
               
               
                 201 
                 0   
                 8.55 
                 Cloudy solid 
                 Cloudy Solid 
                 Cloudy liquid- 
                 Cloudy Solid 
                 Cloudy Solid 
               
               
                   
                   
                   
                   
                   
                 Homogeneous 
               
               
                   
               
               
                   
                   
                 Tributyl 2- 
               
               
                   
                 HAN 
                 acetylcitrate 
               
               
                   
               
               
                 202 
                 6.41 
                 2.14 
                 Clear liquid 
                 Cloudy Solid 
                 Hazy Liquid 
                 Hazy liquid- 
                 Hazy liquid- 
               
               
                   
                   
                   
                   
                   
                   
                 slight 
                 precipitate at 
               
               
                   
                   
                   
                   
                   
                   
                 precipitate at 
                 bottom 
               
               
                   
                   
                   
                   
                   
                   
                 bottom 
               
               
                 203 
                 4.28 
                 4.28 
                 Clear liquid 
                 Cloudy Solid 
                 Opaque Gel 
                 Opaque Gel 
                 Opaque Gel 
               
               
                 204 
                 2.14 
                 6.41 
                 Hazy liquid 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 Cloudy 
                 Cloudy 
               
               
                   
                   
                   
                   
                 Homogeneous 
                 Homogeneous 
                 Liquid-two 
                 Liquid-two 
               
               
                   
                   
                   
                   
                   
                   
                 phase 
                 phase 
               
               
                 205 
                 0   
                 8.55 
                 Cloudy solid 
                 Cloudy Solid 
                 Cloudy liquid- 
                 Cloudy 
                 Cloudy 
               
               
                   
                   
                   
                   
                   
                 solid top layer 
                 Liquid-two 
                 Liquid-solid 
               
               
                   
                   
                   
                   
                   
                   
                 phase 
                 top layer 
               
               
                   
               
               
                   
                   
                 Ethyl L- 
               
               
                   
                 HAN 
                 lactate 
               
               
                   
               
               
                 206 
                 6.41 
                 2.14 
                 Clear liquid 
                 Cloudy Solid 
                 Hazy Liquid 
                 Hazy Liquid 
                 Hazy Liquid 
               
               
                 207 
                 4.28 
                 4.28 
                 Hazy liquid 
                 Cloudy Solid 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 Cloudy liquid- 
               
               
                   
                   
                   
                   
                   
                 Homogeneous 
                 two phase 
                 two phase 
               
               
                 208 
                 2.14 
                 6.41 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 Cloudy liquid- 
               
               
                   
                   
                   
                 Homogeneous 
                 solid top layer 
                 solid top 
                 solid top 
                 solid top 
               
               
                   
                   
                   
                   
                   
                 layer-clear 
                 layer-clear 
                 layer-clear 
               
               
                   
                   
                   
                   
                   
                 bottom layer 
                 bottom layer 
                 bottom layer 
               
               
                 209 
                 0   
                 8.55 
                 Cloudy liquid- 
                 Cloudy Solid 
                 Cloudy liquid 
                 Cloudy liquid- 
                 Cloudy liquid- 
               
               
                   
                   
                   
                 solid top layer 
                   
                 top-clear 
                 solid top 
                 solid top 
               
               
                   
                   
                   
                   
                   
                 liquid bottom 
                 layer-clear 
                 layer-clear 
               
               
                   
                   
                   
                   
                   
                   
                 bottom layer 
                 bottom layer 
               
               
                   
               
               
                   
                   
                 Glycol 
               
               
                   
                   
                 Ether 
               
               
                   
                 HAN 
                 Acetate 
               
               
                   
               
               
                 210 
                 6.41 
                 2.14 
                 Clear liquid 
                 Cloudy Solid 
                 Hazy Liquid 
                 Hazy liquid- 
                 Hazy liquid- 
               
               
                   
                   
                   
                   
                   
                   
                 slight 
                 precipitate at 
               
               
                   
                   
                   
                   
                   
                   
                 precipitate at 
                 bottom 
               
               
                   
                   
                   
                   
                   
                   
                 bottom 
               
               
                 211 
                 4.28 
                 4.28 
                 Clear liquid 
                 Cloudy Solid 
                 Cloudy Solid 
                 Cloudy Solid 
                 Cloudy Solid 
               
               
                 212 
                 2.14 
                 6.41 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 Cloudy liquid 
               
               
                   
                   
                   
                 Homogeneous 
                 Homogeneous 
                 Homogeneous 
                 Homogeneous 
                 bottom layer, 
               
               
                   
                   
                   
                   
                   
                   
                   
                 clear liquid 
               
               
                   
                   
                   
                   
                   
                   
                   
                 top layer 
               
               
                 213 
                 0   
                 8.55 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 Cloudy liquid- 
               
               
                   
                   
                   
                 Homogeneous 
                 Homogeneous 
                 Homogeneous 
                 Homogeneous 
                 Homogeneous 
               
               
                   
               
               
                   
                   
                 Butyl 
               
               
                   
                 HAN 
                 Lactate 
               
               
                   
               
               
                 214 
                 6.41 
                 2.14 
                 Clear liquid 
                 Cloudy Solid 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 Hazy Liquid 
               
               
                   
                   
                   
                   
                   
                 Homogeneous 
                 Homogeneous 
               
               
                 215 
                 4.28 
                 4.28 
                 Clear liquid 
                 Cloudy Solid 
                 Cloudy Gel 
                 Cloudy Gel 
                 Cloudy Gel 
               
               
                 216 
                 2.14 
                 6.41 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 Cloudy liquid 
               
               
                   
                   
                   
                 Homogeneous 
                 Homogeneous 
                 Homogeneous 
                 Homogeneous 
                 bottom layer, 
               
               
                   
                   
                   
                   
                   
                   
                   
                 clear liquid 
               
               
                   
                   
                   
                   
                   
                   
                   
                 top layer 
               
               
                 217 
                 0   
                 8.55 
                 Cloudy slush- 
                 Cloudy slush- 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 Cloudy liquid- 
               
               
                   
                   
                   
                 Homogeneous 
                 Homogeneous 
                 Homogeneous 
                 Homogeneous 
                 Homogeneous 
               
               
                   
               
               
                   
                 HAN 
                 Toluene 
               
               
                   
               
               
                 218 
                 8.55 
                 0   
                 Clear liquid 
                 Hazy Solid 
                 Clear liquid- 
                 Clear liquid- 
                 n/a 
               
               
                   
                   
                   
                   
                   
                 slight 
                 slight 
               
               
                   
                   
                   
                   
                   
                 precipitate at 
                 precipitate at 
               
               
                   
                   
                   
                   
                   
                 bottom 
                 bottom 
               
               
                 219 
                 6.41 
                 2.14 
                 Clear liquid 
                 Hazy Solid 
                 Clear liquid- 
                 Clear liquid- 
                 n/a 
               
               
                   
                   
                   
                   
                   
                 slight 
                 slight 
               
               
                   
                   
                   
                   
                   
                 precipitate at 
                 precipitate at 
               
               
                   
                   
                   
                   
                   
                 bottom 
                 bottom 
               
               
                 220 
                 4.28 
                 4.28 
                 Clear liquid 
                 Hazy Solid 
                 Clear liquid- 
                 Clear liquid- 
                 n/a 
               
               
                   
                   
                   
                   
                   
                 slight 
                 slight 
               
               
                   
                   
                   
                   
                   
                 precipitate at 
                 precipitate at 
               
               
                   
                   
                   
                   
                   
                 bottom 
                 bottom 
               
               
                 221 
                 2.14 
                 6.41 
                 Clear liquid 
                 Hazy Solid 
                 Clear liquid- 
                 Clear liquid- 
                 n/a 
               
               
                   
                   
                   
                   
                   
                 slight 
                 slight 
               
               
                   
                   
                   
                   
                   
                 precipitate at 
                 precipitate at 
               
               
                   
                   
                   
                   
                   
                 bottom 
                 bottom 
               
               
                 222 
                 0   
                 8.55 
                 Clear liquid 
                 Hazy Solid 
                 Clear liquid- 
                 Clear liquid- 
                 n/a 
               
               
                   
                   
                   
                   
                   
                 slight 
                 slight 
               
               
                   
                   
                   
                   
                   
                 precipitate at 
                 precipitate at 
               
               
                   
                   
                   
                   
                   
                 bottom 
                 bottom 
               
               
                   
               
               
                   
                   
                 Propylene 
               
               
                   
                   
                 glycol 
               
               
                   
                   
                 methyl 
               
               
                   
                   
                 ether 
               
               
                   
                 HAN 
                 acetate 
               
               
                   
               
               
                 223 
                 6.41 
                 2.14 
                 Clear liquid 
                 Hazy Solid 
                 Hazy gel 
                 Hazy gel 
                 n/a 
               
               
                 224 
                 4.28 
                 4.28 
                 Clear liquid 
                 Cloudy Solid 
                 Cloudy solid 
                 Cloudy solid 
                 n/a 
               
               
                 225 
                 2.14 
                 6.41 
                 Cloudy liquid- 
                 Cloudy Solid 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 n/a 
               
               
                   
                   
                   
                 Homogeneous 
                   
                 Homogeneous 
                 Homogeneous 
               
               
                 226 
                 0   
                 8.55 
                 Cloudy liquid- 
                 Cloudy thick 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 n/a 
               
               
                   
                   
                   
                 Homogeneous 
                 liquid- 
                 Homogeneous 
                 Homogeneous 
               
               
                   
                   
                   
                   
                 Homogenous 
               
               
                   
               
               
                   
                   
                 Butyl 
               
               
                   
                 HAN 
                 Lactate 
               
               
                   
               
               
                 227 
                 6.41 
                 2.14 
                 Clear liquid 
                 Hazy Solid 
                 Hazy liquid 
                 Hazy liquid 
                 n/a 
               
               
                 228 
                 4.28 
                 4.28 
                 Clear liquid 
                 Cloudy Solid 
                 Hazy solid 
                 Hazy solid 
                 n/a 
               
               
                 229 
                 2.14 
                 6.41 
                 Cloudy liquid- 
                 Cloudy Solid 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 n/a 
               
               
                   
                   
                   
                 Homogeneous 
                   
                 Homogeneous 
                 Homogeneous 
               
               
                 230 
                 0   
                 8.55 
                 Cloudy liquid- 
                 Cloudy Solid 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 n/a 
               
               
                   
                   
                   
                 Homogeneous 
                   
                 Homogeneous 
                 Homogeneous 
               
               
                   
               
               
                   
                   
                 Butyl 
               
               
                   
                 HAN 
                 Carbitol 
               
               
                   
               
               
                 231 
                 6.41 
                 2.14 
                 Clear liquid 
                 Hazy Solid 
                 Clear liquid 
                 Clear liquid 
                 n/a 
               
               
                 232 
                 4.28 
                 4.28 
                 Clear liquid 
                 Cloudy Solid 
                 Cloudy Solid 
                 Cloudy Solid 
                 n/a 
               
               
                 233 
                 2.14 
                 6.41 
                 Cloudy Liquid- 
                 Cloudy Solid 
                 Cloudy Gel 
                 Clear liquid- 
                 n/a 
               
               
                   
                   
                   
                 Homogeneous 
                   
                   
                 top, cloudy 
               
               
                   
                   
                   
                   
                   
                   
                 liquid-bottom 
               
               
                 234 
                 0   
                 8.55 
                 Cloudy Liquid- 
                 Cloudy Liquid- 
                 Cloudy liquid- 
                 Clear liquid- 
                 n/a 
               
               
                   
                   
                   
                 Homogeneous 
                 Homogeneous 
                 Homogeneous 
                 top, cloudy 
               
               
                   
                   
                   
                   
                   
                   
                 liquid-bottom 
               
               
                   
               
               
                   
                   
                 Propylene 
               
               
                   
                   
                 Glycol 
               
               
                   
                 HAN 
                 Diacetate 
               
               
                   
               
               
                 235 
                 6.41 
                 2.14 
                 Clear liquid 
                 Cloudy Solid 
                 Hazy Gel 
                 Hazy Gel 
                 n/a 
               
               
                 236 
                 4.28 
                 4.28 
                 Cloudy liquid- 
                 Cloudy thick 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 n/a 
               
               
                   
                   
                   
                 Homogeneous 
                 liquid 
                 Homogeneous 
                 Homogeneous 
               
               
                 237 
                 2.14 
                 6.41 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 n/a 
               
               
                   
                   
                   
                 Homogeneous 
                 solid top layer 
                 solid top layer 
                 solid top layer 
               
               
                 238 
                 0   
                 8.55 
                 Cloudy liquid- 
                 Cloudy Solid 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 n/a 
               
               
                   
                   
                   
                 Homogeneous 
                   
                 solid top layer 
                 solid top layer 
               
               
                   
               
               
                   
                   
                 Dipropylene 
               
               
                   
                   
                 Glycol 
               
               
                   
                   
                 Methyl 
               
               
                   
                   
                 Ether 
               
               
                   
                 HAN 
                 Acetate 
               
               
                   
               
               
                 239 
                 6.41 
                 2.14 
                 Clear liquid 
                 Hazy Solid 
                 Clear liquid 
                 Hazy Gel 
                 n/a 
               
               
                 240 
                 4.28 
                 4.28 
                 Clear liquid 
                 Cloudy Solid 
                 Cloudy solid 
                 Cloudy solid 
                 n/a 
               
               
                 241 
                 2.14 
                 6.41 
                 Cloudy liquid- 
                 Cloudy Solid 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 n/a 
               
               
                   
                   
                   
                 Homogeneous 
                   
                 Homogeneous 
                 Homogeneous 
               
               
                 242 
                 0   
                 8.55 
                 Cloudy liquid- 
                 Cloudy think 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 n/a 
               
               
                   
                   
                   
                 Homogeneous 
                 liquid- 
                 Homogeneous 
                 Homogeneous 
               
               
                   
                   
                   
                   
                 Homogeneous 
               
               
                   
               
               
                   
                   
                 PMA 
               
               
                   
                   
                 Glycol 
               
               
                   
                   
                 Ether 
               
               
                   
                 Toluene 
                 Acetate 
               
               
                   
               
               
                 243 
                 6.41 
                 2.14 
                 Clear liquid 
                 Cloudy Solid 
                 Hazy liquid 
                 Hazy liquid- 
                 n/a 
               
               
                   
                   
                   
                   
                   
                   
                 slight 
               
               
                   
                   
                   
                   
                   
                   
                 precipitate at 
               
               
                   
                   
                   
                   
                   
                   
                 bottom 
               
               
                 244 
                 4.28 
                 4.28 
                 Hazy liquid 
                 Cloudy Solid 
                 Cloudy gel 
                 Cloudy gel 
                 n/a 
               
               
                 245 
                 2.14 
                 6.41 
                 Cloudy liquid- 
                 Cloudy Solid 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 n/a 
               
               
                   
                   
                   
                 Homogeneous 
                   
                 Homogeneous 
                 Homogeneous 
               
               
                 246 
                 0   
                 8.55 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 n/a 
               
               
                   
                   
                   
                 Homogeneous 
                 Homogeneous 
                 Homogeneous 
                 Homogeneous 
               
               
                   
               
               
                   
                   
                 Butyl 
               
               
                   
                 Toluene 
                 Lactate 
               
               
                   
               
               
                 247 
                 6.41 
                 2.14 
                 Clear liquid 
                 Cloudy Solid 
                 Hazy liquid- 
                 Hazy liquid- 
                 n/a 
               
               
                   
                   
                   
                   
                   
                 slight 
                 slight 
               
               
                   
                   
                   
                   
                   
                 precipitate at 
                 precipitate at 
               
               
                   
                   
                   
                   
                   
                 bottom 
                 bottom 
               
               
                 248 
                 4.28 
                 4.28 
                 Hazy liquid 
                 Cloudy Solid 
                 Cloudy gel 
                 Cloudy gel 
                 n/a 
               
               
                 249 
                 2.14 
                 6.41 
                 Cloudy liquid- 
                 Cloudy Slush 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 n/a 
               
               
                   
                   
                   
                 Homogeneous 
                   
                 Homogeneous 
                 Homogeneous 
               
               
                 250 
                 0   
                 8.55 
                 Cloudy liquid- 
                 Cloudy Slush 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 n/a 
               
               
                   
                   
                   
                 Homogeneous 
                   
                 Homogeneous 
                 Homogeneous 
               
               
                   
               
               
                   
                   
                 Butyl 
               
               
                   
                 Toluene 
                 Carbitol 
               
               
                   
               
               
                 251 
                 6.41 
                 2.14 
                 Clear liquid 
                 Cloudy Solid 
                 Hazy liquid 
                 Hazy liquid 
                 n/a 
               
               
                 252 
                 4.28 
                 4.28 
                 Hazy liquid 
                 Cloudy Solid 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 n/a 
               
               
                   
                   
                   
                   
                   
                 Homogeneous 
                 Homogeneous 
               
               
                 253 
                 2.14 
                 6.41 
                 Cloudy liquid- 
                 Cloudy slush 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 n/a 
               
               
                   
                   
                   
                 Homogeneous 
                   
                 Homogeneous 
                 slight 
               
               
                   
                   
                   
                   
                   
                   
                 separation 
               
               
                 254 
                 0   
                 8.55 
                 Cloudy liquid- 
                 Cloudy slush 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 n/a 
               
               
                   
                   
                   
                 Homogeneous 
                   
                 Homogeneous 
                 Homogeneous 
               
               
                   
               
               
                   
                   
                 Propylene 
               
               
                   
                   
                 Glycol 
               
               
                   
                 Toluene 
                 Diacetate 
               
               
                   
               
               
                 255 
                 6.41 
                 2.14 
                 Clear liquid 
                 Cloudy solid 
                 Hazy Gel 
                 Hazy Gel 
                 n/a 
               
               
                 256 
                 4.28 
                 4.28 
                 Hazy liquid- 
                 Cloudy solid 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 n/a 
               
               
                   
                   
                   
                 solid top layer 
                   
                 solid top layer 
                 solid top layer 
               
               
                 257 
                 2.14 
                 6.41 
                 Cloudy liquid- 
                 Cloudy solid 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 n/a 
               
               
                   
                   
                   
                 solid top layer 
                   
                 solid top layer 
                 solid top layer 
               
               
                 258 
                 0   
                 8.55 
                 Cloudy liquid- 
                 Cloudy solid 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 n/a 
               
               
                   
                   
                   
                 solid top layer 
                   
                 solid top layer 
                 solid top layer 
               
               
                   
               
               
                   
                   
                 Dipropylene 
               
               
                   
                   
                 Glycol 
               
               
                   
                   
                 Methyl 
               
               
                   
                   
                 Ether 
               
               
                   
                 Toluene 
                 Acetate 
               
               
                   
               
               
                 259 
                 6.41 
                 2.14 
                 Clear liquid 
                 Cloudy solid 
                 Hazy liquid 
                 Hazy liquid 
                 n/a 
               
               
                 260 
                 4.28 
                 4.28 
                 Hazy liquid 
                 Cloudy solid 
                 Cloudy solid 
                 Cloudy solid 
               
               
                 261 
                 2.14 
                 6.41 
                 Cloudy liquid- 
                 Cloudy slush 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 n/a 
               
               
                   
                   
                   
                 Homogeneous 
                   
                 Homogeneous 
                 Homogeneous 
               
               
                 262 
                 0   
                 8.55 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 Cloudy liquid- 
                 n/a 
               
               
                   
                   
                   
                 Homogeneous 
                 Homogeneous 
                 Homogeneous 
                 Homogeneous 
               
               
                   
               
               
                   
                   
                 PMA 
               
               
                   
                   
                 Glycol 
               
               
                   
                   
                 Ether 
               
               
                   
                 HAN 
                 Acetate 
               
               
                   
               
               
                 263 
                 8.05 
                 0.50 
                 Clear liquid 
                 Clear solid 
                 Hazy Liquid 
                 Hazy Liquid 
                 n/a 
               
               
                 264 
                 7.55 
                 1.00 
                 Clear liquid 
                 Clear solid 
                 Hazy Liquid 
                 Hazy Liquid 
                 n/a 
               
               
                   
               
               
                   
                   
                 Butyl 
               
               
                   
                 HAN 
                 Lactate 
               
               
                   
               
               
                 265 
                 8.05 
                 0.50 
                 Clear liquid 
                 Clear solid 
                 Hazy Liquid 
                 Hazy Liquid 
                 n/a 
               
               
                 266 
                 7.55 
                 1.00 
                 Clear liquid 
                 Clear solid 
                 Hazy Liquid 
                 Hazy Liquid 
                 n/a 
               
               
                   
               
               
                   
                   
                 Butyl 
               
               
                   
                 HAN 
                 Carbitol 
               
               
                   
               
               
                 267 
                 8.05 
                 0.50 
                 Clear liquid 
                 Clear solid 
                 Hazy Liquid 
                 Hazy Liquid 
                 n/a 
               
               
                 268 
                 7.55 
                 1.00 
                 Clear liquid 
                 Clear solid 
                 Hazy Liquid 
                 Hazy Liquid 
                 n/a 
               
               
                   
               
               
                   
                   
                 Propylene 
               
               
                   
                   
                 Glycol 
               
               
                   
                 HAN 
                 Diacetate 
               
               
                   
               
               
                 269 
                 8.05 
                 0.50 
                 Clear liquid 
                 Clear solid 
                 Hazy Liquid 
                 Hazy Liquid 
                 n/a 
               
               
                 270 
                 7.55 
                 1.00 
                 Clear liquid 
                 Clear solid 
                 Hazy Liquid 
                 Hazy Liquid 
                 n/a 
               
               
                   
               
               
                   
                   
                 Dipropylene 
               
               
                   
                   
                 Glycol 
               
               
                   
                   
                 Methyl 
               
               
                   
                   
                 Ether 
               
               
                   
                 HAN 
                 Acetate 
               
               
                   
               
               
                 271 
                 8.05 
                 0.50 
                 Clear liquid 
                 Clear solid 
                 Hazy Liquid 
                 Hazy Liquid 
                 n/a 
               
               
                 272 
                 7.55 
                 1.00 
                 Clear liquid 
                 Clear solid 
                 Hazy Liquid 
                 Hazy Liquid 
                 n/a 
               
               
                   
               
               
                   
                 Toluene 
                 none 
               
               
                   
               
               
                 273 
                 8.55 
                 n/a 
                 Clear liquid 
                 Clear solid 
                 Clear liquid 
                 Clear liquid 
                 n/a 
               
               
                   
               
               
                   
                 HAN 
                 none 
               
               
                   
               
               
                 274 
                 8.55 
                 n/a 
                 Clear liquid 
                 Clear solid 
                 Hazy Liquid 
                 Hazy Liquid 
                 n/a 
               
               
                   
               
               
                   
                 HAN 
                 none 
               
               
                   
               
               
                 275 
                 8.55 
                 n/a 
                 Clear liquid 
                 Clear solid 
                 Clear liquid 
                 Clear liquid 
                 n/a 
               
               
                   
               
            
           
         
       
     
     Examples 276-279 
     Using the General Procedure, 1.4 g of Polymer 3 was blended with the components and in the amounts shown in Table 9. Examples 276 and 277 were solid at −40° C., while Examples 278 and 279 were pourable liquids at −40° C. 
     
       
         
           
               
             
               
                 TABLE 9 
               
             
            
               
                   
               
               
                 Compositions of Examples 276-279. 
               
            
           
           
               
               
               
               
               
            
               
                   
                   
                   
                   
                 Propylene 
               
               
                   
                   
                   
                 Ethylene 
                 glycol 
               
               
                   
                   
                 Solvent 
                 glycol butyl 
                 methyl ether 
               
               
                   
                 Ex. 
                 195 
                 ether acetate 
                 acetate 
               
               
                   
               
               
                   
                 276 
                 3.6 
                 5.0 
                   
               
               
                   
                 277 
                   
                 8.6 
                   
               
               
                   
                 278 
                 3.6 
                   
                 5.0 
               
               
                   
                 279 
                   
                   
                 8.6 
               
               
                   
               
            
           
         
       
     
     Examples 280-301 
     Using the General Procedure, the indicated polymers were mixed with Solvent 195 (SOLVESSO® 195, obtained from ExxonMobil Chemical Co. of Irving, Tex.) using varying amounts of ethylene glycol butyl ether acetate, and the mixtures tested according to the General Procedure except that all the compositions were solids at −40° C. and the amount of time between taking the bottle out of the freezer and subjecting it to ambient laboratory temperature and the time that the composition begins to flow is noted in seconds. DBS is a dodecylbenzenesulfonic acid salt. The mixtures of Examples 280-301 were observed solely after mixing followed by 18 hours storage at −40° C. Compositions and results are shown in Table 10. 
     
       
         
           
               
             
               
                 TABLE 10 
               
             
            
               
                   
               
               
                 Compositions and time to flow for the compositions of Examples 280-301. 
               
            
           
           
               
               
               
            
               
                   
                 Component, g 
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                   
                   
                   
                   
                   
                   
                   
                 Ethylene 
                   
                 Observation 
               
               
                   
                   
                   
                   
                   
                   
                   
                 glycol 
                   
                 Time to 
               
               
                   
                   
                   
                   
                   
                   
                   
                 butyl ether 
                   
                 flow, s 
               
               
                 Ex. 
                 Polymer 3 
                 Polymer 1 
                 Polymer 2 
                 Polymer 6 
                 Polymer 5 
                 Solvent 195 
                 acetate 
                 DBS 
                 after −40° C. 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                 280 
                 1.45 
                   
                   
                   
                 0.05 
                 7.70 
                 0.50 
                 0.30 
                 103 
               
               
                 281 
                 1.45 
                   
                   
                   
                 0.05 
                 6.70 
                 1.50 
                 0.30 
                 106 
               
               
                 282 
                 1.45 
                   
                 0.05 
                   
                   
                 6.70 
                 1.50 
                 0.30 
                 109 
               
               
                 283 
                 1.45 
                   
                   
                   
                 0.05 
                 6.70 
                 1.50 
                 0.30 
                 109 
               
               
                 284 
                 1.45 
                   
                 0.05 
                   
                   
                 6.70 
                 1.50 
                 0.30 
                 114 
               
               
                 285 
                 1.45 
                   
                 0.05 
                   
                   
                 7.70 
                 0.50 
                 0.30 
                 117 
               
               
                 286 
                 1.45 
                   
                   
                 0.05 
                   
                 7.70 
                 0.50 
                 0.30 
                 127 
               
               
                 287 
                 1.45 
                   
                   
                 0.05 
                   
                 6.70 
                 1.50 
                 0.30 
                 134 
               
               
                 288 
                 1.45 
                   
                 0.05 
                   
                   
                 5.20 
                 3.00 
                 0.30 
                 151 
               
               
                 289 
                 1.45 
                   
                   
                   
                 0.05 
                 5.20 
                 3.00 
                 0.30 
                 159 
               
               
                 290 
                 1.45 
                   
                   
                 0.05 
                   
                 5.20 
                 3.00 
                 0.30 
                 177 
               
               
                 291 
                   
                 1.45 
                   
                   
                 0.05 
                 7.70 
                 0.50 
                 0.30 
                 194 
               
               
                 292 
                   
                 1.45 
                 0.05 
                   
                   
                 7.70 
                 0.50 
                 0.30 
                 227 
               
               
                 293 
                   
                 1.45 
                   
                   
                 0.05 
                 6.70 
                 1.50 
                 0.30 
                 232 
               
               
                 294 
                   
                 1.45 
                 0.05 
                   
                   
                 6.70 
                 1.50 
                 0.30 
                 266 
               
               
                 295 
                   
                 1.45 
                   
                 0.05 
                   
                 7.70 
                 0.50 
                 0.30 
                 272 
               
               
                 296 
                   
                 1.45 
                   
                   
                 0.05 
                 5.20 
                 3.00 
                 0.30 
                 324 
               
               
                 297 
                   
                 1.45 
                 0.05 
                   
                   
                 5.20 
                 3.00 
                 0.30 
                 328 
               
               
                 298 
                   
                 1.45 
                   
                   
                 0.05 
                 5.20 
                 3.00 
                 0.30 
                 329 
               
               
                 299 
                   
                 1.45 
                   
                 0.05 
                   
                 6.70 
                 1.50 
                 0.30 
                 344 
               
               
                 300 
                   
                 1.45 
                   
                 0.05 
                   
                 6.70 
                 1.50 
                 0.30 
                 369 
               
               
                 301 
                   
                 1.45 
                   
                 0.05 
                   
                 5.20 
                 3.00 
                 0.30 
                 417 
               
               
                   
               
            
           
         
       
     
     Examples 302-321 
     The components shown in Table 11 were mixed according to the General Procedure. Note that all components are described fully above. All of the mixtures were observed to be clear or hazy liquids upon initial observation. Then the example mixtures were subjected to stability cycling according to the following protocol in the indicated order: 1 st  cold cycle; 1 st  heat cycle; 2 nd  cold cycle, 2 nd  heat cycle, 3 rd  cold cycle; 3 rd  heat cycle; 4 th  cold cycle, wherein the protocol for each of the cooling and heating cycles were carried out according to the General Procedure. The results of the observations during the stability cycling is shown in Table 12. 
     
       
         
           
               
             
               
                 TABLE 11 
               
             
            
               
                   
               
               
                 Components of Examples 302-321. 
               
            
           
           
               
               
            
               
                   
                 Component, g 
               
               
                   
               
            
           
           
               
               
               
               
               
               
            
               
                   
                   
                 Acetyl Triethyl 
                   
                 Tergitol 
                   
               
               
                 Ex. 
                 HAN 
                 Citrate 
                 Toluene 
                 15-S-3 
                 Polymer 2 
               
               
                   
               
               
                 302 
                 53.80 
                 33.80 
                 0.00 
                 0 
                 12.4 
               
               
                 303 
                 33.48 
                 31.98 
                 22.15 
                 0 
                 12.4 
               
               
                   
               
               
                   
                   
                 Triacetin 
               
               
                   
               
               
                 304 
                 37.23 
                 25.23 
                 22.15 
                 0 
                 12.4 
               
               
                 305 
                 33.48 
                 31.98 
                 22.15 
                 0 
                 12.4 
               
               
                   
               
               
                   
                   
                 Propylene 
                   
                   
                   
               
               
                   
                   
                 Glycol Diacetate 
               
               
                   
               
               
                 306 
                 43.30 
                 41.30 
                 0.00 
                 3 
                 12.4 
               
               
                 307 
                 44.80 
                 42.80 
                 0.00 
                 0 
                 12.4 
               
               
                 308 
                 33.48 
                 31.98 
                 22.15 
                 0 
                 12.4 
               
               
                   
               
               
                   
                   
                 Acetyl Triethyl 
                   
                   
                   
               
               
                   
                   
                 Citrate 
               
               
                   
               
               
                 309 
                 52.30 
                 32.30 
                 0.00 
                 3 
                 12.4 
               
               
                 310 
                 32.48 
                 30.98 
                 21.15 
                 3 
                 12.4 
               
               
                   
               
               
                   
                   
                 Triacetin 
               
               
                   
               
               
                 311 
                 39.23 
                 24.23 
                 21.15 
                 3 
                 12.4 
               
               
                   
               
               
                   
                   
                 Acetyl Triethyl 
                 Solvent 
                   
                   
               
               
                   
                   
                 Citrate 
                 150 
               
               
                   
               
               
                 312 
                 52.30 
                 32.30 
                 0.00 
                 3 
                 12.4 
               
               
                   
               
               
                   
                   
                 Triacetin 
               
               
                   
               
               
                 313 
                 39.23 
                 24.23 
                 21.15 
                 3 
                 12.4 
               
               
                   
               
               
                   
                   
                   
                 Toluene 
                   
                   
               
               
                   
               
               
                 314 
                   
                 24.23 
                 60.38 
                 3 
                 12.4 
               
               
                   
               
               
                   
                   
                 Propylene 
                   
                   
                   
               
               
                   
                   
                 Glycol Diacetate 
               
               
                   
               
               
                 315 
                   
                 30.98 
                 53.63 
                 3 
                 12.4 
               
               
                   
               
               
                   
                 Solvent 
                 Acetyl Triethyl 
                   
                   
                   
               
               
                   
                 150 
                 Citrate 
               
               
                   
               
               
                 316 
                 52.30 
                 32.30 
                 0.00 
                 3 
                 12.4 
               
               
                 317 
                 32.48 
                 30.98 
                 21.15 
                 3 
                 12.4 
               
               
                   
               
               
                   
                   
                 Triacetin 
               
               
                   
               
               
                 318 
                 39.23 
                 24.23 
                 21.15 
                 3 
                 12.4 
               
               
                   
               
               
                   
                 Solvent 
                 Acetyl Triethyl 
                   
                   
                   
               
               
                   
                 195 
                 Citrate 
               
               
                   
               
               
                 319 
                 52.30 
                 32.30 
                 0.00 
                 3 
                 12.4 
               
               
                   
               
               
                   
                   
                 Triacetin 
               
               
                   
               
               
                 320 
                 39.23 
                 24.23 
                 21.15 
                 3 
                 12.4 
               
               
                   
               
               
                   
                 Solvent 
                   
                   
                   
                   
               
               
                   
                 150 
               
               
                   
               
               
                 321 
                 40.23 
                 25.23 
                 22.15 
                 0 
                 12.4 
               
               
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 12 
               
             
            
               
                   
               
               
                 Observations regarding stability cycling of Examples 302-321. 
               
            
           
           
               
               
               
               
               
               
               
               
            
               
                   
                 1st Cold 
                 1st Heat 
                 2nd Cold 
                 2nd Heat 
                 3rd Cold 
                 3rd Heat 
                 4th Cold 
               
               
                   
                 Cycle 
                 Cycle 
                 Cycle 
                 Cycle 
                 Cycle 
                 Cycle 
                 Cycle 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
               
               
               
               
            
               
                   
                 −40° 
                   
                 +60° 
                   
                 −40° 
                   
                 +60° 
                   
                 −40° 
                   
                 +60° 
                   
                 −40° 
                   
               
               
                 Ex. 
                 C. 
                 RT 
                 C. 
                 RT 
                 C. 
                 RT 
                 C. 
                 RT 
                 C. 
                 RT 
                 C. 
                 RT 
                 C. 
                 RT 
               
               
                   
               
               
                 302 
                 Clear 
                 Cloudy 
                 Clear 
                 Slightly 
                 Cloudy 
                 Cloudy 
                 Clear 
                 Slightly 
                 Cloudy 
                 Cloudy 
                 Clear 
                 Barely 
                 Opaque 
                 Cloudy 
               
               
                   
                 liquid 
                 liquid 
                 liquid 
                 hazy 
                 liquid 
                 liquid 
                 liquid 
                 hazy 
                 liquid 
                 liquid 
                 liquid 
                 hazy 
                 slush 
                 liquid 
               
               
                   
                   
                   
                   
                 liquid 
                   
                   
                   
                 liquid 
                   
                   
                   
                 liquid 
               
               
                 303 
                 Clear 
                 Cloudy 
                 Clear 
                 Slightly 
                 Clear 
                 Cloudy 
                 Clear 
                 Slightly 
                 Clear 
                 Cloudy 
                 Clear 
                 Barely 
                 Cloudy 
                 Cloudy 
               
               
                   
                 liquid 
                 liquid 
                 liquid 
                 hazy 
                 solid 
                 liquid 
                 liquid 
                 hazy 
                 slow 
                 liquid 
                 liquid 
                 hazy 
                 flowing 
                 liquid 
               
               
                   
                   
                   
                   
                 liquid 
                   
                   
                   
                 liquid 
                 flowing 
                   
                   
                 liquid 
                 gel 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 liquid 
               
               
                 304 
                 Clear 
                 Hazy 
                 Clear 
                 Clear 
                 Clear 
                 Barely 
                 Clear 
                 Clear 
                 Clear 
                 Hazy 
                 Clear 
                 Barely 
                 Clear 
                 Hazy 
               
               
                   
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                 hazy 
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                 hazy 
                 liquid 
                 fluff 
               
               
                   
                   
                   
                   
                   
                   
                 liquid 
                   
                   
                   
                   
                   
                 liquid 
                   
                 over 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 clear 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 liquid 
               
               
                 305 
                 Clear 
                 Chunky 
                 Clear 
                 Separated 
                 Separated 
                 Clear 
                 Clear 
                 Separated 
                 Separated 
                 Chunky 
                 Clear 
                 Clear 
                 Separated 
                 Separated 
               
               
                   
                 solid 
                 cloudy 
                 liquid 
                 hazy 
                 clear 
                 gel; 
                 liquid 
                 hazy 
                 clear 
                 hazy 
                 liquid 
                 liquid 
                 cloudy 
                 hazy 
               
               
                   
                 over 
                 liquid 
                   
                 liquid 
                 solid 
                 cloudy 
                   
                 liquid 
                 solid 
                 liquid 
                   
                 over 
                 solid 
                 liquid 
               
               
                   
                 clear 
                   
                   
                   
                   
                 fluff; 
                   
                   
                   
                   
                   
                 hazy 
               
               
                   
                 liquid 
                   
                   
                   
                   
                 hazy 
                   
                   
                   
                   
                   
                 liquid 
               
               
                   
                   
                   
                   
                   
                   
                 liquid 
               
               
                 306 
                 Opaque 
                 Opaque 
                 Clear 
                 Hazy 
                 Slush 
                 Opaque 
                 Clear 
                 Hazy 
                 Opaque 
                 Opaque 
                 Clear 
                 Cloudy 
                 Opaque 
                 Settled 
               
               
                   
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                   
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                 solid 
                 cloudy 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 liquid 
               
               
                 307 
                 Opaque 
                 Opaque 
                 Clear 
                 Hazy 
                 Clear 
                 Chunky 
                 Clear 
                 Separated 
                 Separated 
                 Opaque 
                 Clear 
                 Chunky 
                 Opaque 
                 Settled 
               
               
                   
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                 solid 
                 opaque 
                 liquid 
                 hazy 
                 opaque 
                 solid 
                 liquid 
                 cloudy 
                 solid 
                 cloudy 
               
               
                   
                   
                   
                   
                   
                   
                 liquid 
                   
                 liquid 
                 solid 
                 over 
                   
                 liquid 
                   
                 liquid 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 opaque 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 liquid 
               
               
                 308 
                 Clear 
                 Hazy 
                 Clear 
                 Clear 
                 Clear 
                 Hazy 
                 Clear 
                 Clear 
                 Clear 
                 Cloudy 
                 Clear 
                 Clear 
                 Cloudy 
                 Cloudy 
               
               
                   
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                 solid 
                 liquid 
                 liquid 
                 liquid 
                 slow 
                 liquid 
                 liquid 
                 liquid 
                 flowing 
                 liquid 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 flowing 
                   
                   
                   
                 gel 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 liquid 
               
               
                 309 
                 Clear 
                 Hazy 
                 Clear 
                 Clear 
                 Slush 
                 Cloudy 
                 Clear 
                 Clear 
                 Clear 
                 Cloudy 
                 Clear 
                 Clear 
                 Cloudy 
                 Cloudy 
               
               
                   
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                   
                 liquid 
                 liquid 
                 liquid 
                 slow 
                 liquid 
                 liquid 
                 liquid 
                 flowing 
                 liquid 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 flowing 
                   
                   
                   
                 gel 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 liquid 
               
               
                 310 
                 Clear 
                 Hazy 
                 Clear 
                 Clear 
                 Slush 
                 Cloudy 
                 Clear 
                 Clear 
                 Clear 
                 Cloudy 
                 Clear 
                 Clear 
                 Cloudy 
                 Cloudy 
               
               
                   
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                   
                 liquid 
                 liquid 
                 liquid 
                 solid 
                 liquid 
                 liquid 
                 liquid 
                 flowing 
                 liquid 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 gel 
               
               
                 311 
                 Clear 
                 Hazy 
                 Clear 
                 Clear 
                 Clear 
                 Clear 
                 Clear 
                 Clear 
                 Clear 
                 Hazy 
                 Clear 
                 Clear 
                 Clear 
                 Hazy 
               
               
                   
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                 fluff 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 over 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 clear 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 liquid 
               
               
                 312 
                 Clear 
                 Hazy 
                 Clear 
                 Clear 
                 Clear 
                 Cloudy 
                 Clear 
                 Clear 
                 Clear 
                 Cloudy 
                 Clear 
                 Clear 
                 Cloudy 
                 Cloudy 
               
               
                   
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                 solid 
                 liquid 
                 liquid 
                 liquid 
                 solid 
                 liquid 
                 liquid 
                 liquid 
                 flowing 
                 liquid 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 gel 
               
               
                 313 
                 Clear 
                 Hazy 
                 Clear 
                 Clear 
                 Clear 
                 Barely 
                 Clear 
                 Clear 
                 Clear 
                 Very 
                 Clear 
                 Clear 
                 Clear 
                 Hazy 
               
               
                   
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                 hazy 
                 liquid 
                 liquid 
                 liquid 
                 hazy 
                 liquid 
                 liquid 
                 liquid 
                 fluff 
               
               
                   
                   
                   
                   
                   
                   
                 liquid 
                   
                   
                   
                 liquid 
                   
                   
                   
                 over 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 clear 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 liquid 
               
               
                 314 
                 Clear 
                 Barely 
                 Clear 
                 Clear 
                 Cloudy 
                 Clear 
                 Clear 
                 Clear 
                 Clear 
                 Hazy 
                 Clear 
                 Clear 
                 Cloudy 
                 Hazy 
               
               
                   
                 liquid 
                 hazy 
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                 liquid; 
                 fluff 
               
               
                   
                   
                 liquid 
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 cloudy 
                 over 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 solid 
                 clear 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 ring 
                 liquid 
               
               
                 315 
                 Clear 
                 Cloudy 
                 Clear 
                 Clear 
                 Slush 
                 Cloudy 
                 Clear 
                 Clear 
                 Clear 
                 Opaque 
                 Clear 
                 Separated 
                 Opaque 
                 Cloudy 
               
               
                   
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                   
                 liquid 
                 liquid 
                 liquid 
                 slow 
                 liquid 
                 liquid 
                 slightly 
                 slush 
                 liquid 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 flowing 
                   
                   
                 hazy 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 liquid 
                   
                   
                 liquid 
               
               
                 316 
                 Clear 
                 Cloudy 
                 Clear 
                 Clear 
                 Clear 
                 Cloudy 
                 Clear 
                 Clear 
                 Clear 
                 Cloudy 
                 Clear 
                 Clear 
                 Cloudy 
                 Cloudy 
               
               
                   
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                 solid 
                 liquid 
                 liquid 
                 liquid 
                 solid 
                 liquid 
                 liquid 
                 liquid 
                 flowing 
                 liquid 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 gel 
               
               
                 317 
                 Clear 
                 Cloudy 
                 Clear 
                 Clear 
                 Clear 
                 Cloudy 
                 Clear 
                 Clear 
                 Clear 
                 Cloudy 
                 Clear 
                 Clear 
                 Cloudy 
                 Cloudy 
               
               
                   
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                 solid 
                 liquid 
                 liquid 
                 liquid 
                 solid 
                 liquid 
                 liquid 
                 liquid 
                 flowing 
                 liquid 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 gel 
               
               
                 318 
                 Clear 
                 Hazy 
                 Clear 
                 Clear 
                 Clear 
                 Clear 
                 Clear 
                 Clear 
                 Clear 
                 Hazy 
                 Clear 
                 Clear 
                 Clear 
                 Clear 
               
               
                   
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                 liquid 
               
               
                 319 
                 Opaque 
                 Barely 
                 Clear 
                 Clear 
                 Opaque 
                 Clear 
                 Clear 
                 Clear 
                 Opaque 
                 Hazy 
                 Clear 
                 Clear 
                 Opaque 
                 Hazy 
               
               
                   
                 liquid 
                 hazy 
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                 fluff 
               
               
                   
                   
                 liquid 
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 over 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 clear 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 liquid 
               
               
                 320 
                 Clear 
                 Clear 
                 Clear 
                 Clear 
                 Cloudy 
                 Clear 
                 Clear 
                 Clear 
                 Opaque 
                 Clear 
                 Clear 
                 Clear 
                 Opaque 
                 Hazy 
               
               
                   
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                 liquid 
                 liquid; 
                 liquid 
                 liquid 
                 liquid 
                 solid 
                 material 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 opaque 
                   
                   
                   
                 over 
                 in clear 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 solid 
                   
                   
                   
                 opaque 
                 liquid 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 ring 
                   
                   
                   
                 liquid 
               
               
                 321 
                 Cloudy 
                 Barely 
                 Clear 
                 Clear 
                 Cloudy 
                 Barely 
                 Clear 
                 Clear 
                 Cloudy 
                 Hazy 
                 Clear 
                 Clear 
                 Slow 
                 Clear 
               
               
                   
                 liquid 
                 hazy 
                 liquid 
                 liquid 
                 slush 
                 hazy 
                 liquid 
                 liquid 
                 slush 
                 liquid 
                 liquid 
                 liquid 
                 flowing 
                 liquid 
               
               
                   
                   
                 liquid 
                   
                   
                   
                 liquid 
                   
                   
                   
                   
                   
                   
                 cloudy 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 gel 
               
               
                   
               
            
           
         
       
     
     Working Examples 322-329 
     PIC compositions including the components listed in Table 13 were admixed and tested to determine solidification point. The alkylphenol formaldehyde resin used was Flozol 2252, obtained from Lubrizol, 5-20% solids, and was added to the formulations of examples 142-149 as received and not on the basis of weight percent actives. The balance of each of the PICS listed in Table 13 was toluene, xylene, or HAN. 
     
       
         
           
               
             
               
                 TABLE 13 
               
             
            
               
                   
               
               
                 Components and observed solidification 
               
               
                 point of working examples 322-329. 
               
            
           
           
               
               
               
               
               
            
               
                   
                   
                 Propylene 
                 Propylene 
                   
               
               
                   
                 Alkyl phenol 
                 glycol 
                 glycol 
                   
               
               
                 Working 
                 formaldehyde 
                 methyl ether 
                 diacetate 
                 Solidification 
               
               
                 Example # 
                 Resin (wt %) 
                 acetate (wt %) 
                 (wt %) 
                 Point (° C.) 
               
               
                   
               
            
           
           
               
               
               
               
               
            
               
                 322 
                 20 
                 5 
                 0 
                 &gt;−20 
               
               
                 323 
                 20 
                 10 
                 0 
                 &gt;−40 
               
               
                 324 
                 20 
                 15 
                 0 
                 &gt;−40 
               
               
                 325 
                 20 
                 0 
                 5 
                 &gt;−40 
               
               
                 326 
                 20 
                 0 
                 10 
                 &gt;−40 
               
               
                 327 
                 20 
                 0 
                 15 
                 &gt;−40 
               
               
                 328 
                 20 
                 5 
                 5 
                 &gt;−40 
               
               
                 329 
                 20 
                 10 
                 10 
                 &gt;−40 
               
               
                   
               
            
           
         
       
     
     The formulations of working examples 322-329 all exhibited 20% to 80% inhibition in paraffin deposition when added in the range of 100-2000 ppm to waxy crude oil and tested for paraffin inhibition by cold finger test, when compared to the crude oil without addition of the working examples 332-339 (control). The cold finger test quantitates the amount of paraffin wax deposited from 30° C. crude oil placed on a 5° C. metal surface. 
     Working Examples 330-336 
     Mixtures including 0.7 wt % actives of an esterified C 20  or greater alpha olefin/maleic anhydride copolymer were formed with FLOZOL® 2252, an alkylphenol formaldehyde resin obtained from Lubrizol and the functionalized glycols as shown in Table 14. The working examples 330-336 were then subjected to the following temperature cycle: 1 day at −45° C., followed by 15 hours at 60° C., followed by 3 days at −45° C., followed by 15 hours at 60° C., followed by 3 days at −45° C., followed finally by 15 hours at 60° C. Working examples 331, 333, and 334 were observed to be stable, homogeneous liquids throughout the entirety of the temperature cycle. 
     
       
         
           
               
             
               
                 TABLE 14 
               
             
            
               
                   
               
               
                 Components of working examples 330-336, along with 7 wt % 
               
               
                 actives of an esterified C 20  or greater alpha 
               
               
                 olefin/maleic anhydride copolymer. 
               
            
           
           
               
               
               
               
               
            
               
                   
                 FLOZOL ® 
                   
                 Wt % 
                   
               
               
                 Working 
                 2252 
                 Functionalized 
                 Functionalized 
                 Toluene 
               
               
                 Example # 
                 (wt %) 
                 Glycol 
                 Glycol 
                 (wt %) 
               
               
                   
               
            
           
           
               
               
               
               
               
            
               
                 330 
                 23 
                 Propylene glycol 
                 8 
                 62 
               
               
                   
                   
                 methyl ether acetate 
                   
                   
               
               
                 331 
                 10 
                 Propylene glycol 
                 17 
                 66 
               
               
                   
                   
                 methyl ether acetate 
                   
                   
               
               
                 332 
                 10 
                 Ethylene glycol di 
                 8 
                 75 
               
               
                   
                   
                 acetate 
                   
                   
               
               
                 333 
                 12.3 
                 Ethylene glycol di 
                 16 
                 74 
               
               
                   
                   
                 acetate 
                   
                   
               
               
                 334 
                 10 
                 Ethylene glycol di 
                 20 
                 63 
               
               
                   
                   
                 acetate 
                   
                   
               
               
                 335 
                 10 
                 2-Methyl propylene 
                 8 
                 75 
               
               
                   
                   
                 glycol acetate 
                   
                   
               
               
                 336 
                 10 
                 2-Methyl propylene 
                 16 
                 67 
               
               
                   
                   
                 glycol acetate 
               
               
                   
               
            
           
         
       
     
     Working Examples 337-346 
     A mixture including 7 wt % of esterified C 20  or greater alpha olefin/maleic anhydride copolymer (as supplied and not as actives) was formed by blending a 5 wt % actives solution of the polymer of in xylene with FLOZOL® 2252, propylene glycol methyl ether acetate, 2-pyridone, and toluene in the amounts indicated in Table 16. After mixing, the working examples were stored at 4.5 days at −45° C., followed by observation regarding whether the mixture was a liquid at that temperature. Observations are recorded in Table 16. 
     
       
         
           
               
             
               
                 TABLE 15 
               
             
            
               
                   
               
               
                 Components of working examples 343-358, along with 7 wt % of 
               
               
                 esterified C 20  or greater alpha olefin/maleic anhydride 
               
               
                 copolymer as supplied, and observed results after storing 
               
               
                 the working examples at −45° C. for 4.5 days. 
               
            
           
           
               
               
               
               
               
               
            
               
                   
                   
                 Propylene 
                   
                   
                   
               
               
                   
                   
                 glycol 
                   
                   
                   
               
               
                   
                   
                 methyl 
                 2- 
                   
                 Liquid 
               
               
                 Working 
                 FLOZOL ® 
                 ether 
                 Pyridone 
                 Toluene 
                 after 4.5 d 
               
               
                 Example # 
                 2252 (g) 
                 acetate (g) 
                 (g) 
                 (g) 
                 @−45° C.? 
               
               
                   
               
            
           
           
               
               
               
               
               
               
            
               
                 337 
                 23 
                 8 
                 0 
                 62 
                 no 
               
               
                 338 
                 10 
                 17 
                 0 
                 66 
                 yes 
               
               
                 339 
                 10 
                 10 
                 0 
                 73 
                 no 
               
               
                 340 
                 10 
                 15 
                 0 
                 68 
                 yes 
               
               
                 341 
                 10 
                 20 
                 0 
                 63 
                 yes 
               
               
                 342 
                 23 
                 8 
                 2 
                 60 
                 no 
               
               
                 343 
                 10 
                 17 
                 2 
                 64 
                 no 
               
               
                 344 
                 10 
                 10 
                 2 
                 71 
                 no 
               
               
                 345 
                 10 
                 15 
                 2 
                 66 
                 no 
               
               
                 346 
                 10 
                 20 
                 2 
                 61 
                 no 
               
               
                   
               
            
           
         
       
     
     The invention illustratively disclosed herein can be suitably practiced in the absence of any element which is not specifically disclosed herein. Additionally each and every embodiment of the invention, as described herein, is intended to be used either alone or in combination with any other embodiment described herein as well as modifications, equivalents, and alternatives thereof. In various embodiments, the invention suitably comprises, consists essentially of, or consists of the elements described herein and claimed according to the claims. It will be recognized that various modifications and changes may be made without following the example embodiments and applications illustrated and described herein, and without departing from the scope of the claims.