PLASTICIZER COMPOSITIONS COMPRISING ALKYLENE OXIDE-ALKYL PHENOL ADDUCT AND ESTER PLASTICIZER, AND CAULKING COMPOSITIONS CONTAINING THEM

Abstract: Plasticizer compositions and caulks or sealants containing them are disclosed. The plasticizer comprises (1) a water insolu­ ble adduct of ethylene or propylene oxide and an alkyl phenol and (2) a polyester plasticizer and is preferably used in aqueous latex caulks or sealants.

Description: PLASTICIZER COMPOSITIONS COMPRISING ALKYLENE OXIDE-ALKYL PHENOL ADDUCT AND POLYESTER AND CAULKING COMPOSITIONS CONTAINING THEM This invention is concerned with plasticizing compositions comprising certain alkylene oxide-alkyl phenol adducts and polyesters and caulking or sealant compositions containing them. The caulks or sealants may be used for filling structural joints in buildings. U.S. Patents Nos. 2 865 877 and 2 865 878 disclose coating compositions comprising a water soluble salt of a maleic anhydride/olefin copolymer and a water insoluble condensate of ethylene oxide and a C8- C18 alkyl phenol, the condensate containing an average of 1 to 5 oxyethylene units. The condensate may have a plasticizing effect on the copolymer and the two materials can serve as the sole binder in coatings, or can be used with acrylic polymers in dispersed or solubilized form. The water soluble salts are extremely hard and inflexible and are unsuitable as major components of caulks. U.S. Patent No. 2 889 297 discloses permanently tacky polyvinylacetate adhesives plÅasticized with polyglycol ethers of phenols which are similar to the adducts used in this invent ion. U.S. Patent No. 3 554 942 discloses aqueous spackling or sealant compositions comprising water soluble acrylic copolymer and a water soluble cellulose ether. U.S. Patent No. 3 561 996 discloses caulking compositions comprising thermoplastic polymer and, as adhesion promoter, certain silanes. One specific example in the patent describes a caulking composition of 82.6% solids formulated by mixing 195.1 kg of a 55% aqueous dispersion of an emulsion copolymer of 81.5% ethylacrylate, 15% methylmethacrylate and 3.5% itaconic acid; 4.29 kg of tert-octylphenoxypoly(39)ethoxy ethanol; 4.83 kg of sodium hexametaphosphate; 56.,34 kg of plasticiser for the copolymer (an oxypropylene ,derivative of m,p-cresylic acid); 12.21 kg mineral spirits; 0.576 kg of 30% aqueous polymethacrylic acid; 313.9 kg of pigment grade calcium carbonate extender and 7.81 kg of titanium dioxide pigment. U.S. Patents 3 759 915, 3 786 020 and 3 919 146 disclose caulks and sealants comprising polymer containing units having air curable radicals. The compositions are generally organic solvent based and may also contain oil modified alkyd or maleic polyester plasticizers. As noted above, acrylic latex caulks have been proposed in the past in which a plasticizer is recommended, the plasticizer being an adduct of propylene oxide and cresol in a mole ratio of 6:1. Aqueous caulks prepared from emulsion vehicles which are predominently acrylate or vinyl acetate require substan- tial amounts of plasticizer if they are to perform acceptably. The plasticizer enables the wet caulk to resist cracking as it dries and the dried, cured caulk to maintain its integrity and adhesion in the joint as it is subjected to stresses produced, for example, by temperature fluctuations. Caulk properties determined in the laboratory which bear directly on performance under use conditions are hardness, low temperature flexibility, tensile strength and % elongation. In addition to these properties the plasticizer should lend itself to production of caulks of low and stable consistency at normal solids content and should have low cost. Plasticizers presently in use in caulks are usually of two general types. One type, representing the greater volume of plasticizer used consists of relatively non-volatile monomeric esters such as the dialkyl phthalates and glycol dibenzoates. While such plasticizers are inexpensive, caulks containing them are generally deficient in one or more properties. The other type is certain aromatic polyethers which may provide improved properties but are relatively expensive. We have now found that plasticizers consisting essentially of certain alkylene oxide alkylphenol adducts and polyesters are useful in caulks containing an elastomeric synthetic polymer binder (as distinguished from the hard polymers for coatings mentioned above) especially latex addition polymers prepared by emulsion polymerization (although solvent-based caulks may also be used). We have also found, surprisingly, that the plasticizer properties and consistency of the compositions of this invention are generally better than either component alone. According to the invention there is provided a puttylike mastic, caulking or sealant composition containing a binder comprising an elastomeric synthetic polymer and a water insoluble plasticizer, in the weight ratio of plasticizer to binder of from 0.01:1 to 5:1, and optionally one or more additives in the form of an emulsifier, a dispersant, a base, a defoamer, a thickener, an organic solvent in the latex system, a dye, a pigment, a filler and an adhesion promoter wherein the plasticizer comprises (1) water insoluble or water-immiscible adduct of ethylene oxide and/ or propylene oxide with alkyl phenol, said adduct having the formula: : EMI3.1 Formula I in which RO is H or CH3, preferably H, x is an average number of from 1 to 7, preferably 2 to 6, more preferably 3 to 5, R is C1 to C12 alkyl, preferably C4 to C12 alkyl, more preferably C8 to C10 alkyl, y is 1 or 2, preferably 1, and (2) a water insoluble plasticizer being polyester of alcohol, preferably alkanol and aliphatic and/or aromatic carboxylic acid or ester thereof, the weight ratio of (1) to (2) being from about 10:90 to about 90:10, preferably from about 15:85 to about 60:40, and the consistency of the composition being from 5 to 100 seconds, more preferably 10 to 50 seconds, most preferably 10 to 35 seconds. Preferred water-insoluble polyester plasticizers for a balance of cost, availability and performance are one or more of those having the formulae: EMI4.1 Formula II wherein R1 and R2 are the same or different radicals and are C4-C12 alkyl, EMI4.2 Formula III wherein R3 and R4 are the same or different radicals and are H or C1-C10 alkyl, R5 is H or CH3, and z is 1 to 3, EMI4.3 Formula IV wherein R6, R7 and R8 are the same or different radicals and are C1-C8 alkyl, and R9OOC-(CH2)m-CooR10 Formula V where in R9 and R10 are the same or different radicals and are C1-C10 alkyl, and m is 2-8. In the compounds of Formula I, the ring position of the radical R preferably is predominantly para to the alkylene oxide substituent. The products used in the examples herein are such that y is predominantly 1, and the alkyl radical R is predominantly para to the alkylene oxide substituent. This water-insoluble ethylene oxide or propylene oxide condensate of the higher alkylphenol may be that derived from alkylphenols in which the alkyl group R may be methyl, isobutyl, n-octyl, t-octyl, nonyl, or dodecyl. The alkyl group is preferably of branched-chain character, such as in the case of t-octyl (1,1,3,3-tetramethyl butyl and 1,3,5trimethyl hexyl ("nonyl). Those condensates having an average of 5 or less oxyalkylene units (x is 5 or less, preferably 3 to 5) are generally the most advantageous, since they are more hydrophobic and are characterised by freedom from foaming and minimum sensitivity to water. While the value of x is an average number, the distribution, or deviation from a given value of x, is such that the material of Formula I is water-immiscible. Similar alkylene oxide adducts have been used in the past as surfactants to disperse pigments in coating compositions. The ester plasticizer (2) is conventional as a plasticizer for poly merit materials, and is prepared by known methods. Thus, the polyester may be prepared by reaction of a monohydric alcohol with an aliphatic or aromatic polycarboxylic acid or an ester of such acid, or by reaction of a polyhydric alcohol and an aliphatic or-aromatic monocarboxylic acid or an ester of such acid. For example, esters of Formula II can he prepared from phthalic; isophthalic, or terephthalic acids or lower (e.g. C1-C4) esters thereof, such as the methyl ester, and n-butanol, t-octanol, 2-ethylhexanol, isooctanol, dodecanol, or mixed alkanols. Compounds of Formula III can be prepared from diethylene glycol, triethylene glycol or tripropylene glycol and benzoic acid. Butyl, octyl, and ethylhexyl are typical alkyl substituents in Formula IV. Suitable alkyl groups in Formula V may be derived from the corresponding alkanols as noted above for the other formulae, and for Formula V materials, suitable dicarboxylic acids are adipic and sebacic. When either the material of Formula I or a material of one of Formulae II-V is used alone (as is shown by the Examples), the caulks are not wholly satisfactory in respect of properties such as low temperature flexibility, plasticizer efficiency, plasticizer permanence, consistency or viscosity, wood channel cracking or acceptable cost. Compounds of Formula I in which x is greater than about 7, e.g. an average of 8.0 to 10, become progressively more water sensitive. While such water soluble alkylene oxide adducts may appear to be satisfactory in the initial caulk, with weathering, the caulk loses the compound by leaching and becomes hard. The consistency or viscosity of the caulk increases as the value of x decreases; thus the most preferred values of x are 3-5. At any value of x in the range of 1-7, compounds of Formula I where RO is H cannot be used in the absence of the ester plasticizers of Formulas II-V, because of this increased viscosity. If a volatile diluent such as water is used in large quantities to assuage the viscosity problem, shrinkage of the caulk upon drying is too great. The weight ratio of adduct/polyester plasticizer elastomeric binder solids in the compositions of the invention is from about 0.01:1 to about 5:1, preferably from about 0.05:1 to about 2:1. The weight ratio of inorganic pigment and/or filler to elastomeric binder is from 0:1 (clear or translucent) to about 5:1, such as 1:1 to 5:1, preferably about 1:1 to 4:1, more preferably 1.5:1 to 3:1. In the plasticizer composition, the weight ratio of (1) to (2) is from about 10:90 to about 90:10, preferably from about 15:85 to about 60:40, more preferably about 20:80 to about 30:70, provided that a useful consistency is obtained and the cured caulk flexibility is satisfactory. Consistency of the formulated caulk, determined in the manner described below, is from 5 to 100 seconds, preferably 10-50 seconds, and most preferably 10-35 seconds. Caulking compositions must be fluid enough as measured by consistency to be applied easily, and yet must not slump or flow to a great extent after being applied to the substrate, nor shrink excessively upon drying or curing. An significant compositional feature of caulks to give these properties is the solids content, "solids" being defined as the total materials present which are nonvolatile under ordinary conditions of use. For aqueous latex, based caulking or sealing compositions according to the invention, the solids content should be from about 65% to about 90% by weight, preferably at least 75%, such as about 75% to about 85%, more preferably from about 80% to about 85%. Solids content is kept as high as possible while achieving a useful consistency. Organic solvent based sealants or caulks according to the invention also have as low a nonvolatile content as is possible, usually less than 15%, and greater than 5%, while providing a useable viscosity or consistency. If the solvent is a reactive or curable solvent such as a drying oil or a liquid polymerizable material, solids content may even be 100%. The binder may be formed of any organic solvent based or aqueous latex based elastomeric material, especially an aqueous latex of addition polymer of olefinically unsaturated monomers. Silicone rubbers and 1,3-diene rubbers such as styrene-butadiene copolymer latexes or butadiene-acrylonitrile latex polymers are examples of suitable binders. However, preferred compositions of the present invention, especially aqueous caulks and sealants, contain a vinyl addition polymer binder, preferably one predominantly (more than 50% by weight) of 1,3-diene, vinyl acetate or (meth)acrylic ester, such as polyvinyl acetate and copolymers of vinyl acetate with 0.5 to 40% by weight of acid, such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, acryloxyacetic acid and methacryloxypropionic acid and vinyl acetate-ethylene copolymers containing, for instance, 30-90% by weight of vinyl acetate units. More preferred, for a desirable balance of properties, is polymer containing units of at least one ester of acrylic and/or methacrylic acid with at least one alkanol or alkoxy lkarol containing up to 14 carbon atoms. For superior performance these polymers will have a Tg of less than 100C. Especially preferred elastomers are the polymers of acrylic acid esters, methacrylic acid esters, copolymers of lwo or more such esters with each other, copolymers' of one or more such esters with each other, and also copblymers of one or more such esters with one or more of the following monoethylenically unsaturated compounds: vinyl acetate, vinyl chloride, vinylidene chloride, acrylonitrile, styrene, vinyltoluene, acrylamide, methacrylamide or of any of the acids mentioned above as components of vinyl acetate copolymers. The most important of the acrylic esters are: ethyl acrylate, methyl acrylate, methyl methacrylate, butyl acrylate and methacrylate, and 2-ethylhexyl acrylate and methacrylate. Copolymers of these esters may be used, especially copolymers of one or more of these esters with 0.5 to 40% by weight of one of the acids mentioned above, preferably of acrylic acid, methacrylic acid, or itaconic acid. High molecular weight polymers, e.g. 10,000 to several millions, obtained by emulsion polymerisation and of waterinsoluble character under neutral or acid conditions are generally used in such caulking compositions. The elastomer preferably has a molecular weight of 10,000 to 600,000. When the vinyl polymer contains acid, it is generally neutralized partially or completely with ammonia or other volatile base, an alkali metal hydroxide, or an alkaline earth metal hydroxide. Examples of suitable caulking compositions in which the plasticizer composition of this invention may be used and acrylic latex elastomers which may be used in the caulks and sealants of this invention are disclosed in U.S. Patent No. 3 561 996, which is incorporated herein by reference to the extent necessary to show such latexes and caulk and sealant formulations. The elastomers suitable for caulks and sealants are well known to those skilled in the art, as are methods of preparing them. An important property of the solid elastomeric polymer is its T g and consequently the selection of monomers and their proportions depends upon their influence on the Tg. The T of the polymer should be below 100C (i.e., it must give g n rubbery product) preferably below OOC., and is more preferably below -lO0C. "tug" is a conventional criterion of poly g mer hardness and is described by Flory, "principal of Polymer Chemistry," pp. 56 and 57 (1953), Cornell University Press. See also "Polymer Handbook," Brandrup and Immergut, Sec. III, pp. 61-63, Interscience (1966). While actual measurement of the Tg is preferred, it may be calculated as described by Fox, Bull. Am. Physics Soc. 1, 3, p. 123 (1956). Examples of the T of homopolymers and the inherent Tg thereof which g permits such calculations are as follows: Homopolymer of T n-octyl acrylate -800C n-decyl methacrylate -600C 2-ethylhexyl acrylate -7O0C n-butyl acrylate -560C octyl methacrylate -200C methyl acrylate 90C t-butyl acrylate 430C methyl methacrylate 1050C acrylic acid 1060C These or other monomers may be blended to give the desired T of the copolymer. g Preferably, the caulk and sealant compositions of the invention contain one or more of pigment, dye and filler. Fillers or pigments, if used, are present in an amount depending upon the consistency desired and the presence or absence of thickening agents. - Suitable inert fillers and pigments include calcite, limestone (calcium carbonate), mica, talc, asbestos fiber or powder, diatomaceous earth, barytes, alumina, slate flour, calcium silicate, clay, colloidal silica, magnesium carbonate, titanium dioxide, carbon black, iron oxide, chrome green, phthalocyanine blue and magnesium silicate. The amounts of solvent, if any, filler, if any, and polymer solids are such as to give the caulking or sealant composition a putty-like or dough-like consistency. The usual surfactants and emulisifers commonly used in preparing or formulating latex polymers may be present. These include anionic, nonionic, and cationic materials. It is helpful, in some cases, to use a silane to improve wet adhesion to glass by the caulk. Suitable silanes include vinyltriethoxysilane, y-methacrloxypropyltrimthoxysilane, y-mercaptopropyltrimethoxysilane, y-glycidoxypropyltrimethoxysilane, ss-(3,4-epoxycyclohexl)ethyltrimethoxysilane, y-aminopropyltriethoxysilane, and N-(dimethoxymethylsilyl- isobutyl)-ethylenediamine. The silane may comprise from about 0.05 percent and 0.5 percent by weight of the total caulking composition. Higher amounts may be used but do not result in proportional improvements in adhesion. A base may be present as noted above, for example to neutralize carboxylic acid groups occuring in the elastomeric polymer. Suitable is a volatile base such as ammonia or a volatile water-soluble amine such as dimethylamine, triethylamine, triethanolamine, morpholine, N-methyl morpholine or picoline as well as inorganic bases. .4 The caulks and sealants of the invention may be contained in plastic lined paper tubes and may be for interior "or exterior use to seal crevices and gaps, such as by a bead between two substrates to be joined, such as around windows, doors and bathroom appliances. This invention also provides a plasticizing composition which comprises (1) water insoluble adduct of ethylene and/or propylene oxide with alkyl phenol, said adduct having the formula: EMI10.1 Formula I in which RO is H or CH3, preferably H, x is an average number of from 1 to 7, preferably 2 to 6, more preferably 3 to 5, R is C1-C12 alkyl, preferably C4-C12 alkyl, more preferably C8-C10 alkyl, and y is 1 or 2, preferably 1, and (2) a water insoluble plasticizer being polyester of alcohol preferably alkanol, and aliphatic and/or aromatic acid or ester of such acid, the weight ratio of (1) to (2) being from 10:90 to 90:10, preferably 15:85 to 60:40, more preferably 20:80 to 30:70. Component (2) is preferably polyester of oneor more of Formulae II, III, IV and V above, especially preferred is dioctyl phthalate for low cost. The same preferences and description of components (1) and (2) given above in respect of the caulking and sealant compositions also applies to the plasticizer compositions comprising these two components. Test Methods The test methods for determining the properties specified in the following examples are well known in the art and may be found in U.S. Patents Nos. 3 561 996 and 3 919 146 and Resin Review, V, XVI, No. 3, (1966) "Test Procedures for Evaluating Aqueous Caulking Components and Elastomeric Solvent-Base Sealants", Rohm and Haas Company, Philadelphia 19105. These documents are incorporated herein by reference to the extent necessary to enable use of the methods. Consistency - The test method is that of U.S. Federal Specification TTS-00230. A sample of compound and a 177.4 ml conventional cylindrical caulking tube (15.24 x 4 cm outside diameter) are conditioned for at least 16 hours under standard conditions (25 + l.loC, relative humidity 50 + 5%). At the end of the conditioning period the tube with plunger in place is filled to capacity with compound from the nozzle end and placed in an air-powered Semco caulking gun. A standard Semco nozzle with a 3.18 mm diameter orifice (used in all the following examples) is attached to the cartridge. The compound is then gunned at 35153 kg m 2 pressure into an empty container while a stopwatch is used to time the extrusion through the orifice. Gunning time is recorded in seconds. For solvent-base sealants, the procedure is the same except that no nozzle is attached to the cartridge and extrusion is through a 11.18 mm orifice. Wood Channel Cracking - White pine channels 19.05 mm wide by 9.53 mm deep are filled with caulk and the surface of the caulk is levelled flush with the wood channels. The filled channels are then allowed to dry under the specified conditions (e.g. at 500C for seven days) and the condition of aulk is assessed for cracking. Each test gives comparable results. Low Temperature Flexibility - A slab of caulk 6.35 x 38.1 x 114.3 mm when wet is cast atop a 0.79 x 66.7 x 146.1 mm aluminium sheet using a brass frame which is filled with excess caulk applied with a caulk gun and levelled off with a tongue depresser blade. The frame is removed and the sample is stored for a week under the standard conditions. The sample is then transferred to an oven for another week at OOC for cure. Subsequently the sample is placed in a refrigerated box at the specified temperature and equilibriated for at least one hour. The sample is then slowly bent in sequence over mandrels of diameter 101.6 mm, 50.8 mm, 25.4 mm and finally bent through 1800 upon itself. (This sequence is abbreviated where noted in the examples.) Any cracking is taken as an indication of failure. Shore "A" Hardness - A sample of compound is stored for 16 to 24 hours at the standard conditions. A brass frame with inside dimensions 38.1 mm wide by 127 mm long by 6.35 mm deep is centred on a 76.2 mm by 152.4 mm plate of 16 to 24 gauge aluminium and filled with the conditioned compound. Excess compound is struck off with a flat spatula. A thin knife is then run along the inside edge of the frame to free the compound, and the frame is removed. Two such specimens are prepared and allowed to cure at the standard conditions for 14 days. After the curing, Shore "A" hardness measurements are made with a Shore Durometer, Three readings are taken on each specimen and the average of the six readings is the accepted value. Readings are.taken by the instantaneous method, using l-kilogram pressure. Tensile Strength and Elongation - A sample of compound is stored for 16 to 24 hours at the standard conditions. A brass frame with inside dimensions 76.2 mm wide by 127 mm long by 6.35 mm deep is placed on a Teflon-coated steel plate and filled with the conditioned compound. Excess compound is struck off with a flat spatula. A thin knife is then run along the inside edge of the frame to free the compound, and the frame is removed. The prepared specimen is then air-cured at the standard conditions until it is cured through. (Not less than 2 weeks). When cure is complete, the specimen is cut with a dumbbell-shaped die measuring 76.2 mm long by 19.05 mm wide and having a neck width of 6.35 mm. The Instron Tensile Tester is then used to determine the tensile and elongation properties of the dumbbell-shaped specimen of cured compound, at the following settings: Crosshead speed 5.08 mm/min. Chart speed 5.08 mm/min. Gauge length 12.7 mm opening Calibration variable, according to compound Integrator automatic Results can be computed with the following formulas: Tensile Strength T= f tw where T = tensile strength in kg m 2 f = force at break in kg w = sample width in m t = sample thickness in m Elongation EMI14.1 where E = percent elongation 1 = gauge length 0 1 = length of sample at break Slump - A sample of compound is stored for 16 to 24 hours at the standard conditions. A rectangular channel of 302 stainless steel with inside dimensions 19.05 mm wide by 152.4 mm long by 12.7 mm deep and with the bottom or long surface extended 50.8 mm at one end, is conditioned at the standard conditions for 1 hour. The channel is then filled with compound using a spatula and positioned vertically with the 50.8 mm extended portion down. At the end of 1 hour the sag of the compound at the lower end of the channel is measured to the nearest 1.6 mm. Freeze Thaw Stability - A sample of compound is placed in an 227 ml glass jar, leaving at least 13 mm of air space at the top. The jar is capped and placed in a freezer at -100C for 16 hours, then held at room temperature for 8 hours. This cycle is repeated twice, making three complete freezethaw cycles in all. After each freeze-thaw cycle the consistency and pH of the sample are measured and any significant changes are noted. It is also an advisable precaution to run peel-adhesion tests on several substrates to ensure that no changes in adhesion properties have occurred. l8Oo Peel Adhesion - A 76.2 mm by 127 mm sample of each test surface is washed with detergent solution, rinsed with clear water, and finally cleaned with methyl ethyl ketone. Porous substrates should be at least 6.35 mm in thickness and should be virgin surfaces that have been brushed with a stiff-bristle paint brush to remove loose or foreign particles. The surfaces are primed if such treatment is demanded. After the test surfaces are clean, a strip of 25.4 mm Teflon masking tape is placed across the width of each in such a way that the lower edge of the tape is parallel to and at least 50.8 mm from the shorter edge of the test surface base. A sample of compound that has been stored for 16 to 24 hours at the standard conditions is spread with a spatula or forced in a heavy bead from a caulking gun to give a thickness of not less than 3.18 mm over the entire area of the test surface. Spare bases of the same thickness as the test surface base are placed on either side of the test base, butting against it. Spacer.bars measuring 50.8 mm wide by 152.4 mm long by 1.59 mm thick are placed on the assembly in such a way that they just bridge the joints between the test base and the spare bases on either side. Two 25.4 mm by 254 mm strips of desized, grade-A airplane fabric (0.133 kg per metre, 80/84 thread count) are laid lengthwise over the specimen of compound. The entire assembly is then covered with a 254 mm by 304.8 mm sheet of 25.4 vm Mylar, which serves as a release member. A cylinder of practical size and sufficiently rigid to depress the compound when pressure is applied is rolled across the assembly, in such a manner as to avoid ent:lapping air, until the thickness of the compound between tEle cloth and the test surface is reduced to 1.59 mm. The Mylar sheet is then withdrawn carefully so that the assembly beneath is not disturbed. When the compound has set up to a point where no distortion of the test structure will occur, a thin (0.79 mm or less) coating of compound is applied over the cloth strips to protect against moisture ant to minimize adhesion failure between the cloth and the compound specimen. Following preparation the test specimens are allowed to air-cure for 7 days at the standard conditions. The specimens are then divided into two lots, one lot receiving an additional 7 days' cure at the standard conditions and the other lot being completely immersed in distilled water at the standard conditions for 7 days. Immediately following this 14-day cure, the specimens which have been immersed in water are removed and wiped dry. For compounds which do not reach full cure in 2 weeks at standard conditions, the following accelerated curing technique is employed. The samples are cured for 3 days at the standard conditions, then for 7 days at 87.780C. The specimens are divided into two lots, with one lot being tested immediately and the other lot receiving 7 days' additional cure immersed in water before testing. Cured specimens of compound are prepared for testing by cutting the compound through to the test surface with a razor blade, along the edges of the cloth strips. The portions of compound on either side and between the cloth strips are removed from the test surface and discarded. The specimen is then placed in an Instron Tensile Tester and the cloth is pulled back on itself at an angle of 1800 to peel the compound from the test surface. The rate of separation of the jaws of the machine is maintained at 50.8 mm per minute, giving a peel rate of 25.4 mm per minute. Care should be taken to run the integrator during a 25.4 mm length of delamination which does not include the initial or final periods of stress, to avoid shock of loading and decay. If the cloth strip begins to peel away from the compound during the test, the strip of compound is cut across with a sharp razor blade at that point in order to get separation at the interface between the compound and test surface. A minimum of five strips is tested for each condition (water soak and air cure) on each substrate. The average peel strength in kg/m is obtained during each determination by using the integrator attachment and calculating by the following formula P = XS Xo where P = average peel strength in kg/m X = integrator reading over period of test Xo = integrator reading when full scale load is applied S = full scale load in kg Some preferred embodiments of the invention will now be more particularly described in any of the following examples in which all parts and percentages are by weight unless otherwise stated. Comparative examples are provided and noted as such. In the following examples, the basic formulation given below was used, the difference being in the identity of the plasticizer. The abbreviations used have the following meanings; and in the example numbers "C" means a comparative example. Abbreviation Meaning X-l Adduct of Formula I, RO = CH3, x = 6, y = 1, R = methyl. X-3 Adduct of Formula I, RO = H, x = 3, y = 1, R = 1,1,3,3-tetramethyl butyl (tert.-otyl). 1-C(CH )2CH2C(CH3) X-4 Adduct of Formula I, RO = H, x = 5, y = 1, R = 1,1,3,3-tetramethyl butyl. N-4 Adduct of Formula I, RO = H, x = 4, y = 1, R = trimethyl hexyl ("nonyl"). N-5 Adduct of Formula I, RO = H, x = 5, y = 1, R = trimethyl hexyl. N-6 Adduct of Formula I, RO = H, x = 6, y = 1, R = trimethyl hexyl. DOP Dioctyl phthalate Dt3P Dibutyl phthalate DIBP Diisobutyl phthalate DINP Diisononyl phthalate BIDP Butyl isodecyl phthalate DPGD Dipropylene glycol dibenzoate It should be noted that commercially available alkyl phenols used to prepare the adducts of Formula I are mixtures of compounds in that R may represent a mixture of isomers, particularly as the number of carbon atoms in the radical increases, and that 'monosubstituted' materials (the pre ferred case where y is 1) may contain small quantities (up to about 10%) of, usually, disubstituted compounds. For example, octylphenol contains approximately 85-90% mono-derivative of which about 98% is the para-isomer, the balance being ortho. The dioctyl content is about 5-10%. Nonylphenol contains about 3-5% dinonylphenol and less than 1% of the ortho derivative. In the case where R is "nonyl", that is, trimethyl hexyl, about 75% is the 1,3,5-trimethyl hexyl isomer on a molar basis, with the remainder being other trimethyl hexyl isomers. The alkyl phenols used in preparing the adducts are usually mixtures of the meta or ortho and para isomers, and may contain small amounts of impurities. In the adducts identified as X-3, X-4, N-4, N-5, and N-6, R is about 90:10 p:o, molar basis, with respect to the alkylene oxidesubsti- tuent. In the X-l adduct, R is about 80% para, meta, with about 2% ortho cresol, the remainder being xylenols and other impurities. Comparative Example 1 The following prior art formulation is used to prepare a caulk by mixing the components in the order given in a high shear mill, such as a Sigma mixer. Milling time is 90 minutes and the defoamer is added during the last five minutes of mixing. All materials are.added directly to the mill without preparing solutions or emulsions of liquid and solid components. The caulks in the following examples are prepared by the same method from the formulation below by substituting the new plasticizers for that in the formulation. The formulation below may be referred to as the basic formulation. Component Parts EA/MMA/IA 87.5/10/2.5 emulsion copolymer 430.17 55% solids* Octyl phenol reacted with ethylene oxide 9.146 approximately 1/40 molar ratio, 70% solids (Tritone X-405, emulsifier) Sodium polyphosphate (pigment dispersant) 10.65 Adduct of cresol reacted with propylene oxide, 124.21 1/6 molar ratio (plasticizer)** Milleral solvent thinner ("Varsol"TM) 26.91 Component (continued) Parts Glycidoxypropyltrimethoxy silane (wet 0.59 adhesion promoter, premixed with plasticizer or solvent) Sodium polymethacrylate, 30% solids in water 1.27 (pigment dispersant) Ammonium hydroxide 28% 1.84 Ground calcium carbonate, ave 4 u, oil 692.06 adsorption 14 (filler) Titanium dioxide (rutile), oil adsorption 17.72 24 (pigment) polydimethyl siloxane defoamer, 10% 1.0 solids (Sag 470TM) * EA is ethyl acrylate, MMA is methyl methacrylate, IA is itaconic acid. As elsewhere herein, all parts are by weight unless otherwise specified. The polymer has a minimum film forming temperature of less than 20C, the T is about -90C, and the pH of the latex is about 4.5. The latex is anionic. ** This plasticizer when used alone, is not as desirable as the plasticizer combination of the invention. For example, cost is a factor. Other factors appear in connection with the examples. TABLE I Example Consistency Wood Chancel No Plasticizer (sec) Cracking C2 X-l 15 Pass C3 X-3 very high 300 complete adhesion loss C4 X-4 very high 300 Pass C5 tJ-4 1745 Pass C6 N-5 1565 Adhesion loss C7 N-6 2905 Adhesion loss C8 DOP 356 Pass 9 N-4/DOP 25/75 18 Pass 10 N-4/DOP 50/50 64 Pass 11 X-3/DOP 25/75 25 Pass 12 X-3/D0P 50/50 57 Pass TABLE I continued Shore "A" 4 Hardness Film Properties Air Dried Low Temp 3 Air 2 wk Tensile Elonga Example Flexibility Dried + 3 wk Strength tion No -2610C -17.80C 2 wk 7O0C kg/m (%) C2 Pass Pass 8 42 40778 424 C3 Fail Pass 5 39 CLi CS Fail Pass 0 31 Fail Pass 12 42 C7 Fail Pass 9 41 C8 Fail Pass 32 50 85071 , 225 9 Pass Pass 13 42 51324 303 10 Pass Pass 0 39 11 Pass Pass 17 42 12 Pass Pass 12 39 1 Time to gun a 177.4 ml cartridge under 35153 kg/mê pressure. Consistency given is for freshly made caulk. 2 19.05 mm x 9.53 mm pine wood channel. 3 1800 bend. Tensile strength and % elongation at maximum shear. 5 Consistency increased greatly on aging at R.T. (room temperature, about 21.1 C). Consistency doubled on aging at R.T. TABLE II Example Consistency Wood Chancel No Plasticizer (sec) Cracking Cl3 N-4 1748 Pass C14 DIBP 8 Pass 15 N-4/DIBP 25/75 13 Pass 16 N-4/DIBP 50/50 31 Pass C17 DINP 318 Severe cracking 18 N-4/DINP 25/75 14 Pass 19 N-4/DINP 50/50 45 Pass C20 BIDP 15 Pass 21 N-4/BIDP 25/75 24 Pass 22 N-4/BIDP 50/50 62 Pass C23 DPGD 9 Pass 24 N-4/DPGD 25/75 26 Pass 25 N-4/DPGD 50/50 298 Pass TABLE II continued Shore "A" Hardness Low Temp. Air Dried Example Flexibility7 Air Dried 2 wk + 3 wk No -26.10C -17.80C 2 wk 700C C13 Fail Pass 12 42 C14 Pass- Pass 48 55 15 Pass Pass 11 47 16 Pass Pass 0 40 C17 Fail Fail 36 47 18 Fail Pass 20 40 19 Pass Pass 0 38 C20 Pass Pass 45 51 21 Pass Pass 20 49 22 Pass Pass 0 47 C23 Fail Pass 30 50 24 Fail Pass 22 53 25 Pass Pass 7 48 7 25.4 mm diameter mandrel. 8 Consistency increased greatly on aging at R.T. Approximate relative costs of some of the materials are of interest. TABLE III Plasticizer Cost ($/kg bulk) X-l $0.34 X-3 0.23 N-4 0.23 DOP 0.14 DBP 0.16 DIBP 0.16 DINP 0.14 DPGD 0.16 BIDP 0.14 These materials are water-immiscible liquids at 21.10C. The caulking materials of Tables IV-VI were prepared using the basic formulation but in quantities four times the amount to give 3.785 dm3 samples. TABLE IV Consistency (sec) Tensile Example 1 month (max stress No Plasticizer Initial 50 C Slump kg/m C26 X-1 15 (13)1 - (13) 0 40778 27 N-4/DOP 18 (33) 25 (42) 0 51324 25/75 28 N-4/DIBP 22 (17) 25 (20) 0 46403 25/75 29 N-4/DPGD 25 (22) 31 (23) 0 45700 25/75 C3O DOP 35 (38) 85 (44) 0 85071 C31 DIBP 19 (15) 18 (16) 0 81556 C32 DBGD 28 (19) 33 (17) 0 76635 TABLE IV continued Wood Channel Cracking Elongation Example Weatherometer (% at max. No AT9 5009 500 hour10 stress) C26 Pass (Pass) Pass (Pass) Pass 424 27 Pass (Pass) Pass (Pass) Pass 303 28 Pass (Pass) Pass (Pass) Pass 329 29 Pass (Pass) Pass (Pass) Pass 332 C30 Pass (Pass) Pass (Pass) Pass 225 C31 Pass (Pass) Pass (Pass) Pass 202 C32 Pass (Pass) Pass (Pass) Pass 215 TABLE IV continued Low Temperature Flex. (-26.l0C)2 3 days RT 3 days RT 7 days 500C 7 days 50 C Example Weatherometer No ¯¯¯¯¯¯¯¯¯ ¯¯¯¯¯¯¯¯¯¯¯ 500 hours C26 Pass (Pass) Fail6 27 Pass (Pass) Pass 28 Pass (Pass) Pass-7 29 Fail3 (Fail4) Pass-7 C30 Fail5 (Fail5) Fail8 C31 Fail3 (Fail4) Fail5 C32 Fail5 (Fail5) Fails TABLE IV continued Shore "A" Hardness 3 days RT 7 days 50 C Example 2 weeks RT Weatherometer No 2 weeks RT 3 weeks 70 C 500 hours C26 0 (22) 42 (44) 53 27 13 (23) 42 (47) 48 28 11 (21) 42 (48) 53 29 10 (27) 46 (49) 53 C30 32 (40) 50 (53) 57 C31 27 (32) 55 (58) 63 C32 23 (34) 51 (55) 59 Values shown in parentheses are repeat preparations made using a different lot of acrylic latex. 2 Test sequence: film bent around 101.6 mm, 50.8 mm, 25.4 mm diameter cylindrical mandrels, then 1800 flex, BT = room temperature (about 21.10C). 3 Pass 25.4 mm, fail 1800. Crack 25.4 mm, fail 1800.. Pass 50.8 mm, fail 25.4 mm. 6 Pass 101.6 mm, fail 50.8 mm.(Pass- = Pass minus). Cracking 1800. 8 Crack 50.8 mm, fail 25.4 mm. 9 12.7 mm x 19.05 mm. 1O 6.35 mm x 12.7 mm. TABLE V1 Freeze Peel Strength (kg/m) Thaw Stability Aluminium Glass Wood Ex. (cycles No. Plasticizer passed) Dry Wet Dry Wet Dry Wet C33 X-1 3 144.6 0 162.5 44.65 44.65 5.36 CP3 A CP CP A A 34 N-4/DOP 3 37.5 0 139.3 irr.ê 30.36 3.57 25/75 A/LC A CP A A 35 N-4/DIBP 1 37.5 0 135.7 1.78 42.86 3.57 25/75 A/LC A CP A A/LC A 36 N-4/DPGD 3 60.72 0 126.8 35.72 48.22 5.36 25/75 A/LC A CP CP A/LC A C37 DOP 2 23.22 0 30.36 8.93 19.64 3.57 A/LC A A/C CP A A C38 DIBP O - 80.36 0 67.86 14.29 30.36 12.5 CP A CP CP A A C39 DPGD 0 76.79 0 80.36 17.86 35.72 8.93 <RTI ID=30.13> CP A CP CP A A 1 Caulks are the same as repeat preparation in Table IV. 2 Irregular values varied widely in different areas; 25.0 CP, 10.7 CP, 3.57 A.; probably this sample incompletely cured. 3 A is adhesive failure between the solid substrate and the caulking material. C is cohesive failure within the body of the caulk layer. CP is the case in which the adhesion to the substrate is greater than to the fabric top layer. LC is light cohesive failure of the caulk. Small patches or spots remain on the substrate; failure is thus mostly adhesive. TABLE VI Weiffht Loss of Caulks on Hot Water (at 7O0C for 1 month) Extraction Weight Loss (%)2 Water Example Same Water Changed No Plasticizer Throughout Weekly C40 X-1 3.9 6.4 41 N-4/DOP (25/75) 1.8 2.1 42 N-4/DIBP (25/75) 4.9 5.2 43 N-4/DPGD (25/75) 3.0 3.4 1 Caulk samples air dried to constant weight before extraction. 4.5 gm disc of cured caulk, 6.35 mm thick, extracted in 250 ml water. Plasticizer is about 12% of caulk solids. In considering the test results of Tables III-VI, it should be borne in mind that the caulks under study were prepared by "plugging in" the various plasticizers in the standard Basic Formulation. No attempt was made, by even minor compounding modifications, to alter properties found wanting. The results place in perspective the mixtures of alkyl phenol/alkylene oxide adducts with ester plasticizers vis-a-vis the prior art caulk plasticizer X-l by itself and the ester plasticizers themselves. Overall the plasticizer combination mixtures approximate X-l in performance at lower cost and show advantages over the ester plasticizers. This is especially true of the mixture with dioctyl phthalate which is the lowest cost ester plasticizer readily available. In caulk performance properties reflecting plasticizer cfficiency, i.e., Shore hardness, reduction in Tg, low temperature flexibility and tensile/elongation the plasticizer mixtures are near matches for X-1 and are superior to the ester plasticizer. In plasticizer permanence the mixtures appear to have advantages over both X-l and the ester plasticizers (Weatherometer data under LTF and Shore hardness, Table IV, and extraction data, Table VI). The mixtures show deficiencies in caulk consistency and adhesion. Caulk consistency is higher than is produced with X-l and varies considerably as DOP source and latex lot is varied, but is affected only slighly by accelerated or natural caulk aging. Caulks, at the consistencies produced by the mixtures, are usable and there is not a serious consistency problem; consistency can be lowered by reducing total solids content, even a very slight lowering in some cases, but must be controlled to avoid seriously affecting shrinkage. Nevertheless, routine study of consistency is justified. Adhesion data reported are for one week drying only, and at this drying time, drying intervals and after minor formulation and mixing procedure modificatios are within the realm of routine experimentation. Herein, whenever a range of values is given, such as "from 1 to 7", "1-7", or "between 1 and 7", it is intended that the range be inclusive of the stated values, in this case, 1 and 7. "(Meth)acrylic" acid refers to methacrylic acid or acrylic acid. TABLE VII Properties of Caulks Containing Dioctyl Phthalate/Plasticizer X-l Mixtures in Place of X-l Alone Consistency Wood Channel (sec) Crack Resistance Example DOP/X-1 30 Days RT No Ratio Initial 500C (200 to 220C) SO0C C44 100/0 34 60 Excellent Excellent IS 75/25 17 23 Excellent Excellent 46 50/50 15 18 Excellent Excellent 47 25/75 10 12 Excellent Excellent C48 0/100 9 13 Excellent Excellent TABLE VII continued Low Temp. Flexi bility (-26.10C)1 Shore "A" hardness Ex. 2 Weeks 2 Weeks 2 Weeks 2 Weeks RT + 2 Weeks RT + No. RT 500C RT 2 Weeks 5O0C 3 Weeks 50 C C144 Failed Failed 36 58 52 1800 50.8mm Flex Mandrel 45 Passed Failed 35 51 46 1800 1800 Flex Flex 46 Passed Passed 30 52 50 1800 1800 Flex Flex 47 Passed Passed 26 47 45 1800 1800 Flex Flex C48 Passed Passed 25 45 43 1800 1800 Flex Flex 1 Test Sequence: 101.6 mm mandrel, 50.8 mm mandrel, 25.4 mm mandrel, 1800 Flex, as in Table IV.

Claims: Claims: 1. A putty-like mastic, caulking, or sealant composition containing a binder comprising an elastomeric synthetic polymer and a water insoluble plasticizer, in a weight ratio of plasticizer:binder of from 0.01:1 to 5:1, and optionally containing one or more of an emulsifier, dispersant, organic solvent, base, pigment, filler, dye, defoamer, thickener and adhesion promoter, wherein the plasticizer comprises (1) water-insoluble adduct of ethylene and/or propylene oxide with alkyl phenol, said adduct having the formula EMI35.1 in which RO is H or CH3, x is an average number of fro 1 to 7, R is C1 to C12 alkyl, and y is 1 or 2, and (2) a water insoluble plasticizer being polyester of alcohol and aliphatic and/or aromatic carboxylic acid, or ester of such 2zid, the weight ratio of C1) to (2) being from 10:90 to 90:10, and the composition having a consistency of from 5 to 100 seconds. 2. A composition as claimed in claim 1 wherein the binder comprises an aqueous latex of an addition polymer containing units of at least one of a 1,3-diene, vinyl acetate and an acrylic and/or methacrylic acid ester. 3. A composition as claimed in claim 2 wherein the polymer contains units of at least one ester of acrylic and/or methacrylic acid with at least one alkanol or alkoxyalkanol containing up to 14 carbon atoms, the Tg of the polymer being less than lO0C. 4. A composition as claimed in any of claims 1 to 3 wherein component (2) comprises polyester of one or more of the following formulae EMI36.1 wherein R1 and R2 are the same or different radicals and are C4-C12 alkyl EMI36.2 wherein R3 and R are the same or different radicals and are H or C1-C10 alkyl, R5 is H or CH3, and z is 1 to 3, EMI36.3 wherein R6 R7 and R8 are the same or different radicals and are C1-C8 alkyl, and R9OOC-(CH2)m-COOR10 wherein R9 and R10 are the same or different radicals and are C1-C10 alkyl, and m is 2 to 8. 5. A composition as claimed in any of claims 1 to 4 containing pigment and/or filler in a weight ratio to elastomer of from 1:1 to 5:1 in which the weight ratio of component (1) to component (2) is from 15:85 to 60:40 and the consistency is from 10 to 50 seconds. 6. A composition as claimed in any preceding claim in which the consistency is from 10 to 35 seconds. 7. A composition as claimed in any preceding claim in which RO is H and R is C4-C12 alkyl. 8. A composition as claimed in any preceding claim in which x is 2 to 6. 9. A composition as claimed in claim 8 in which x is 3 to 5 and R is C8-C1O alkyl. 10. A composition as claimed in any of claims 2 to 9 in which component (2) comprises dioctyl phthalate. 11. A plastIcizer composition comprising (1) water-insoluble adduct of ethylene and/or.propylene oxide with alkyl phenol, said adduct having the formula: EMI37.1 in which RO is H or CH3, x is an average number of from 1 to 7, R is C1 to C12 alkyl, and y is 1 or 2, and (2) a water insoluble plasticizer being polyester of alcohol and aliphatic and/or aromatic carboxylic acid, or ester thereof, the weight ratio of (1) to (2) being from 10:90 to 90:10. 12. A composition as claimed in claim 11 in which component (2) comprises polyester of one or more of the following formulae: EMI38.1 wherein R1 and R2 are the same or different radicals and are C4-C12 alkyl EMI38.2 wherein R3 and R are the same or different radicals and are H or C1-C10 alkyl, R5 is H or CH3, and. z is 1 to 3 EMI38.3 wherein R6, R7 and R8 are the same or different radicals and are C1-C8 alkyl, and R900C-(CH2)m-COOR10 wherein R9 and R10 are the same or different radicals and are C1-C10 alkyl, and m is 2 to 8. 13. A composition as claimed in claim 11 or 12 in, which the weight ratio of component (1) to (2) is from 15:85 to 60:40. 14. A composition as claimed in any of claims 11 to 13 in which RO is H and R is C4-C12 alkyl. 15. A composition as claimed in any of claims 11 to 14 in which x is 2 to 6. 16. A composition as claimed in claim 15 in which x is 3 to 5 and R is C8-C10 alkyl. 17. A composition as claimed in any of claims 12 to 16 in which component (2) comprises dioctyl phthalate.

Inventors: JORDAN, JR., ARTHUR DAVID, LAVELLE, JOSEPH ARTHUR
Applicants: ROHM AND HAAS COMPANY
Application year: 1979
Main classification: C09D5
IPC codes: C09K3, C09D5, C08L33, C08L67, C08L71, C09D133