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Patent US6258761 - Lubricating oil additives - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inAdvanced Patent SearchPatentsA composition prepared by reacting (A) an esterified carboxy-containing interpolymer, said interpolymer being derived from at least two monomers, (i) one of said monomers being at least one vinyl aromatic monomer and (ii) the other of said monomers being at least one alpha, beta-unsaturated acylating...http://www.google.com/patents/US6258761?utm_source=gb-gplus-sharePatent US6258761 - Lubricating oil additivesAdvanced Patent SearchPublication numberUS6258761 B1Publication typeGrantApplication numberUS 09/329,891Publication dateJul 10, 2001Filing dateJun 10, 1999Priority dateJun 10, 1999Fee statusLapsedAlso published asCA2376635A1, DE60016406D1, DE60016406T2, EP1190021A1, EP1190021B1, WO2000077131A1Publication number09329891, 329891, US 6258761 B1, US 6258761B1, US-B1-6258761, US6258761 B1, US6258761B1InventorsRichard M. Lange, James R. Shanklin, Jr., Jeffry G. Dietz, Richard Yodice, Naresh C. MathurOriginal AssigneeThe Lubrizol CorporationExport CitationBiBTeX, EndNote, RefManPatent Citations (26), Referenced by (3), Classifications (36), Legal Events (5) External Links: USPTO, USPTO Assignment, EspacenetLubricating oil additivesUS 6258761 B1Abstract A composition prepared by reacting
(B) a hydrocarbyl substituted carboxylic acid or functional derivative thereof wherein the hydrocarbyl group comprises from about 10 to about 400 carbon atoms, and (C) an amine having an average of more than 1 condensable N�H group, in any order or simultaneously, or with the preformed reaction product of (B) and (C) wherein said preformed reaction product has at least one condensable N�H group. Depending upon the relative amounts of reactant (A) and (B) used, a composition which acts primarily as a viscosity improver with dispersant properties (DVM) or primarily as a dispersant with viscosity improving properties (VMD) may be prepared or compositions with properties intermediate between these.
(A) an esterified carboxy-containing interpolymer, said interpolymer being derived from at least two monomers, (i) one of said monomers being at least one vinyl aromatic monomer and (ii) the other of said monomers being at least one alpha, beta-unsaturated acylating agent, and having, before esterification, {overscore (M)}n determined by gel permeation chromatography ranging from about 8,000 to about 350,000, wherein from about 80% to about 99% of the carboxylic groups of said interpolymer are esterified, wherein from about 80 to about 100% of the ester groups contain from 8 to about 23 carbon atoms and from 0 to about 20% of the ester groups contain from 2 to 7 carbon atoms, with (B) a hydrocarbyl substituted carboxylic acid or functional derivative thereof wherein the hydrocarbyl group comprises from about 10 to about 400 carbon atoms, and (C) an amine having an average of more than 1 condensable N�H group, in any order or simultaneously, or with the preformed reaction product of (B) and (C) wherein said preformed reaction product has at least one condensable N�H group. 2. The composition of claim 1 wherein said esterified groups of interpolymer (A) are characterized by the presence of at least one member of the group consisting of
(A) an esterified carboxy-containing interpolymer, said interpolymer being derived from at least two monomers, (i) one of said monomers being at least one vinyl aromatic monomer and (ii) the other of said monomers being at least one alpha, beta-unsaturated acylating agent, and having, before esterification, {overscore (M)}n determined by gel permeation chromatography ranging from about 8,000 to about 350,000, wherein from about 80% to about 99% of the carboxylic groups of said interpolymer are ester groups, wherein from about 80 to about 100% of said ester groups contain from 8 to about 19 carbon atoms and from 0 to about 20% of said ester groups contain from 2 to 7 carbon atoms, with (B) a hydrocarbyl substituted carboxylic acid or functional derivative thereof wherein the hydrocarbyl group comprises from about 10 to about 400 carbon atoms, and (C) an amine having at least 1 condensable N�H group, said reacting being conducted in any order or simultaneously, or with the preformed reaction product of (B) and (C) wherein said preformed reaction product has at least one condensable N�H group. 36. The process of claim 35 wherein the esterified interpolymer (A) is reacted with the preformed reaction product of hydrocarbyl substituted carboxylic acid or functional derivative thereof (B) and amine (C).
FIELD OF THE INVENTION This invention relates to performance improving additives for lubricating oils. In particular, the invention relates to additives useful for improving viscosity and dispersancy characteristics of lubricating oils.
SUMMARY OF THE INVENTION It is desirable to enable the formulator to prepare compositions which provide a broad spectrum of performance benefits. The instant invention relates to a composition prepared by reacting
(C) an amine having an average of more than 1 condensable N�H group, in any order or simultaneously, or with the preformed reaction product of (B) and (C) wherein said preformed reaction product has at least one condensable N�H group.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS It is to be understood that the expression �before esterification� when used in reference to the carboxy containing interpolymer includes reference to an interpolymer which may be derived from one or more ester group containing monomers, but which has not been subjected to further esterification such that at least about 80% of the carboxylic groups of the interpolymer are esterified.
As used herein, the terms �hydrocarbon�, �hydrocarbyl� or �hydrocarbon based� mean that the group being described has predominantly hydrocarbon character within the context of this invention. These include groups that are purely hydrocarbon in nature, that is, they contain only carbon and hydrogen. They may also include groups containing substituents or atoms which do not alter the predominantly hydrocarbon character of the group. Such substituents may include halo-, alkoxy-, nitro-, etc. These groups also may contain hetero atoms. Suitable hetero atoms will be apparent to those skilled in the art and include, for example, sulfur, nitrogen and oxygen. Therefore, while remaining predominantly hydrocarbon in character within the context of this invention, these groups may contain atoms other than carbon present in a chain or ring otherwise composed of carbon atoms provided that they do not adversely affect reactivity or utility of the process or products of this invention.
The expression �lower� is used throughout the specification and claims. As used herein to describe various groups, the expression �lower� is intended to mean groups containing no more than 7 carbon atoms, more often, no more than 4, frequently one or two carbon atoms.
In the context of this invention the terms �interpolymer� and �copolymer� mean a polymer derived from two or more different monomers. Thus, a polymer derived from a mixture of, for example, methyl-, butyl-, C9-11-, and C12-18-methacrylates, or a polymer having two or more distinct blocks, is an interpolymer or copolymer as defined herein. The copolymers of this invention also may contain units derived from nitrogen-containing monomers.
The expression �substantially inert� is used in reference to diluents. When used in this context, �substantially inert� means the diluent is essentially inert with respect to any reactants or compositions of this invention, that is, it will not, under ordinary circumstances, undergo any significant reaction with any reactant or composition, nor will it interfere with any reaction or composition of this invention.
Mixtures of two or more compatible (i.e., nonreactive to one another) interpolymers which are separately prepared are contemplated herein for use in preparation of the esterified interpolymer. Thus, as used herein, and in the appended claims, the terminology �interpolymer� refers to either one separately prepared interpolymer or a mixture of two or more of such interpolymers. A separately prepared interpolymer is one in which the reactants and/or reaction conditions are different from the preparation of another interpolymer.
Instrumentation for determining molecular weights of the interpolymers includes a Waters 2690 separations module, an Eppendorf CH-460 multiple column heater (500 watt) with TC-55 dual channel heater control, Waters 410 Differential Refractometer and Waters Millenium Gel Permeation Chromatography (GPC) software for data acquisition and processing. Columns are 3� PLgel 5 μm Mixed C (excl. limit �6 M); 300�7.5 mm; Cat. #1110-6500 and 1� PLgel 5 μm 100A; 300�7.5 mm; Cat #1110-6520.
The vinyl ester of a carboxylic acid may be represented by the formula R3CH═CH�O(O)CR4 wherein R3 is a hydrogen or hydrocarbyl group having from 1 to about 30, or to 12 carbon atoms, or just hydrogen, and R4 is a hydrocarbyl group having 1 to about 30, or to about 12, or to about 8. Examples of vinyl esters include vinyl acetate, vinyl 2-ethylhexanoate, vinyl butanoate, vinyl crotonate. Vinyl carboxylates include vinyl acetate, vinyl butanoate, etc.
Preferred vinyl aromatic monomers are styrene or a substituted styrene (either ring substituted or substituted on the aliphatic �C═C group), most preferably, styrene.
EXAMPLE A-1 A reactor is charged with 2850 parts of a 21.1% solids in toluene slurry of a maleic anhydride/styrene/methyl methacrylate (1:1:0.05 mole ratio) terpolymer having {overscore (M)}n about 8400 and {overscore (M)}w about 30,000, and 846 parts of Alfol 1218 (a mixture of predominantly straight chain primary alcohols having from 12 to 18 carbon atoms). The materials are heated at 115-120� C. for 3.5 hours while toluene is removed and collected in a Dean-Stark trap (2350 parts by volume removed). A mixture of 244 parts Alfol 810 (a mixture of predominantly straight chain primary alcohols having from 8 to 10 carbon atoms) and 31.4 parts 70% methanesulfonic acid is added to the reaction mixture over 1.5 hours while the temperature is increased to 150� C. The reaction is continued at 150� C. for 14 hours; 52 parts by volume aqueous distillate is collected and a total of 2565 parts by volume toluene is collected. Total acid no=22.4 and strong acid no=3.71. An additional 25 parts Alfol 810 and 100 parts by volume toluene are added and reaction is continued for 14 hours. Toluene, 200 parts by volume, is added dropwise and heating is continued at 150� C. for 14 hours. Total acid no=15, infrared spectrum shows no �OH. The sulfonic acid is neutralized with 18.4 parts 50% aqueous NaOH by mixing at 150� C. for 2 hours. Total acid no=14.6. Viscosity @ 100� C.=2844 centistokes.
EXAMPLE A-2 A reactor is charged with 2485 parts of Alfol 1218 alcohol, 3183 parts of a 24% by weight solids in toluene slurry of a maleic anhydride/styrene/methyl methacrylate (1:1:0.05 mole ratio) terpolymer having {overscore (M)}n about 10,000, 3343 parts of a 25.9% solids in toluene slurry of a maleic anhydride/styrene/methyl methacrylate (1:1:0.05 mole ratio) terpolymer having {overscore (M)}n about 10,000, and 712 parts of Alfol 810 alcohol. The temperature is increased to 66� C. while removing toluene, 91.5 parts methane sulfonic acid are added, then the temperature is ramped to 138� C. over 8.5 hours followed by heating at 138-149� C. for 10 hours, removing distillate; acid number of residue=5.6. The batch is neutralized with a total of 50.7 parts 50% aqueous NaOH, followed by vacuum stripping at about 120� C. The residue is filtered. TAN is about 12.2.
EXAMPLE A-3 A reactor is charged with 1831 parts Alfol 1218 alcohol and 4298 parts of a 28.2% by weight solids in toluene slurry of maleic anhydride/styrene (1:1 molar) copolymer having {overscore (M)}n about 35,000 which is stripped at 104� C., under reduced pressure near end of stripping procedure. A portion (100 parts by volume) distillate is returned to the reactor then 522 parts Alfol 810 alcohol and 64.8 parts methane sulfonic acid are added. The temperature is ramped to 150� C. over 5 hours while removing distillate. A portion of the distillate (180 parts by volume) is returned to the reactor and the reaction is continued for 5 hours at about 150� C. The catalyst is neutralized with a total of 31.8 parts 50% aqueous NaOH then vacuum stripped at about 150� C., the vacuum is released and 1188 parts mineral oil are added under N2 blanket. The temperature is reduced to 67� C. and the oil solution is filtered. Neat TAN=4.8.
EXAMPLE A-4 The procedure of Example A-3 is repeated employing 4505 parts of a 26.9% by weight solids in toluene slurry of maleic anhydride/styrene (1:1 molar) copolymer having {overscore (M)}n about 35,000, 3456 parts mineral oil, 1746 parts Alfol 1218 alcohols, 498 parts Alfol 810 alcohols and 61.8 parts methane sulfonic acid. The catalyst is neutralized with a total of 29.4 parts 50% aqueous NaOH. Neat TAN=17.9.
EXAMPLE A-5 A reactor is charged with 1583 parts mineral oil, 766 parts Alfol 1218 alcohol and 4626 parts of a 26.2% by weight solids in toluene slurry of maleic anhydride/styrene (1:1 molar) copolymer having {overscore (M)}n about 35,000 which is stripped at 107� C., under reduced pressure near end of stripping procedure. To the residue are added 1189 parts Alfol 810 alcohol and 63.3 parts methane sulfonic acid. The temperature is ramped to 150� C. over 5 hours while removing aqueous distillate and allowing organic distillate to return to reactor. The reaction is continued for 16 hours at about 150� C. Net neutralization number=7.6 (acid). A mixture of 30 parts Alfol 1218 and 70 parts Alfol 810 is prepared and 54 parts of the mixture are added to the reactor. The reaction is continued for 9.5 hours whereupon the catalyst is neutralized with a total of 31 parts 50% aqueous NaOH. The materials are vacuum stripped at about 150� C. The vacuum is released and 1583 parts mineral oil are added under N2 blanket. The temperature is reduced to 120� C. and the oil solution is filtered. Neat TAN=12.2.
EXAMPLE A-6 A reactor is charged with 1752 parts mineral oil (Mobil 100N) and 1784 parts Alfol 1218 alcohols. The materials are mixed then 4590.9 parts of a 26.4% in toluene slurry of a maleic anhydride/styrene (1:1 molar) copolymer having {overscore (M)}n about 35,000 are added followed by heating to 103� C. and stripping at 103� C.-110� C. for 1 hour. The pressure is reduced to 249 mm Hg and additional distillate is removed. To the residue are added 508 parts Alfol 810 alcohols and 63 parts methane sulfonic acid followed by heating to 143� C. over 5 hours while collecting additional distillate. At this point strong acid number=9.55 and weak acid number=3.53. Heating is continued for 3 hours at 148� C. Strong acid number=7.67 and weak acid number=3.47. The strong acid is neutralized with 66.6 parts 50% aqueous NaOH at 145� C. for 1 hour, the materials are stripped to 141� C. at 40 mm Hg, 1752 parts additional mineral oil are added and the solution is filtered. Neat TAN=7.2.
EXAMPLE A-7 Following essentially the procedure of Example A-1 an ester is prepared with 3183 parts of a 24% by weight solids in toluene slurry of a maleic anhydride/styrene/methyl methacrylate (1:1:0.05 mole ratio) terpolymer having {overscore (M)}n about 11,000, 3343 parts of a 25.9% solids in toluene slurry of a maleic anhydride/styrene/methyl methacrylate (1:1:0.05 mole ratio) terpolymer having {overscore (M)}n about 11,000, 1450 parts of Alfol 1218 alcohols, 1452 parts Alfol 810 alcohols and 91.5 parts methane sulfonic acid. The product is filtered. Neat TAN=12.3.
EXAMPLE A-8 A reactor is charged with 3927 parts of a 18% in toluene slurry of a maleic anhydride/styrene (1:1 molar) copolymer having {overscore (M)}n about 65,000 and 976 parts of Alfol 1218 alcohols. After the mixture is heated to 100� C., 171 parts Alfol 810 alcohols and 13.6 parts methanesulfonic acid are added over 0.1 hour, heated at 100� C.-110� C. for 1 hour, then is heated to 150� C. After heating for 4 hours while removing distillate, net neutralization number=6.29. To the reaction are charged 93 parts n-butanol and 3.9 parts methanesulfonic acid and the reaction is continued for 4 hours whereupon net neutralization no=2.24. An additional 93 parts n-butanol and 3.9 parts methanesulfonic acid are added and the reaction was continued for 2 more hours at which time no further distillate forms. The temperature is reduced to 120� C. and 8.4 parts hindered phenol are added. The temperature is increased to 150� C. and is maintained for 6 hours while an additional amount of distillate is removed. Neat neutralization numbers are 3.42 (total) and 1.24 (strong acid).
EXAMPLE A-9 A reactor is charged with 757.5 parts of a maleic anhydride/styrene (1:1 molar) copolymer having {overscore (M)}n about 65,000, 3119 parts mineral oil (Shell HVI-100), 332 parts toluene and 1042 parts Alfol 1218 alcohols. The materials are stirred and heated to 100� C. whereupon a solution of 20.8 parts methanesulfonic acid and 184 parts Alfol 810 alcohols are charged, the materials are heated to 150� C. and are refluxed for 4.5 hours. To the reaction are added , over 0.2 hour, 100 parts n-butanol and the materials are refluxed for 1.5 hours then an additional 100 parts n-butanol are charged and the materials are refluxed for 16 hours. Neutralization numbers are 4.9 (total) and 0.9 (strong acid). The strong acid is neutralized with 50% aqueous NaOH, 9.75 parts hindered phenol are added and the materials are stripped to 150� C. at 80 mm Hg pressure. A second portion of 9.75 parts hindered phenol and 1100 parts mineral oil (Shell HVI-100) are added and the solution is filtered. TAN=2.2.
The compositions of this invention are obtained by reacting a mixture of the esterified interpolymer (A) and (B) a hydrocarbyl group substituted carboxylic acid or functional derivative thereof with (C) an amine having an average of more than 1, preferably at least 1.1, often at least about 1.5 condensable N�H groups, or with the preformed reaction product of (B) and (C), wherein said preformed reaction product contains at least one condensable N�H group. A functional derivative is one which can react with (C) to generate N-containing derivatives analogous to the products prepared from the corresponding carboxylic acid. Examples of functional derivatives include esters, especially lower alkyl esters, anhydrides, acyl halides and the like.
R3C(O)(R4)nC(O)OR5 (IV) and reactive sources thereof such as compounds of the formula wherein each of R3, R5 and each R9 is independently H or a hydrocarbyl group, R4 is a divalent hydrocarbylene group, preferably lower alkylene, more preferably methylene, ethylene or propylene, and n is 0 or 1, preferably, 0. Examples of (V) include the acetals and hemiacetals, esters, and others. Glyoxylic acid, its hydrate and glyoxylic acid methyl ester, methyl hemiacetal are particularly preferred reactants of this type.
The polyalkenes from which the carboxylic acids (B) are derived are homopolymers and interpolymers of polymerizable olefin monomers of 2 to about 16 carbon atoms; usually 2 to about 6 carbon atoms. The interpolymers are those in which two or more olefin monomers are interpolymerized according to well-known conventional procedures to form polyalkenes having units within their structure derived from each of said two or more olefin monomers. Thus, �interpolymer(s)� as used herein is inclusive of copolymers, terpolymers, tetrapolymers, and the like. As will be apparent to those of ordinary skill in the art, the polyalkenes from which the substituent groups are derived are often conventionally referred to as �polyolefin(s)�.
�C�C═C�C� can also be used to form the polyalkenes. When internal olefin monomers are employed, they normally will be employed with terminal olefins to produce polyalkenes which are interpolymers. For purposes of this invention, when a particular polymerized olefin monomer can be classified as both a terminal olefin and an internal olefin, it will be deemed to be a terminal olefin. Thus, 1,3-pentadiene (i.e., piperylene) is deemed to be a terminal olefin.
A number of methods are available for reacting the α,β-unsaturated carboxylic compounds with the polyalkene or chlorinated derivative thereof or with a suitable olefin. Illustrative methods include the �ene� reaction wherein the carboxylic compound is reacted, with heating, with the unsaturated reagent, by blowing with halogen, usually chlorine, or by combinations of these methods. The (B) reactant may be prepared by any of these techniques or by others known in the art.
EXAMPLE B-1 A mixture of 6400 parts (4 moles) of a polybutene comprising predominantly isobutene units and having a molecular weight of about 1600 and 408 parts (4.16 moles) of maleic anhydride is heated at 225-240� C. for 4 hours. It is then cooled to 170� C. and an additional 102 parts (1.04 moles) of maleic anhydride is added, followed by 70 parts (0.99 mole) of chlorine; the latter is added over 3 hours at 170-215� C. The mixture is heated for an additional 3 hours at 215� C., vacuum stripped at 220� C. and filtered. The product is the desired polybutenyl-substituted succinic anhydride having a saponification number of 61.8.
EXAMPLE B-2 A monocarboxylic acid is prepared by chlorinating a polyisobutene having a molecular weight of 750 to a product having a chlorine content of 3.6% by weight, converting the product to the corresponding nitrile by reaction with an equivalent amount of potassium cyanide in the presence of a catalytic amount of cuprous cyanide and hydrolyzing the resulting nitrile by treatment with 50% excess of dilute aqueous sulfuric acid at reflux temperature.
EXAMPLE B-3 A high molecular weight mono-carboxylic acid is prepared by telomerizing ethylene with carbon tetrachloride to a telomer having an average of 35 ethylene radicals per molecule and hydrolyzing the telomer to the corresponding acid in according with the procedure described in British Patent No. 581,899.
EXAMPLE B-4 A polybutenyl succinic anhydride is prepared by the reaction of a chlorinated polybutylene with maleic anhydride at 200� C. The polybutenyl radical has an average molecular weight of 805 and contains primarily isobutene units. The resulting alkenyl succinic anhydride is found to have an acid number of 113 (corresponding to an equivalent weight of 500).
EXAMPLE B-5 A lactone acid is prepared by reacting 2 equivalents of a polyolefin ({overscore (M)}n about 900) substituted succinic anhydride with 1.02 equivalents of water at a temperature of about 90� C. in the presence of a catalytic amount of concentrated sulfuric acid. Following completion of the reaction, the sulfuric acid catalyst is neutralized with sodium carbonate and the reaction mixture is filtered.
EXAMPLE B-6 An ester acid is prepared by reacting 2 equivalents of an alkyl substituted succinic anhydride having an average of about 35 carbon atoms in the alkyl group with 1 mole of ethanol.
EXAMPLE B-7 A reactor is charged with 1000 parts of polybutene having a molecular weight determined by vapor phase osmometry of about 950 and which consists primarily of isobutene units, followed by the addition of 108 parts of maleic anhydride. The mixture is heated to 110� C. followed by the sub-surface addition of 100 parts Cl2 over 6.5 hours at a temperature ranging from 110 to 188� C. The exothermic reaction is controlled as not to exceed 188� C. The batch is blown with nitrogen then stored.
EXAMPLE B-8 The procedure of Example B-7 is repeated employing 1000 parts of polybutene having a molecular weight determined by vapor phase osmometry of about 1650 and consisting primarily of isobutene units and 106 parts maleic anhydride. Cl2 is added beginning at 130� C. and added at a nearly continuous rate such that the maximum temperature of 188� C. is reached near the end of chlorination. The residue is blown with nitrogen and collected.
EXAMPLE B-9 A reactor is charged with 3000 parts of a polyisobutene having a number average molecular weight of about 1000 and which contains about 80 mole % terminal vinylidene groups and 6 parts 70% aqueous methanesulfonic acid. The materials are heated to 160� C. under N2 followed by addition of 577.2 parts 50% aqueous glyoxylic acid over 4 hours while maintaining 155-160� C. Water is removed and is collected in a Dean-Stark trap. The reaction is held at 160� C. for 5 hours, cooled to 140� C. and filtered. The filtrate has total acid no. (ASTM Procedure D-974)=34.7 and saponification no. (ASTM Procedure D-74)=53.2. {overscore (M)}n (Gel permeation chromatography (GPC))=1476 and {overscore (M)}w (GPC)=3067; unreacted polyisobutene (Thin layer chromatography-Flame ionization detector (TLC-FID))=8.6%.
EXAMPLE B-10 A polyisobutylene chloride is obtained using 1 mole of polyisobutylene ({overscore (M)}n 2136) and 0.91 mole chlorine in hexane at 70-75� C. with removal of hexane following chlorination. This chloride (500 parts, 0.2205 mole) and 32 parts maleic anhydride (0.3265 mole) are heated at 150� C.-190� C. under N2 purge for 1 hour and held at 190� C. for 7 hours. After cooling to about 150� C., 15.5 parts maleic anhydride are charged, N2 is stopped and 12.5 parts (0.175 mole) Cl2 are blown into the mixture over 2 hours. N2 is resumed and the temperature is ramped from 150� C. to 190� C. and is held for 7 hours. The mixture is then heated to 220� C. for 4 hours to total acid number of 77. The product has degree of succination about 1.5 and about 1600 parts per million residual Cl.
EXAMPLE B-11 An aliphatic group substituted succinic anhydride is prepared by the direct alkylation reaction (thermal reaction) of a polyisobutylene ({overscore (M)}n=1000) with maleic anhydride. The resulting product has total acid number of about 76, about 100 parts per million Cl and contains no more than 0.4% by weight unreacted maleic anhydride.
EXAMPLE B-12 A reactor charged with 592 parts 50% aqueous glyoxylic acid is heated to 70� C., a vacuum is applied and the materials are stripped to 80� C. at 25 mm Hg., collecting 231 parts water. The reactor is cooled to room temperature whereupon 200 parts of the polyisobutene of Example 2, Part A and 3 parts 70% aqueous methane sulfonic acid are added followed by heating for a total of 8 hours at 160� C. while collecting 207 parts aqueous distillate. The materials are diluted with 717.3 parts mineral oil, mixed and filtered at 130� C. The filtrate has saponification no.=65.9.
EXAMPLE B-13 A reactor is charged with 4830 parts of the reaction product derived by heating 1 mole polyisobutylene (Glissopal 2300, BASF) having {overscore (M)}n about 2300 and about 90% terminal vinylidene groups and 0.9 moles maleic anhydride, 422 parts glyoxylic acid methyl ester methyl hemiacetal, 15 parts 70% methane sulfonic acid, 0.1 part silicone antifoam agent and 1000 parts mineral oil. The materials are heated to 135� C. over 0.5 hour, under N2 and the temperature is maintained for 4 hours followed by stripping to 25 mrn Hg for 1 hour. An additional 2426 parts mineral oil are added, the materials are mixed, then filtered.
The amine used to prepare the compositions of the instant invention contains an average of more than 1, preferably at least 1.1 condensable N�H groups, often an average of at least 1.5, preferably an average of at least 2 condensable N�H groups, up to about 10, often up to about 6 condensable N�H groups. In one embodiment, the amine (C) is reacted with a mixture of (B) the hydrocarbyl substituted carboxylic acid or functional derivative thereof and the esterified interpolymer (A). In another embodiment, the esterified interpolymer (A) is reacted with the preformed reaction product of (B) and (C) wherein said preformed reaction product has at least one condensable N�H group.
Suitable amine reactants, as defined herein, include hydrazines, or polyamines. Monoamines may be used in admixture with polyamines but not as the sole amine reactant. The amine reactant must contain an average of more than 1 condensable N�H group. The amines may be aliphatic, cycloaliphatic, aromatic and heterocyclic.
The monoamines generally contain from 1 to about 24 carbon atoms, preferably 1 to about 12, and more preferably 1 to about 6. Examples of monoamines useful in the present invention include primary amines, for example methylamine, ethylamine, propylamine, butylamine, octylamine, and dodecylamine. Examples of secondary amines include dimethylamine, diethylamine, dipropylamine, dibutylamine, methylbutylamine, ethylhexylamine, etc. Tertiary monoamines do not possess an N�H group.
In another embodiment, the monoamine may be a hydroxyamine. Typically, the hydroxyamines are primary or secondary alkanolamines or mixtures thereof. As stated above, tertiary monoamines do not possess an N�H group; however, tertiary alkanol monoamines sometimes can react to form a tertiary amino group containing ester. Alkanol amines that possess an N�H group can be represented, for example, by the formulae: wherein each R4 is independently a hydrocarbyl group of one to about 22 carbon atoms or hydroxyhydrocarbyl group of two to about 22 carbon atoms, preferably one to about four, and R′ is a divalent hydrocarbyl group of about two to about 18 carbon atoms, preferably two to about four. The group �R′�OH in such formulae represents the hydroxyhydrocarbyl group. R′ can be an acyclic, alicyclic or aromatic group. Typically, R′ is an acyclic straight or branched alkylene group such as an ethylene, 1,2-propylene, 1,2-butylene, 1,2-octadecylene, etc. group. When two R4 groups are present in the same molecule they can be joined by a direct carbon-to-carbon bond or through a heteroatom (e.g., oxygen, nitrogen or sulfur) to form a 5-, 6-, 7- or 8-membered ring structure. Typically, however, each R4 is independently a methyl, ethyl, propyl, butyl, pentyl or hexyl group.
Alkylene polyamines are represented by the formula wherein n has an average value between about 1 and about 10, preferably about 2 to about 7, more preferably about 2 to about 5, and the �Alkylene� group has from 1 to about 10 carbon atoms, preferably about 2 to about 6, more preferably about 2 to about 4. Each R5 is independently hydrogen, an aliphatic group, an amino- or hydroxy-substituted aliphatic group of up to about 30 carbon atoms and the like. Preferably R5 is H or lower alkyl, most preferably, H.
Ethylene polyamines, such as some of those mentioned above, are preferred. They are described in detail under the heading Ethylene Amines in Kirk Othmer's �Encyclopedia of Chemical Technology�, 2d Edition, Vol. 7, pages 22-37, Interscience Publishers, New York (1965). Such polyamines are most conveniently prepared by the reaction of ethylene dichloride with ammonia or by reaction of an ethylene imine with a ring opening reagent such as water, ammonia, etc. These reactions result in the production of a complex mixture of polyalkylene polyamines including cyclic condensation products such as the aforedescribed piperazines. Ethylene polyamine mixtures are useful.
Other useful types of polyamine mixtures are those resulting from stripping of the above-described polyamine mixtures to leave as residue what is often termed �polyamine bottoms�. In general, alkylene polyamine bottoms can be characterized as having less than two, usually less than 1% (by weight) material boiling below about 200� C. A typical sample of such ethylene polyamine bottoms obtained from the Dow Chemical Company of Freeport, Tex., designated �E-100� has a specific gravity at 15.6� C. of 1.0168, a percent nitrogen by weight of 33.15 and a viscosity at 40� C. of 121 centistokes. Gas chromatography analysis of such a sample contains about 0.93% �Light Ends� (most probably diethylenetriamine), 0.72% triethylenetetramine, 21.74% tetraethylenepentamine and 76.61% pentaethylene hexamine and higher (by weight). Another example of polyamine bottoms is one having an equivalent weight of 40.5 based on % N, sold as HPA-X by Union Carbide. These alkylene polyamine bottoms include cyclic condensation products such as piperazine and higher analogs of diethylenetriamine, triethylenetetramine and the like.
The preferred polyoxyalkylene polyamines include the polyoxyethylene and polyoxypropylene diamines and the polyoxypropylene triamines having average molecular weights ranging from about 200 to 4000 or from about 400 to about 2000. The polyoxyalkylene polyamines are commercially available an may be obtained, for example, from the Texaco Company, Inc. under the trade names �Jeffamines D-230, D-400, D-1000, D-2000, T-403, etc.�.
As noted hereinabove, ammonia and hydrazines having an average of at least 1.1 condensable N�H group are also useful. Preferably there are at least two hydrogens bonded directly to hydrazine nitrogen and, more preferably, both hydrogens are on the same nitrogen. Substituents which may be present on the hydrazine include alkyl, alkenyl, aryl, aralkyl, alkaryl, and the like. Usually, the substituents are alkyl, especially lower alkyl, phenyl, and substituted phenyl such as lower alkoxy-substituted phenyl or lower alkyl-substituted phenyl. Specific examples of substituted hydrazines are methylhydrazine, NN-dimethyl-hydrazine, N,N′-dimethylhydrazine, phenylhydrazine, N-phenyl-N′-ethylhydrazine, N-phenyl-N′-cyclohexylhydrazine, and the like.
EXAMPLE P-1 About 1330 parts (11.71 equivalents) polyisobutylene acylating agent prepared as in example B-10 is mixed with 1383 parts 100 neutral mineral oil and heated to 99� C. To this is charged 100 parts (2.4 equivalents) of polyethyleneamine bottoms (HPA-X, Union Carbide) followed by heating to about 100� over 2 hours. The temperature is then increased to 149� C. over 3 hours under N2 purge and is maintained at 149� C. for 1 hour while removing distillate. The materials are filtered yielding a product having total base number (TBN) of about 27.5 and TAN 1.3.
EXAMPLE P-2 A reactor is charged with 350 parts of the product of Example B-9, 17.2 parts diethylene triamine and 267.5 parts mineral oil diluent, is heated under N2 to 160� C. and held at 160� C. for 5 hours then filtered 145� C. Filtrate contains 1.02% N.
EXAMPLE P-3 A reactor is charged with 350 parts of the product of Example B-12, 26.6 parts of polyamine bottoms having an equivalent weight of 40.5 per N (HPA-X, Union Carbide) and 105.3 parts mineral oil. The materials are heated, under N2, to 160� C. and are held at temperature for 5 hours, cooled to 145� C. and filtered. The filtrate contains 1.77% N.
EXAMPLE P-4 A reactor is charged with 2845 parts of the product of Example B-13, 148.8 parts HPA-X polyamine bottoms and 99.3 parts mineral oil. The materials are heated, under N2, to 180� C. and are held at 180� C. for a total of 9 hours, then cooled to 145� C. and filtered.
EXAMPLE P-5 A reactor is charged with 2381 parts of the product of Example B-11 and 860 parts mineral oil. The materials are heated to 110� C. whereupon 123 parts HPA-X polyamines are added. The temperature is held at 110� C. for 1 hour then is increased to 160� C. and is held at 160� C. for 6 hours while collecting about 19 parts aqueous distillate. The hot materials are filtered yielding an oil solution of a 1 C═O:1.1N reaction product.
EXAMPLE P-6 A solution is prepared by mixing 1220 parts of the product of Example P-5 and 244 parts of mineral oil (Mobil 100N).
EXAMPLE P-7 Following essentially the procedure of Example P-5, a 50% in oil solution of a 1 C═O:1.5N reaction product is obtained.
EXAMPLE P-8 Following essentially the procedure of Example P-5, a solution of 53 parts of the product of Example B-7 in 43.85 parts mineral oil is reacted with 4.35 parts of a mixture of 15 parts diethylenetriamine and 85 parts E-100 amine bottoms.
EXAMPLE P-9 The procedure of Example P-8 is repeated with 56.8 parts of the product of Example B-7, 38.8 parts mineral oil and 6.1 parts of the mixture of amines.
EXAMPLE P-10 A reactor is charged with 720 parts mineral oil and 1000 parts of the N2 blown product of Example B-7 while mixing under an N2 purge. The temperature is adjusted to 88� C. followed by addition of 111.3 parts of the product obtained by reacting 1000 parts of an ethylene polyamine bottoms identified as HPA-X (Union Carbide) and 613 parts of 40% aqueous tris-hydroxymethylamino-methane (THAM) under N2 purge in the presence of 15.9 parts 85% aqueous phosphoric acid at 177� C. with reflux of the amine while allowing water to be removed from the system then at 227� C.-232� C. for 10 hours while refluxing the amines, stripping at 232-238� C. for 6 hours, then rapidly cooling to 93�, water washing and neutralization of the catalyst with 22.1 parts 50% aqueous NaOH. The batch is mixed for 2 hours at 82-96� C., then the temperature is increased to 152� C. over 5.5 hours. At 152� C. the N2 purge is discontinued and submerged N2 is begun. The batch is heated at 149-154� C. until % H2O is no more than 0.30% by weight. The materials are cooled and filtered at 138-149� C. and adjusted with oil to give total oil of about 40% by weight. The product contains 1.65% N.
EXAMPLES 1-7 The products of Examples A-1 and P-1 are reacted, under N2 purge, in the amounts (parts by weight) and under the conditions indicated in the following Table.
EXAMPLES 8-12 In each example, HPA-X polyamine bottoms is added, subsurface and dropwise at about 110� C. over 0.25 hour for each of Examples 8, 10 and 12, 0.5 hour for Example 11 and over 0.7 hour for Example 9, to a mixture of the product of Example B-11, mineral oil and the product of the indicated Example of esterified interpolymers in the amounts (parts by weight) in the following Table and reacted for 2 hours at 160� C., while removing aqueous distillate.
EXAMPLE 13 The procedure of Example 6 is followed except the reaction is conducted in the presence of 10 parts mineral oil (PetroCanada 100N). The product is viscous but is not a gel. Viscosity=3447.7 centistokes.
EXAMPLE 14 A reactor is charged with 180 parts of the product of Example P-4 and 20 parts of the product of Example A-1. The materials are heated under N2 blanket for 2 hours. TBN=26.98; viscosity=790.8 centistokes.
EXAMPLE 15 A reactor is charged with 700 parts of the product of Example P-6, the material is heated to 110� C. whereupon 175 parts of the product of Example A-S are added. The temperature is increased to 160� C. and is maintained for 2 hours under N2. TAN=3.0.
EXAMPLE 16 A mixture of 150 parts of the product of Example P-6 and 10.5 parts mineral oil is heated to 110� C. whereupon 52.5 parts of the product of Example A-3 are charged. The temperature is increased to 160� C. and is maintained for 2 hours under N2. TAN=2.5, TBN=14.2, viscosity=259.55.
EXAMPLE 17 The procedure of example 16 is repeated with 200 parts of the product of Example P-6, 5.6 parts mineral oil and 30.4 parts of the product of Example A-3. TAN=2.4, TBN=17.3, viscosity=126.
EXAMPLE 18 The procedure of example 16 is repeated with 100 parts of the product of Example P-7, 14.4 parts mineral oil and 72 parts of the product of Example A-3. TAN=1.23, TBN=16.6 and viscosity=584
EXAMPLE 19 The procedure of example 16 is repeated with 114 parts of the product of Example P-7, 8 parts mineral oil and 40 parts of the product of Example A-3. TAN=1.86, TBN=22.4 and viscosity=200.
EXAMPLE 20 A reactor is charged with 100 parts of the product of Example B-10, 24 parts of the product of Example A-2 and 131.8 parts mineral oil (PetroCanada 100N). The materials are heated to 110� C. and mixed, under N2, for 0.5 hour. To this solution, 7.8 parts HPA-X polyamine bottoms are added dropwise, subsurface over 0.5 hour while maintaining temperature. The temperature is increased to 160� C., is held at temperature for 4 hours, then the materials are filtered. TAN=0.57; TBN=24.1; Viscosity=218.7 centistokes.
EXAMPLE 21 A reactor is charged with 800 parts of the product of Example A-6 and 160 parts PetroCanada 100N which is heated under N2 purge to 130� C., whereupon 107 parts of the product of Example P-1 are charged. Heating is continued to 160� C. and the temperature is maintained for 2 hours yielding a very viscous product.
EXAMPLE 22 A solution is prepared by mixing for 0.5 hour at 120� C. 96 parts of the product of Example 19 and 4 parts of polyethylene glycol dilaurate (Stepan Chemicals). Viscosity=1690.
EXAMPLE 23 The procedure of Example 21 is followed using 300 parts of PetroCanada 100N. Viscosity=967.
EXAMPLE 24 A solution is prepared as in Example 22 using 96 parts of the product of Example 21. Viscosity=687.
EXAMPLE 25 The procedure of Example 21 is followed using 350 parts of the product of Example A-7, 120 parts mineral oil and 50 parts of the product of Example P-1. Viscosity=594.
EXAMPLES 26-27 The products of Examples A-8 and P-8 are reacted for 1 hour, under N2 purge, in the amounts (parts by weight) and the temperatures indicated in the following Table.
EXAMPLE 28 A reactor is charged with 300 parts of the product of Example A-8 and 20 parts of the product of Example P-9. The materials are reacted for a total of 2 hours at 160-170� C. The materials are mixed at 120� C. with 36 parts diphenylalkane (Vista Chemical) and filtered. Viscosity @ 100� C.=1267 centistokes.
EXAMPLES 29-32 The products of Examples A-9 and P-8 are reacted, under N2 purge, in the amounts (parts by weight) and under the conditions indicated in the following Table. After reaction, each product is mixed with the indicated amount of diphenylalkane (DPA).
EXAMPLE 33 A mixture of 100 parts of the product of Example A-9 and 16 parts of the product of Example B-7 is heated, under N2 purge, to 80� C. whereupon 0.72 part diethylentriamine is rapidly added. The temperature is increased to 155� C. over 0.5 hour and is maintained for 1.5 hours. The temperature is reduced to 125� C., 16 parts diphenylalkane are added followed by stirring for 0.5 hour.
EXAMPLE 34 A reactor charged with 200 parts of the product of Example A-9 is heated, with N2 sparge, to 100� C. followed by addition of 10 parts of the product of Example P-10 and 24 parts of diphenylalkane. The materials are heated to 150� C. and are maintained at 150� C. for 2 hours. Viscosity @ 100� C.=1732 centistokes.
EXAMPLES 35-37 The products of Examples A-4 and P-6 are reacted, under N2 purge, at 160� C. for 2 hours in the amounts (parts by weight) indicated in the following Table.
EXAMPLES 38-39 The procedures of Examples 35-37 are repeated employing the reactants indicated in the following table.
EXAMPLES 40-41 The procedure of Example 16 is repeated using the amounts of oil and products of Examples A-2 and P-5 indicated in the following table.
EXAMPLE 42 The procedure of Example 16 is repeated with 100 parts of the product of Example P-6, 72 parts of the product of Example A-3 and 14.4 parts oil. Viscosity=580, TAN=2.3 and TBN=10.11.
EXAMPLE 43 The procedure of Example 16 is repeated replacing the product of Example P-5 with the product of Example P-4.
COMPARATIVE EXAMPLES The following examples are prepared and analytical values are obtained as set forth in examples 1-7 except the mixing is conducted under blending conditions, i.e., 70� C.:
Other oxidation inhibiting agents include materials such as alkylated diphenyl amines, hindered phenols, especially those having tertiary alkyl groups such as tertiary butyl groups in the position ortho to the phenolic �OH group, and others. Such materials are well known to those of skill in the art.
Pour point depressants may be included in the additive concentrates and lubricating oils described herein. Those which may be used are described in the literature and are well-known to those skilled in the art; see for example, page 8 of �Lubricant Additives� by C. V. Smalheer and R. Kennedy Smith (Lezius-Hiles Company Publisher, Cleveland, Ohio, 1967). Pour point depressants useful for the purpose of this invention, techniques for their preparation and their use are described in U.S. Pat. Nos. 2,387,501; 2,015,748; 2,655,479; 1,815,022; 2,191,498; 2,666,748; 2,721,877; 2,721,878; and 3,250,715 which are expressly incorporated by reference for their relevant disclosures.
(2) Reaction products of relatively high molecular weight aliphatic or alicyclic halides with amines, preferably polyalkylene polyamines. These may be characterized as �amrine dispersants� and examples thereof are described for example, in the following U.S. patents:
EXAMPLE AC-1 An additive concentrate is prepared by mixing together 7.6 parts of a zinc salt of mixed isopropyl-methyl amyl (46.8:53.2 by weight) dithiophosphoric acid, 5.45 parts di(nonylphenyl) amine, 2.73 parts of a sulfurized olefin, 2.83 parts of a calcium overbased (MR 3.5) sulfurized alkyl phenol, 1.76 parts of calcium overbased (MR 11) alkyl benzene sulfonic acid, 1.0 part sodium overbased (MR 16) polyisobutylene ({overscore (M)}n 950) substituted succinic anhydride, 1.55 parts magnesium overbased (MR 14.7) alkyl benzene sulfonic acid, 49.09 parts of the product of example 2, 0.08 parts of a kerosene solution of a silicone antifoam agent and sufficient mineral oil diluent to bring the total of all ingredients up to 100 parts.
EXAMPLE L-1 A 5W-30 lubricating oil composition is prepared by combining 10.4 parts of the additive concentrate of Example AC-1 which contains the product of Example 2, 7.5 parts of a 9% in oil solution of a ethylene-propylene-diene terpolymer viscosity improver, 0.09% of a styrene maleate copolymer neutralized with aminopropylmorpholine, in sufficient mineral oil basestock (Exxon stocks) to prepare 100 parts of lubricant. Viscosity @ 40� C.=58.4; @ 100� C.=10.28.
COMPARATIVE EXAMPLE L-1 Example L-1 is repeated replacing the additive concentrate AC-1 with an additive concentrate identical in every respect except replacing the composition of Example 2 with that of Example Comp-1. Viscosity @ 40� C.=56.24; @ 100� C.=9.82. It is apparent from Example L-1 and Comparative Example L-1 that in otherwise identical lubricating oil compositions greater viscosities are observed using composition prepared under reaction conditions compared to one prepared under blend conditions.
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