MXPA01003532A - Latex polymer compositions - Google Patents

Abstract

Novel latex polymers containing highly branched neo vinyl esters and ethylenically unsaturated reactive surfactants are disclosed. Aqueous compositions containing these latex polymers are particularly suitable for use in coatings, adhesives, caulks and sealants where exceptionally high water and alkali resistance is desirable.

Description

LATEX POLYMER COMPOSITIONS FIELD OF THE INVENTION This invention relates to novel latex polymers and aqueous compositions containing the same, which are capable of exceptionally high water resistance when used in coatings and other applications. The aqueous latex compositions containing the novel polymers are prepared by the emulsion polymerization of ethylenically unsaturated monomers including highly branched neovinyl esters and ethylenically unsaturated reactive surfactants. Aqueous latex compositions containing these polymers are especially suitable for use in coatings, adhesives, caulks and sealants where excellent water resistance is desirable. Such polymers are also suitable for use as additives, modifiers, inks, binders for dyes and pigments, and textile treatments.

BACKGROUND OF THE INVENTION Water resistance is an important property for protective compositions used as surface coatings, adhesives, caulks and sealants. It is known that water penetrates porous materials and contributes to their deterioration. Examples of such damage include warping and swelling of wood, splitting and quartering of concrete and masonry caused by freeze / thaw cycles and dissolved salts and corrosion of reinforcing steel in concrete caused by chloride ions found in thawed salts. Protective compositions containing a variety of polymers have been suggested for use in the elimination or reduction of such damage. Many of these compositions require the presence of organic solvents. Due to its recognized environmental toxicity and flammability problems, a significant effort is being made to replace these solvent-based systems with water-based systems. Considerable effort has been devoted to the development of water-based polymer systems which have sufficient water resistance to be useful in protective coating compositions. Such water-based polymer compositions are prepared by well-known emulsion polymerization techniques which usually require the presence of one or more surfactants, often in combination with water-soluble protective colloids, to emulsify the monomer reagents and stabilize the product. of late polymer latex. Conventional surfactants do not react with the monomers and residual amounts of these surfactants in coatings and other protective compositions can have a negative effect on properties such as water resistance. These surfactants can migrate through the polymer and form aggregates in the polymer matrix. Surfactants can also • migrate to the surface of the dried polymer as well as to the polymer and interface of the substrate. Surfactants and water soluble protective colloids are water sensitive materials that can cause flushing and bleaching as well as swelling of the dry latex polymer when in contact with water. Blushing, bleaching and swelling of water-dried latex polymers can destroy the integrity of the polymer latex and eventually cause the protective composition to fail. It would be desirable to have a polymer latex made by emulsion polymerization that does not have the sensitivity to water resulting from the presence of the conventional surfactants or protective colloids required for emulsifier monomers and to stabilize the polymer latex during polymerization and after handling. . An improvement in the water resistance of protective compositions containing aqueous polymer latexes has been achieved by replacing a class of compounds known as reactive surfactants by part or all of the surfactants conventional materials used in the preparation of polymer latexes. The reactive surfactants are covalently bound to the latex polymer and thus are not subjected to migration and other problems associated with conventional surfactants. Reactive surfactants are similar to conventional surfactants with surface activity imparted by the hydrophilic and hydrophobic portions in the molecules. The hydrophilic portion can be either ionic or non-ionic in nature. The reactive surfactants also ethylenically contain unsaturated double bonds for the reaction of free radical with other monomers during the polymerization. The North American Patent No. 4, 224, 555, describes the preparation of reactive surfactants which are comprised of sulfonated media moieties of the maleic anhydride ring with alkoxylated alkylarylsols and their applications for imparting stability to polymers made by emulsion polymerization. U.S. Patent Nos. 4,075,411, 5,563,214, 5,296,627, 5,332,854, 4,939,283, 5,324,862, 4,814,514 are examples that describe other representative types of reactive surfactants and their use as emulsifiers in emulsion polymerization. In an article presented at Eurocoat 95, entitled "A New Class of Latex Binders for Water-Bourne Wood Coatings," M. Slinckx and S. Spanhove, International Congress Eurocoat, Lyon, pp. 19-21, highly branched neovinyl esters such as vinyl neodecanoate and vinyl neononanoate are described as providing improved water resistance when incorporated into acrylic polymers. This article describes such neovinyl esters polymerized with methyl methacrylate and 2-ethylhexyl acrylate. These monomers are polymerized in emulsion in the presence of conventional surfactants. While the compositions exhibit improved water resistance, they are not good as solvent based systems and neovinyl esters are recognized as being difficult to polymerize with certain monomers. Therefore, the protective compositions industry is still looking for an aqueous polymer system that offers exceptional water resistance and exterior durability provided by solvent-based systems.

COMPENDIUM OF THE INVENTION __ _ This invention relates to novel latex polymers having excellent water resistance, comprising: (a) at least one neovinyl ester, (b) at least one reactive surfactant, (c) optionally, at least one ethylenically unsaturated monomer which is different from (a) or (b) and (d) optionally, at least one ethylenically unsaturated monomer that is different from (a), (b) or (c). The novel latex polymers are prepared by emulsion polymerization of the ethylenically unsaturated monomers. Aqueous compositions containing the novel latex polymers are useful for imparting superior water resistance to architectural coatings and in other applications where protection against water is desirable.

DETAILED DESCRIPTION OF THE INVENTION This invention relates to novel latex polymers and aqueous compositions containing the same made by emulsion polymerization exhibiting exceptionally high resistance to water and alkali. The novel latex polymers of this invention comprise (a) about 5 to about 99.9 weight percent of highly branched neovinyl esters; (b) 0 to about 94.9 weight percent of one or more alkyl esters of acrylic or methacrylic acid; (c) 0 to about 50 weight percent of other ethylenically unsaturated monomers; and (d) about 0.1 to 10.0 weight percent of one or more ethylenically unsaturated reactive surfactants. The highly branched neovinyl esters useful in this invention typically contain from 8 to 18 carbon atoms and are prepared from suitable highly branched carboxylic acids by methods well known in the art. Commercially available neovinyl ester products are usually a mixture that contains a predominance of one species. Neovinyl ester compositions suitable for use in the present invention include, but are not limited to, vinyl neononanoate (VeoVa 9), vinyl neodecanoate (VeoVa 10), and vinyl esters of branched, branched carboxylic acids (VeoVa 11), sold by Shell Chemical Company, and mixed C10-13 branched carboxylic acid vinyl esters, (EXXAR Neo-12), sold by Exxon Chemical Corp., and the like. The aqueous polymer compositions of the present invention may contain as little as about 5% by weight of highly branched neovinyl esters as much as about 99.9% by weight. When polymerized with other comonomers such as acrylates, the neovinyl esters are preferably present in an amount of from about 10% to about 80%, and more preferably from about 15% to about 70% by weight, based on the weight of all the monomers . Useful polymers have been prepared containing about 98.7% by weight of neovinyl esters and 1.3% by weight of one or more reactive surfactants. The reactive surfactants useful in the novel latex polymers of the present invention may be any compound containing ethylenically unsaturated double bonds for free radical reaction with neovinyl esters and other monomers during polymerization, while also containing hydrophilic and hydrophobic portions similar to those conventional surfactants that impart surface activity. The example of the compounds that are useful as surfactants in the novel latex polymers of the present invention include the compounds prepared by reacting esters sulphonated media of maleic anhydride with alkoxylated alkylaryls described in US Pat. No. 4,224,455; nonyl phenoxy (ethyleneoxy) 10-0 ethyl non-phenoxy (ethyleneoxy) 10-40 ethylacrylate and nonyl phenoxy (ethyleneoxy) crotonate 10-40 are described in US Patent No. 4,075,411; the N-acryloyl-piperazine based compounds described in U.S. Patent No. 5,563,214; the compounds having a hydrophobic portion having terminal ethylenic unsaturation and a hydrophilic portion containing a poly (alkyleneoxy) segment and an ionic segment described in US Patent No. 5,296,627; Compounds containing portions of nonylphenoxy propenyl described in US Patent No. 5,332,854 and US Patent No. 5,324,862; the compounds containing alum unsaturation described in U.S. Patent No. 4,939,283 and U.S. Patent No. 4,814,514; The description of all the above patents is incorporated herein by reference, and the sodium dodecylallylsulfosuccinat (Trem LF-40) sold by Henkel Corporation. Generally, the amount of ethylenically unsaturated reactive surfactants incorporated into the latex polymers of the present invention will vary from about 0.1% to about 10% by weight based on • the total weight of the polymer, and preferably d about 0.5% to about 8% by weight. Surfactants reactive with nonylphenoxy propenyl group or other groups structurally similar to styryl groups behave similarly to styrene in copolymerization with highly branched neovinyl esters, ie the polymerization of monomer d neovinylester is severely retarded in the presence of these compounds. It has been noted that the presence of certain other monomers such as the acrylic-alkyl and methacrylic alkyl esters appear to function as a bridge between branched neovinyl esters and reactive surfactants containing structurally similar groups styryl groups allowing stable latices to be made. Other surfactants reactive with ethylenically unsaturated moieties not similar to styryl groups generally react well in, or show less retardation toward, the polymerization of highly branched neovinyl esters. Copolymers of highly branched neovinyl esters with other ethylenically unsaturated monomers all polymers of vinyl esters and copolymers can be made with these reactive surfactants. Conventional non-reactive surfactants may also be present in the novel latex polymers of the present invention, but minimal use of such surfactants is preferred to achieve better results in the practice of this invention. Comonomers which can be copolymerized with highly branched neovinyl esters and reactive surfactants include those ethylenically unsaturated addition monomers readily recognized by one skilled in the art as useful in the preparation of latex polymers. Particularly useful monomers include ethylenically unsaturated alkyl esters of acrylic acid and methacrylic, such as, but not limited to, one or more of the following: n-butyl acrylate, isobutyl acrylate, isopropyl acrylate, ethyl acrylate, methyl acrylate , 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, isooctyl acrylate, nonyl acrylate, oleyl acrylate, dodecyl acrylate, stearyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, methacrylate nonyl, lauryl methacrylate, isobutyl methacrylate, isobornyl methacrylate, isobornyl acrylate, pentyl acrylate, mixtures thereof. Generally, the amount of ethylenically unsaturated alkyl esters of methacrylic acrylic present in the novel latex polymers of the present invention ranges from about 0% to about 95% by weight based on the total weight of the polymer. Particularly good results are obtained when such monomers are present in an amount of from about 20% to about 90% by weight, preferably from about 30% to about 80% by weight, based on the total weight of the polymer. It has been found that highly branched neovinyl esters react slower when copolymerized with alkyl esters of acrylic and methacrylic acid due to differences in the reactivity speed of the monomer. The alkyl esters of acrylic and methacrylic acid are completely closer reactants in short form after the addition of the monomer has been completed during the polymerization as long as they are typically substantial measurable amounts of highly branched neovinyl esters that remain unreactive. The inventors have found that substantial measurable amounts of highly branched n-linked neovinyl esters can be conducted toward completion by adding additional initiators and continuing the polymerization. Following this procedure, the latex particles structured core / shell latex particles can be obtained with highly branched neovinyl esters deposited in the outer layers or framework layers of latex particles. Thus another feature of this invention is a chemical medium for preparing structured latex particles with outer shell layers or layers having a very low oxygen content and low water permeability. Other ethylenically unsaturated monomers can be used in the preparation of latex polymers of the present invention included, but not limited to: vinyl esters, for example, vinyl acetate, vinyl propionate, vinyl formate, vinyl n-butyrate, vinyl laurate, vinyl stearate, vinyl pivalate, vinyl 2-ethylhexanoate, and the like; vinyl ethers, for example, methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether similar; allyl monomers, for example, allyl acetate, allyl propionate, allyl lactate, allylamines; olefins; such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene and the like. Other vinyl monomers, functional monomers and crosslinking monomers, for example, acrylic acid, methacrylic acid, acrylonitrile, styrene, p-methylstyrene, vinyl halides and vinylidene such as vinyl chloride and vinylidene chloride, sodium vinylsulfonate, sodium styrenesulfonate sodium allyl ether sulfonate, acrylamide, methacrylamide, 2-acrylamido-2-methyl-propanesulfonate sodium (AMPS), diacetone acrylamide, N-methylol acrylamide, N-methylol methacrylamide, 2-sulfoethyl methacrylate, 2- sulfopropyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl monomethacrylate 2, 2, 4-trimethyl-l, 3-pentanediol acrylate, 2-cyanoethyl, diethylaminoethyl acrylate, dimethylaminoethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, methacrylate acetoacetoxyethyl, allyl acetoacetamide, allyl methacrylate, trimethylolpropanetrimethacrylate, trifluoroethyl methacrylate, triallyl cyanurate, triallyl isocyanurate, sodium methallyl, ethylimidazolidone methacrylate, methoxyethyl acrylate, metacrilamidoetiletilenurea, allyl derivatives of aminoetiletilenurea (Sipomer WAM), cyclic imides derived from monomers urea / ureido (Cylink WAM; WO 97/49676), de-carboxyethyl acrylate, dicyclopentenyl acrylate, dicyclopentenyl methacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, vinyltrimethoxysilane, vinyltris (2-methoxyethoxysilane), gamma-methacryloxypropyltrimethoxysilane, vinylpyrrolidone, methacrylate phosphate ethylene, maleic acid, fumaric acid, itaconic acid, dimethyl maleate, maleate, di-n-butyl maleate, diethyl maleate, diethylhexyl, diethyl fumarate, butadiene, chloroprene, isoprene, polybutene and oligomers of poly (isobutylene-co butene) containing ethylenically unsaturated double bonds (Indopol series Amoco Chemical Company) dimethacrylate, 1, 4-butanediol, diallyl maleate, divinyl adipate, crotonic acid, mixtures thereof and the like. Typically, these additional ethylenically unsaturated monomers are present in an amount of from about 0% to about 50% by weight, based on the total weight of the polymer, and more typically up to about 30% by weight. Any known emulsion polymerization method can be used to prepare the novel latex polymers of the present invention including semi-batch, phase feed, powder feed, full, continuous batches, seed emulsion polymerization or any other suitable process. Any suitable polymerization conditions can be used. Typically, the reaction temperature will vary from about 0 ° C to about 100 ° C, and preferably from about 40 ° C to about 90 ° C. The polymerization will normally be conducted using polymerization initiators. Suitable polymerization initiators include, but are not limited to: water-soluble persulfates and peroxides capable of generating free radicals such as ammonium persulfate, sodium persulfate, potassium persulfate, acid peroxide, t-butyl hydroperoxide, di-peroxide. -t-butyl, peracetic acid, perbenzoic acid, diacetyl peroxide, t-butyl peracetate, t-butyl perbenzoate, and the like, azo initiators, such as 2,2-azobisisobutyronitrile, and the like, and other radiation compounds and Transition of metal capable of generating free radicals. The amount of such free radical initiators used generally ranges from about 0.05% to about 6% by weight based on the weight of all monomers present. Alternatively, the redox initiators can be used, especially when the polymerization is carried out at lower temperatures. For example, reducing agents can be used in addition to the persulfate and peroxide initiators mentioned above. Typical reducing agents include, but are not limited to: alkali metal salts of hydrosulfites, sufoxylates, thiosulfates, sulfites, bisulfites, reducing sugars such as glucose, sorbose, ascorbic acid, erythorbic acid, and the like. In general, reducing agents are used at levels from about 0.01% to about 6% by weight. Various additives can be added before, during or after polymerization. These include conventional surfactants, regulating agents, neutralizing agents, defoamers, chain transfer agents, plasticizers and polymeric stabilizers. Suitable conventional surfactants include, but are not limited to, one or more: alkyl and / or aryl sulphates, sulfonates, phosphates, or carboxylates such as sodium lauryl sulfate, sodium salt of alkylaryl polyether sulfates, linear ethoxylate phosphate alcohols, alkylphenols ethoxylate phosphate, and the like; oxyalkylated fatty amines, fatty acid amides and / or monoalkylphenols such as oxyethylated lauryl alcohol, oxyethylated oleyl alcohol, oxyethylated stearyl alcohol, oxyethylated p-isooctylphenol, oxyethylated p-n-nonylphenol, oxyethylated p-n-dodecylphenol, and the like; fluorocarbon-based surfactants such as ammonium perfluoroalkylsulfonates, potassium perfluoroalkylsulfonates, amine perfluoroalkylsulfonates, ammonium perfluoroalkylcarboxylates, fluorinated alkylcarboxylates of potassium, fluorinated alkylpolyoxyethyleneethanols, fluorinated alkylalkoxylates, fluorinated alkylesters and the like. The amount of conventional surfactants can vary from about 0% to about 5% by weight, and preferably from about 0% to about 2 by weight. Any polymeric stabilizers capable of stabilizing latex particles can be used, including, but not limited to, cellulose ethers such as hydroxyethylcellulose, hydroxyethylcellulose modified with alkyl, hydroxyethylcellulose modified with arylalkyl, carboxymethylcellulose, alginate, starch, poly (vinyl alcohol) ), polyacrylates, polymethacrylates, maleic styrene-maleic copolymers, polyvinylpyrrolidones, polyacrylamides, polyethers, and the like. The amount of polymeric stabilizers can vary from about 0% to about 5% by weight, and preferably from about 0% to about 2% by weight. The latex polymers of the present invention are usually obtained as an aqueous composition by emulsion polymerization. The techniques are well known to those skilled artisans that can be employed to obtain a latex polymer of the present invention having the desired physical characteristics required for a particular application. The useful aqueous composition containing the latex polymers of the present invention will typically have a solids content of about 10% to about 70% by weight based on the total weight of the composition. The latex polymers of the present invention will be made to measure to obtain any desired molecular weight and viscosity. Typically the latex polymers of the present invention will have a viscosity in the range of about 10 about 5000 cps. The pH of an aqueous composition containing the latex polymer of the present invention will normally be within the range of about 2 about 12, while the particle size of the latex polymer will normally be in the range d about 0.02 to about 2.0 microns. The novel latex polymers of the present invention can be custom-made for use in many applications. Representative examples include architectural coatings for wood that includes paints, varnishes, inks and clear sealers; architectural coatings for other substrates such as plaster, concrete, brick and metal; Finishing apparatus, automotive finishes, coil coatings, tin coatings, marine coatings, aircraft finishes, paper coatings and various adhesives including pressure sensitive adhesives. Other potential uses for novel latex polymers include sealing caulks, additives and modifiers, binders and pigment dyes, modifiers - cement, waterproofing agents, overprint varnishes, flexographic and polishing inks for shoes, floors and furniture.

EXAMPLES The following examples are offered to illustrate the novel aqueous polymer compositions of this invention and are not intended to be limiting in scope. All parts, percentages and proportions mentioned herein are by weight unless otherwise indicated.

EXAMPLE 1 This example illustrates the preparation of an aqueous latex polymer composition with alkyl esters of acrylic and methacrylic acid in the presence of conventional surfactants. A reaction vessel was equipped with an agitator, thermocouple, reflux condenser, nitrogen inlet, water jacket, and suitable addition ports. A pre-emulsion of monomer was prepared by mixing together 60.1 parts of deionized water, the conventional surfactants 0.37 parts of sodium lauryl sulfate (Rhodapon UB supplied by Rhodia Company) and an ethoxylated nonylphenol (Tergitol NP-15 supplied by Union Carbide Corp.) , 46.52 parts of n-butyl acrylate, 52.13 parts of methyl methacrylate, and 1.34 parts of methacrylic acid. The reaction vessel was charged with 72.1 parts of deionized water-, 1.12 parts of Rhodapon UB and 2.26 parts of Tergitol NP-15, 2.75% of the pre-emulsion of the above prepared monomer and 0.05 parts of ammonium persulfate in 1.22 parts of deionized water. The vessel was heated to 80 ° C with continuous stirring and purged with nitrogen. Twenty minutes later, the remainder of the monomer pre-emulsion together with 0.55 parts of an ammonium persulfat in 6.09 parts of deionized water in a separate feed stream were added to the reaction vessel for a period of three hours. The temperature was kept at 80 ° C for 30 minutes after all the additions. 0.29 part of t-butyl hydroperoxide in 2.44 parts of deionized water and 0.12 parts of sodium formaldehyde sulfoxylate in 2.52 parts of deionized water for a period of one hour were added to the reaction vessel. The latex was then cooled to room temperature. The properties of the latex obtained are presented in Table 1.

EXAMPLE 2 This example describes the preparation of an aqueous latex polymer composition with acrylic and methacrylic acid alkyl esters in the presence of conventional surfactant types d which are different from those used in Example 1. The equipment, process ingredients described in - Example 1 were used, except that the conventional surfactants employed to prepare the pre-emulsion of the monomer were 0.24 parts d an ammonium salt of sulphonated nonylphenoxy poly (ethyleneoxy) ethanol (ABEX EP-110 supplied by Rhodia Company) and 0.57 parts of nonylphenoxy poly (ethyleneoxy) ethanol (Igepal CO-630 supplied by Rhodia Company). Initially 1.12 parts of ABEX EP-110 and 2.26 parts of Igepal CO-630 were charged to the reaction vessel. The properties of the latex obtained are presented in Table 1.

EXAMPLE 3 This example describes the preparation of an aqueous latex polymer composition with alkyl ester of acrylic and methacrylic acid in the presence of ethylenically unsaturated reactive surfactants. The equipment, process and ingredients described in Example 1 were used, except that in place of the conventional surfactants, the following ethylenically unsaturated reactive surfactants were used to prepare the pre-emulsion of the monomer, 0.07 parts of nonylphenoxy polyethoxylate sulfate propenyl (Hitenol BC-10 supplied by DKS International, Inc.) and 0. 57 parts polyethoxylated alcohol of nonylphenoxy propenyl (Noigen RN-10 supplied by DKS International, Inc.) 0.34 parts of Hitenol BC-10 and 2.26 parts of Noigen RN-10 were charged to the reaction vessel initially. The properties of the latex obtained are presented in Table 1.

EXAMPLE 4 This example describes the preparation of an aqueous latex polymer of a highly branched neovinyl ester with alkyl esters of acrylic and methacrylic acid in the presence of conventional surfactants. The equipment and procedure described in Example 1 were used. A pre-emulsion of the monomer was prepared by mixing together 58.38 parts of deionized water, 0.58 parts of an ammonium salt of sulphonated nonylphenoxy poly (ethyleneoxy) ethanol (ABX EP-110 supplied by Rhodia Company) and 1.13 parts of a nonylphenoxy poly (ethyleneoxy) ethanol (Igepal CO-630 supplied by Rhodia Company) which are agents conventional surfactants, 37.52 parts of vinyl neodecanoate (VeoVa 10 supplied by Shell Chemical Company), 25.82 parts of n-butyl acrylate, 35.32 parts of methyl methacrylate, and 1.34 parts of methacrylic acid. The reaction vessel was charged with 72.1 parts of deionized water, 0.88 parts of ABEX EP-110 and 1.70 parts of Igepal CO-630, 2.75 percent of the pre-emulsion of the previous prepared monomer, and 0.05 parts of ammonium persulfate in 1.22 parts of deionized water. The vessel was heated to 80 ° C with continuous stirring and purged with nitrogen. Twenty minutes later, the remainder of the monomer pre-emulsion - together with 0.55 parts of ammonium persulfate in 6.09 parts of deionized water in a separate feed stream were added to the reaction vessel over a period of three hours. The VeoVa 10 libr at the end of the addition was found to be approximately 5.5 percent. Free methyl methacrylate was found to be about 0.13 per cent and n-butyl acrylate was not detectable. The temperature of the reaction vessel was maintained at 80 ° C for 3 more minutes and 0.29 parts of t-butyl hydroperoxide and 2.44 parts of deionized water and 0.12 parts of sodium formaldehyde sulfoxylate in 2.52 parts of deionized water were then added during a period of one hour. The residual methyl methacrylate was 0.02 per cent while VeoVa 10 and n-butyl acrylate were not detectable at the end of the addition of the additional initiator. Thus, the additional initiator was able to drive the VeoVa 10 reaction towards completion. It is possible that the structured latex particles or core / shell latex particles were obtained with highly branched neovinyl esters deposited in the outer layers or shell layers of the latex particles. The properties of the obtained latte are presented in Table 1.

EXAMPLE 5 This example illustrates the novel latent polymers of the present invention. Disclosed is the preparation of a highly branched aqueous neovinyl ester aqueous latex polymer with alkylesters of acrylic or methacrylic acid in the presence of unsaturated reactive surfactants containing nonylphenoxy propenyl groups. The equipment, process ingredients described in Example 4 were used, except that the following ethylenically unsaturated reactive surfactants were employed in place of conventional surfactants to prepare the pre-emulsified monomer; 0.15 parts of polyethoxylate-sulphate d nonylphenoxy propenyl (Hitenol BC-10 supplied by DK International, Inc.) and 1.13 parts of polyethoxylated nonylphenoxy propenyl alcohol (Noigen RN-10 supplied by DK International, Inc.), 0.26 parts of Hitenol BC -10 and 1.7 parts of Noigen RN-10 were charged to the reaction vessel initially. At the end of the pre-emulsion of the monomer, and the additions of the initiator, free VeoVa 10 was found to be 3.5 percent, while methyl methacrylate free and n-butyl acrylate were 0.03 and 0.02 percent, respectively. The temperature of the reaction vessel was maintained at 80 ° C for an additional 30 minutes and 0.2 parts of t-butyl hydroperoxide in 2.44 parts of deionized water and 0.12 parts of sodium formaldehyde sulfoxylate in 2.52 parts of deionized water was then added during a period of one hour. VeoVa 10 residual was found to be approximately 0.07 per cent while methyl methacrylate was 0.02 percent and n-butyl acrylate was not detected. In this example, the structured latex particles or core / shell particles can be made with highly branched neovinyl esters deposited in the outer layer or shell layers of the latex particles. Surprisingly, the polymerization of VeoVa 10 was not delayed in the presence of reactive surfactants containing nonylphenoxy propenyl groups as one skilled in the art could have expected. The properties of the latex obtained are presented in Table 1.

Table 1: Latex Compositions and Properties Example Example Example Example Example 1 2 3 4 5 Acrylate of n- 46.52 46.52 46.52 25.82 25.82 butyl methacrylate 52.13 52.13 52.13 35.32 35.32 methyl VeoVa 10 (a) 37.52 37.52 Acid 1.34 1.34 1.34 1.34 1.34 methacrylic Rhodapon UB (b) 1.49 Tergitol NP-15 2.83 (c) ABEX EP-110 (d) 1.36 1.46 Igepal CO-630 2.83 2.83 (e) Hitenol BC-10 0.41 0.41 (f) Noigen RN-10 2.83 2.83 (g) Content of 41.0. 42.27 39.24 41.39 41.1! latex solids% by weight pH 2.12 2.11 2.13 2.1Í 2.18 Size 0.12 0.16 0.19 0.14 0.13 particle, miera Viscosity 20 20 20 20 20 Brookfield cps (a) Vinyl neodecanoate supplied by Shell Chemical Company. (b) Sodium lauryl sulphate (30% in aqueous solution) conventional surfactant supplied by Rhodia Company. (c) Conventional ethoxylated nonylphenol surfactant supplied by Union Carbide Corp. (d) Ammonium salt of conventional sulfonated nonylphenoxy poly (ethyleneoxy) ethanol surfactant (30% in aqueous solution) supplied by Rhodia Company. (e) Conventional nonylphenoxy poly (ethyleneoxy) ethanol surfactant supplied by Rhodia Company. (f) Nonylphenoxy propenyl polyethyloxylated sulphate reactive surfactant supplied by DKS International, Inc (g) Nonylphenoxy propenyl reactive surfactant of polyethoxylated alcohol provided by DKS International, Inc. The test formulations were prepared to examine the water repellent effectiveness of each latex shown in Table 1. Each test formulation contains 100 parts of the latex to be tested, 106.5 parts of deionized water, and 4.5 parts of diethylene glycol monobutyl ether. Each test formulation was balanced for 24 hours Before the test. The effectiveness of the water repellent of each latex was measured gravimetrically. Water absorption was tested using a 1 by 2 by 0.25 inch set of Southern Yellow Pine boards. Four boards were treated with each latex formulation by submerging the boards in the latex formulation for three minutes. The tables are then allowed to dry for three days in a constant temperature and humidity maintained environment (22.22 ° C (72 ° F) and 50% d humidity). Four untreated tables were used as control. All of the treated and untreated tables were weighed, submerging in deionized water for 30 minutes, and weighed again. The difference in pes represents the amount of water absorbed. The effectiveness of water repellent (WRE) of each latex is determined by subtracting the weight of the water absorbed by the table treated with the latex of the weight of the water absorbed by the table n treated, dividing by the weight of the water absorbed by the untreated table and multiplied by 100, as shown in the following equation. WRE = (water absorbed by untreated control - water absorbed by treated table) X 100 (water absorbed by untreated control) The average effectiveness of the water repellent of the four treated tables with each latex of the examples is shown in the Table 2. The results show that the water resistance of the novel aqueous polymer compositions of the present invention represented by Example 5 are significantly better than the water resistance of the prior art compositions.

Table 2: Water Repellent Effectiveness Example Water Repellent Effectiveness 1 - 43. 69 2 4 6. 69 3 57. 41 4 72.75 5 81.28 The following recipes are examples of typical architectural coating formulations employing the novel latex polymer of Example 5: Clear Sealer for Wood or Concrete Ingredients Gallons Water 43.59 Glycol 3., 95 Ammonia 0., 11 Wax Additive 2. 89 Co-solvent 1. 09 Antioxidant 0. 25 Moldings 0. 87 Preservative 0. 17 Latex of Example 5 47 '.05 Wetting agent 0. 02 Total 100% Solids in Weight 20 White Paint / Wood and Concrete Ink Ingredients _ Gallons Water 42.00 Conservative - 0.40 Glycol 4.00 Rheology Modifier 0.40 Dispersant 1.50 Defoamer 0.20 Surface Agent 0.20 Main Pigment 5.00 Extended Pigment 10.00 Latex from Example 5 34.00 Co-solvent 1.50 Mold 0.76 Total 100 % in Weight of Solids 47

Claims (1)

CLAIMS 1. A latex polymer comprising: (a) at least one highly branched neovinyl ester, and (b) at least one reactive surfactant. The polymer of claim 1, further containing: (c) at least one ethylenically unsaturated monomer that is different from (a) or (b). 3. The polymer of claim 2, wherein (c) is at least one alkyl ester of acrylic or methacrylic acid. The polymer of claim 3, further containing: (d) at least one ethylenically unsaturated monomer, which is different from (a), (b) or (c). The polymer according to claim 1, characterized in that the reactive surfactant of (b) contains ethylenic unsaturation and hydrophilic and hydrophobic portions. 6. The polymer of claim 1, wherein (a) is a neovinyl ester containing from 8 to eighteen carbon atoms. The polymer of claim 6, wherein the neovinyl ester is selected from vinyl neononanoate, vinyl neodecanoate, vinyl esters of mixtures of branched C8 to Ci carboxylic acids, or mixtures thereof. The polymer of claim 7, wherein the neovinyl ester is present in an amount of 5% to about 99.9% by weight based on the total weight of the polymer. 9. The polymer of claim 5, wherein the reactive surfactant is present in an amount of 0.1% to 10% by weight based on the total weight of the polymer. 10. A latex polymer comprising: (a) from about 15% to about 70% by weight, based on the total weight of the polymer of a highly branched neovinyl ester selected from vinyl neonononanoate, vinyl neodecanoate, vinyl esters of mixtures of branched Cg to C? 2 carboxylic acids, or mixtures thereof, (b) from about 0.5% to about 8% by weight of at least one reactive surfactant having ethylenic unsaturation and containing hydrophilic portions and hydrophobic; and (c) from about 30% to about 80% of at least one alkyl ester of acrylic or methacrylic acid. 11. The architectural coating composition comprising water and the latex polymer of claim 1. 12. The water resistant coating containing the latex polymer of claim 1. 13. The method for improving the water resistance of a coating composition by adding thereto an effective amount of the latex polymer of claim

1.