WO1989012618A1 - Polymerizable surfactant - Google Patents

Abstract

Describes alpha-beta ethylenically unsaturated poly(alkyleneoxy) compounds that display surfactant activity and that polymerize when used in the emulsion polymerization of ethylenically unsaturated monomers, including vinyl monomers.

Description

POLYMERIZABLE SURFACTANT

DESCRIPTION OF THE INVENTION

In the emulsion (suspension) polymerization of ethylenically unsaturated monomers, one or more surfactants (or emulsifiers) are employed conventionally to emulsify the monomer reactant(s) and the resulting polymer product latex. Such surfactants do not become chemically bonded to the polymer product molecule by carbon to carbon bonding (as distinct from a physical mixture, being adsorbed on the polymer product or the like). It has been suggested that the small amount of surfactant which remains in the polymer product latex may interfere with performance of products, e.g., coatings and adhesives, prepared from such latex. U.S. Patent 3,941,857 reports that coatings prepared from vinyl chloride/olefin copolymers show inconsistent performance in hot water resistance and tend to be sensitive to water in that pitting or "blushing" (a whitening effect) may sporadically occur, particularly after exposure of the coating to boiling water for extended periods. Such a performance characteristic is detrimental to certain end uses for such copolymers, e.g., container and paper coatings, interior and exterior coatings, industrial coatings, automotive coatings and certain adhesives. Various proposals have been made for avoiding the reported adverse effects of surfactant residues in emulsion polymerized polymers. U.S. Patent 3,941,857 describes incorporating a small, amount of an epoxy resin with a vinyl chloride/olefin copolymer resin before casting a film from the resin. U.S. Patent 4,049,608 describes the use of esters of an alkenoic acid selected from the group consisting of cinnamic acid and alkenoic acids of from 4 to 18 carbon atoms with a hydroxyalkane sulfonic acid in the emulsion polymerization of vinyl and other ethylenically unsaturated monomers. These esters serve the dual function of emulsifier and co-monomer. U.S. Patent 4,224,455 describes a class of ringed sulfonated half esters of maleic anhydride and alkoxylated alkyl arylols. These esters are reported to be anionic emulsifiers (surfactants) and reactive functional monomers that are copolymerizable under emulsion polymerization conditions. U.S. Patent 4,337,185 describes use of a reactive polymeric surfactant which is a substantially linear synthetic water-soluble surfactant whose polymeric backbone is derived from the polymerization of one or more ethylenically unsaturated monomers and which polymeric surfactant has a number average molecular weight of from about 500 to about 40,000 and contains various functional groups. The present invention provides a novel group of alpha-beta ethylenically unsaturated poly(alkyleneoxy) compounds that display surfactant activity, i.e., they function as surfactants (emulsifiers) in emulsion (suspension) polymerization processes. Moreover, they are copolymerizable with ethylenically unsaturated monomers, including vinyl monomers, of the type commonly employed in emulsion polymerization processes by virtue of the reactive double bond present in the compounds. In accordance with the present invention, there is provided a novel group of compounds having a hydrophobic portion containing alpha-beta ethylenic unsaturation, and a hydrophilic portion containing a poly(alkyleneoxy) segment and an ionic (anionic, nonionic, or cationic) segment.

DETAILED DESCRIPTION OF THE INVENTION The polymerizable surfactant compounds of the present invention may be represented by the following graphic formula: R-O-4R'O-)_m-(EO-_n-1CH₂CH₂-X (I) wherein R is an organic monovalent radical having alpha-beta olefinic (ethylenic) unsaturation. More particularly, R is an organic radical selected from the group consisting of C₂-C₁₈ alkenyl, e.g., vinyl and allyl, acrylyl, acrylyl (C₁-C₁₀) alkyl, methacrylyl, methacrylyl

(C₁-C₁₀) alkyl, vinylphenyl and vinylphenylene (C₁-C₆) alkyl. More particularly, the C₂-C₁₈ alkenyl group may be represented by the following graphic formula: CH₂=CH-C_aH_2a- (II) wherein a is a number between 0 and 16. When a is 0, the alkenyl group is vinyl, i.e., CH₂=CH-. When a is 1, the alkenyl group is allyl, i.e. , CH₂=CH-CH₂-_. The acrylyl, acrylyl (C₁-C₁₀) alkyl, methacrylyl and methacrylyl (C₁-C₁₀) alkyl groups may be represented by the following graphic formula:

wherein R₁ is hydrogen or methyl and b is a number from 0 to 10. When b is 0 and R₁ is hydrogen, the group is acrylyl [CH₂=CH-C(O)-]. When b is 0 and R₁ is methyl, the group is methacrylyl [CH₂=C(CH₃)-C(O)-]. When R₁ is hydrogen and b is 1, the group is acrylyl methyl [CH₂=CH-C(O)-CH₂-]. The vinylphenylene and vinylphenylene (C₁-C₆) alkyl groups may be represented by the following graphic formula: CH₂=CH-Ar-C_dH_2d- (IV) wherein Ar is phenylene and d is a number between 0 and 6. When d is 0, the group is vinylphenyl and when d is 1, the group is vinylphenylene methyl. In graphic formula I, -R'O- is a bivalent alkyleneoxy

(substituted and unsubstituted) group derived from a cyclic ether other than ethylene oxide or mixture of such cyclic ethers. More particularly, -R'O- may be represented by the graphic formula -CH₂CH(R")-O-, wherein R" is methyl, ethyl, phenyl, phenyloxymethyl,

-CH₂-(CH₂)₂-CH₂-O-, and mixtures thereof. Still more particularly, -R'O- may be described as the bivalent radical derived from cyclicethers selected from the group consisting of propylene oxide, (e.g., 1,2-epoxypropane), butylene oxide (e.g., 1,2-eρoxybutane), styrene oxide [(epoxyethyl) benzene], tetrahydrofuran, phenyl glycidyl ether (1,2-epoxy-3-phenoxypropane) and mixtures thereof. Preferably, -R'O-is the bivalent epoxy group derived from propylene oxide, butylene oxide and mixtures of propylene oxide and butylene oxide. The letter E in graphic formula I is the bivalent ethylene radical, and m and n are each numbers which may vary from about 5 to about 100, preferably between about 5 or 10 and about 50. The ratio of m:n may vary from about 20:1 to about 1:20. The specific ratio of m:n used will depend on the particular polymerization system in which the polymerizable surfactant of the present invention is incorporated. Varying the ratio of m:n will vary the HLB (Hydrophilic-Lipophilic Balance) of the polymerizable surfactant compound. If the polymerization system requires a hydrophobic surfactant, m will be greater than n. Conversely, if the emulsion polymerization system requires a hydrophilic surfactant, then m will be less than n. The ratio of m:n should be chosen so that the resulting compound is capable of reducing the surface tension of water.

Preferably, the surface tension of a 0.1 weight percent aqueous solution of the polymerizable surfactant compound at 25ºC is less than 38 dynes per centimeter. More preferably, the surface tension of such a solution is in the range of 30 to 35 dynes per centimeter. Surface tension may be measured by a Du Nouy tensiometer. X in graphic formula I is selected from the group consisting of hydroxyl (-OH), chloride (-C1), sulfonate (-SO₃), sulfate (-OSO₃), phosphate [-O-P(O)(OH)₂], acetate (-CH₂-C(O)OH), isethionate

(-CH₂-CH₂-SO₃H), and the alkali metal salts of the aforedescribed sulfonate, sulfate, phosphate, acetate and isethionate anionic groups, tertiary amino, i.e., -N(R₂)(R₃)R₄, wherein R₂, R₃ and R₄ are each selected from the group consisting of alkyl and hydroxyalkyl groups, particularly groups containing from 1 to 5 carbon atoms, e.g., a tertiary amine derived from trimethylamine, triethylamine, triethanolamine and diethylmethylamine. Commonly, X will be selected from the group consisting of sulfonate, sulfate, phosphate, acetate

(and alkali metal salts thereof), hydroxyl, chloride and tertiaryamino. As used herein, the term "alkali metal" includes sodium, potassium, lithium and ammonium. The polymerizable surfactant of the present invention may be prepared by reacting the precursor alcohol, ROH, wherein R is as heretofore defined with respect to graphic formula I, with the desired amount of first cyclic ether (R'O), e.g., propylene oxide, butylene oxide or mixtures thereof, and subsequently reacting the resulting epoxy-containing product with the desired amounts of ethylene oxide (EO). The product resulting from this reaction sequence is a material corresponding to graphic formula I wherein X is hydroxyl. Such a material may be used as a non-ionic surfactant.

Preparation of the polymerizable surfactant wherein X is sulfate may be accomplished by reacting the corresponding non-ionic

(hydroxy end-capped) surfactant with chlorosulfonic acid, 100% sulfuric acid or with sulfur trioxide. See, for example, U.S. Patents 2,143,759 and 2,106,716 of H. A. Bruson. Neutralization of the reaction product with an alkaline reagent, e.g., an alkali metal hydroxide such as sodium hydroxide, yields the corresponding salt, e.g., the sodium salt. Similarly, the corresponding non-ionic surfactant may be reacted with polyphosphoric acid (P₂O₅ ● 2H₂O) or chloroacetic acid by known procedures to prepare the phosphate or acetate end-capped polymerizable surfactant.

Sulfonate terminated polymerizable surfactants of graphic formula I may be prepared by first converting the corresponding non-ionic material to the corresponding chloride by reaction with thionyl chloride or carbonyl chloride (followed by subsequent decarboxylation to the chloride) and then reacting the chloride derivative with sodium sulfite. In conducting the sulfonation reaction, the pre-formed sulfonate terminated surfactant product may be used as the reaction medium to improve conversions. Thus, from 0 to 20 weight percent (based on the total amount of reactants) of pre-formed sulfonate product may be added to the reactor.

The chloride capped surfactant may be used itself as a surfactant as well as a precursor for preparing the sulfonate, isethionate or quaternary ammonium terminated surfactant. The isethionate derivative may be prepared by reacting the chloride-capped surfactant with isethionic acid in the presence of a base, e.g., sodium hydroxide. Quaternary ammonium derivatives may be prepared by reacting the corresponding chloride with the tertiary amine , N(R₂)(R₃)R₄, wherein R₂, R₃ and R₄ are the same as defined with respect to X in graphic formula I. Processes for converting the non-ionic polymerizable surfactant to the chloride, sulfate, sulfonate, phosphate ester, acetate, isethionate or quaternary ammonium derivative are well known to the skilled chemist.

The precursor alpha-beta ethylenically unsaturated alcohols used to prepare the polymerizable surfactant materials of graphic formula I may be prepared by methods known in the art. Some, such as allyl alcohol, are readily commercially available. In accordance with a particular embodiment of the present invention, the precursor alcohol is charged to a suitable autoclave and heated to a temperature in the range of from about 110°C. to about 130°C. Propylene oxide and/or 1,2-epoxybutane are metered into the autoclave and reacted with the unsaturated alcohol in the presence of an alkaline reagent such as sodium hydroxide. After the desired amount of propoxylation and/or butoxylation is achieved, ethylene oxide is substituted for the propylene oxide and/or 1,2-epoxybutane reactant(s) and metered into the reactor until the desired level of ethoxylation is achieved. Pressures in the reactor will usually remain at less than 100 pounds per square inch gage during these reactions. The resulting poly(alkyleneoxy) material is removed from the reactor, the alkaline reagent neutralized with acid, and the product recovered by filtration. This non-ionic material may be converted to the sulfate, sulfonate, phosphate ester, acetate, or isethionate (or their salts), or the chloride or quaternary ammonium derivative by the methods heretofore described. The number of epoxy, e.g., alkyleneoxy, groups present in the polymerizable surfactant material will vary as described with respect to graphic formula I. The number of epoxy units present per mole of surfactant of graphic formula I, i.e., the letters "m" and "n", is the average number of moles of cyclic ether present per mole of surfactant and hence the value of m and n may be a fractional number between 5 and 100.

Polymerizable surfactant materials of the present invention may be used in emulsion (or suspension) or solution polymerizations.

Such polymerizations may be carried out by free radical initiated polymerization using batch, continuous, or controlled monomer feed processes, known conditions of stirring time and temperature, and known kinds of additives such as initiators, surfactants, electrolytes, pH adjusting agents, buffering agents and the like. In general, the emulsion or solution polymerization will be carried out from about

20°C. to about 120°C, e.g.. between about 50°C. and about 80°C. Batch polymerization times may vary depending on the method of polymerization and the monomers being polymerized. Such times may vary from about 2 to about 10 hours. The polymerizable surfactant materials of the present invention are particularly useful in emulsion polymerization processes of the liquid phase type wherein water comprises the continuous phase and the monomer(s) is present substantially as a dispersed phase at the initiation of polymerization. The polymerization medium has incorporated therein at a minimum a sufficient amount of the polymerizable surfactant of the present invention to produce a stable, small particle size, dispersed monomer emulsion or suspension. The polymerizable surfactant of the present invention may be added batchwise, semicontinuously or continuously to the polymerizable reaction mixture. The quantity of polymerizable surfactant used in the polymerization of ethylenically unsaturated monomers, particularly when used as the sole emulsion polymerization surfactant, may range from about 1.0 to about 10 weight percent based on the total reactant monomer content employed in the given emulsion polymerization system.

Preferably the amount of such polymerizable surfactant material employed ranges from about 3.0 to about 6 weight percent, similarly based on total monomer. The polymerizable surfactant materials of the present invention may be used in an emulsion polymerization reaction in combination with conventional emulsion polymerization surfactants that are not reactive, i.e., non-copolymerizable with the polymerizable monomers. In selecting cosurfactant materials to be used, anionic and cationic materials should not be used together. Anionic and non-ionic surfactant materials or cationic and non-ionic surfactant materials may be used in combination. The reactive surfactants of the present invention themselves characteristically display excellent capacity for producing emulsion stability characteristics in the emulsion polymerization. It is contemplated that such conventional surfactants will be used in amounts of from 3 to 6 weight percent, based on the total amount of monomer(s).

In another embodiment of the present invention, it is contemplated that polymerizable surfactants of the present invention may be used as comonomers with the ethylenically unsaturated monomer(s) to modify the physical properties of the resulting polymer. The amount of polymerizable surfactant that may be so used may vary, e.g., from about 1 to about 25 weight percent, but will commonly be in the range of from about 1 to about 10, e.g., 3 to 6, weight percent, based on the total reactant monomer content. In this embodiment, conventional emulsion polymerization surfactants also may be used as additives to the polymerization, e.g., in amounts of from about 3 to 6 weight percent, based on the total amount of monomeric reactants to be polymerized. In a further embodiment of the present invention, ethylenically unsaturated monomer(s) and from 1-25 weight percent (as described hereinbefore) of the polymerizable reactive compounds represented by graphic formula I are copolymerized by solution polymerization. Any conventional organic solvent, which may be a solvent for both the monomer(s) and polymer, or just the monomer(s) may be used. Organic free-radical initiators, as described herein, may be used to initiate the solution polymerization. A sufficient quantity of a polymerization initiator (such as a conventional free radical initiator) is introduced into the polymerization medium to cause polymerization of the monomer(s) at the particular temperatures employed. Initiators used in emulsion polymerization processes are of the type which produce free radicals and conveniently are peroxygen compounds, for example: inorganic peroxides such as hydrogen peroxide and inorganic persulfate compounds such as ammonium persulfate, sodium persulfate and potassium persulfate; organic hydroperoxides such as cumene hydroperoxide and tertiary butyl hydroperoxide; organic peroxides such as benzoyl peroxide, acetyl peroxide, lauroyl peroxide, peroxydicarbonate esters such as diisopropyl peroxydicarbonate, peracetic acid and perbenzoic acid - sometimes activated by water-soluble reducing agents such as a ferrous compound, sodium bisulfite or hydroxylamine hydrochloride - and other free radical producing materials such as 2,2'-azobisisobutyronitrile. Conventional cationic nonpolymerizable surfactants include the classes of salts of aliphatic amines, especially the fatty amines, quaternary ammonium salts and hydrates, fatty amides derived from disubstituted diamines, fatty chain derivatives of pyridinium compounds, ethylene oxide condensation products of fatty amines, sulfonium compounds, isothiouronium compounds and phosphonium compounds. Specific examples of the cationic surfactants are dodecylamine acetate, dodecylamine hydrochloride, tetradecylamine hydrochloride, hexadecylamine acetate, lauryl dimethylamine citrate, octadecylamine sulfate, dodecylamine lactate, cetyl trimethyl ammonium bromide, cetyl pyridinium chloride, an ethanolated alkyl guanidine amine complex, stearyl dimethyl benzyl ammonium chloride, cetyl dimethyl amine oxide, cetyl dimethyl benzyl ammonium chloride, tetradecylpyridinium bromide, diisobutyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride, 1-(2-hydroxyethyl)-2-(mixed pentadecyl and heptadecyl)-2-imidazoline, resin amine ethoxylate, oleyl imidazoline, octadecyl ethylmethyl sulfonium methyl sulfate, dodecyl-bis-hydroxyethylsulfonium acetate, dodecylbenzyl-dimethylsulfonium chloride, dodecylbenzyltrimethylphosphonium chloride and S-p-dodecyl-benzyl-N-N-N'-N'-tetraraethylisothioronium chloride.

Representative types of anionic emulsifiers are the alkyl aryl sulfonates, the alkali metal alkyl sulfates, the sulfonated alkyl esters, the fatty acid soaps and the like. Specific examples of these well known emulsifiers are dodecylbenzene sodium sulfonate, sodium butyl naphthalene sulfonate, sodium lauryl sulfate, disodium dodecyldiphenyl ether disulfonate, n-octadecyl disodium sulfosuccinate and dioctyl sodium sulfosuccinate. Typical nonionic emulsifiers (surfactants) are compounds formed by the reaction of an alkylene oxide, such as ethylene oxide, propylene oxide or butylene oxide, with long chain fatty alcohols, long chain fatty acids, alkylated phenols, long chain alkyl mercaptans, long chain alkyl primary amines, for example, cetylamine, the alkylene oxides being reacted in a ratio of from about 5 moles to 20 moles or higher, e.g., up to 50 moles, per mole of the coreactant. Other representative compounds are monoesters, e.g., the reaction products of a polyethylene glycol with a long chain fatty acid, for example, glycerol monostearate, sorbitan, trioleate and partial and complete esters of long chain carboxylic acids with polyglycol ethers of polyhydric alcohols. By "long chain" in the above description is meant an aliphatic group having from six carbon atoms to 20 carbon atoms or more. A further additive that may be introduced into the polymerization reaction media is a conventional chain transfer agent such as an alkyl polyhalide or mercaptan. Examples include: bromoform, carbon tetrachloride, carbon tetrabromide, bromoethane, alkyl mercaptans of 1 to 12 carbon atoms, e.g., dodecylmercaptan, thiophenol and hydroxyalkyl mercaptans, e.g., mercaptoethanol. Ethylenically unsaturated monomer(s) which may be copolymerized with an ethylenically unsaturated, polymerizable material of graphic formula I are well known in the art and are illustrated herein only by representative example. Ethylenically unsaturated monomers are represented by, but not restricted to, mono- and polyunsaturated hydrocarbon monomers, vinyl esters, e.g., vinyl esters of C₁-C₆ saturated monocarboxylic acids, vinyl ethers, monoethylenically unsaturated mono- and polycarboxylic acids and their alkyl esters, e.g., acrylic acid esters and methacrylic acid esters,

(particularly their C₁-C₁₂ alkyl esters), the nitriles, vinyl and vinylidene halides, amides of unsaturated carboxylic acids and amino monomers. Representative examples of hydrocarbon monomers include compounds such as the styrene compounds, e.g., styrene, carboxylated styrene, and alpha-methyl styrene, and conjugated dienes, for example, butadiene, isoprene and copolymers of butadiene and isoprene. Representative examples of vinyl and vinylidene halides include: vinyl chloride, vinylidene chloride, vinyl fluoride and vinylidene fluoride. Acrylic ester and methacrylic ester examples include alkyl acrylates and methacrylates. Typical acrylic esters and methacrylic esters include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, hexyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 3,3-dimethylbutyl acrylate, 3,3-dimethyl butyl methacrylate, and lauryl acrylate. Suitable vinyl esters include aliphatic vinyl esters, such as vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl valerate, and vinyl caproate, and allyl esters of saturated monocarboxylic acids, such as allyl acetate, allyl propionate and allyl lactate.

Typical vinyl ethers include methylvinyl ether, ethylvinyl ether and n-butylvinyl ether. Typical vinyl ketones include methylvinyl ketone, ethylvinyl ketone and isobutylvinyl ketone. Suitable dialkyl esters of monoethylenically unsaturated dicarboxylic acids include dimethyl maleate, diethyl maleate, dibutyl maleate, dioctyl maleate, diisooctyl maleate, dinonyl maleate, diisodecyl maleate, ditridecyl maleate, dimethyl fumarate, diethyl fumarate, dipropyl fumarate, dibutyl fumarate, dioctyl fumarate, diisooctyl fumarate, didecyl fumarate , dimethyl itaconate , diethyl itaconate , dibutyl itaconate and dioctyl itaconate. Suitable monoethylenically unsaturated monocarboxylic acids include acrylic acid, methacrylic acid, ethacrylic acid and crotonic acid; monoethylenically unsaturated dicarboxylic acids, such as maleic acid, fumaric acid, itaconic acid and citraconic acid; and monoethylenically unsaturated tricarboxylic acids, such as aconitic acid and the halogen-substituted derivatives, e.g., alphachloroacrylic acid, and anhydrides of these acids, such as, e.g., maleic anhydride and citraconic anhydride are suitable for use as monomers. Acrylonitrile, alpha-chloro-acrylonitrile and methacrylonitrile are among the corresponding nitriles of such acids which can be used as monomers. Suitable amides of such acids include unsubstituted amides such as acrylamide, methacrylamide and other alpha-substituted acrylamides and N-substituted amides obtained by conventional reaction of the amides of the aforementioned mono- and poly-carboxylic acids with an aldehyde, such as formaldehyde. Typical

N-substituted amides include N-methylolacrylamide, N-methylolmethacrylamide, alkylated N-methylolacrylamides and N-methylolmethacrylamides, such as N-methoxymethylacrylamide and N-methoxymethylmethacrylamide.

Typical amino monomers include substituted and unsubstituted aminoalkyl acrylates, hydrochloride salts of amino monomers and methacrylates, such as beta-aminoethylacrylate, beta-aminoethylmethacrylate, dimethylamino-methylacrylate, beta-methylaminoethylacrylate, and dimethylaminomethylmethacrylate. Hydroxy-containing monomers include beta-hydroxyethylacrylate, beta-hydroxypropylacrylate, gamma-hydroxypropylacrylate and beta-hydroxyethylmethacrylate.

The aforesaid monomers, particularly the acrylic esters and methacrylic esters, may be homopolymerized or copolymerized with other of the described monomers, i.e., one or more different monomers capable of addition type polymerization.

The reactive surfactants of the present invention may find particular use in polymerization systems including various monomer and monomer mixtures to form homopolymers and copolymers, such as vinyl acetate-acrylic monomer mixtures, vinyl acetate monomer, ethylene-vinyl acetate monomer mixtures, styrene, styrene-acrylic monomer mixtures, butadiene-acrylonitrile monomer mixtures, styrene-butadiene monomer mixtures, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, and mixtures of other monomers with each of said vinyl and vinylidene halides, acrylic monomer-acrylonitrile monomer mixtures, and all acrylic monomer mixtures. The term "acrylic" as used herein is intended to mean and include one or more acrylic esters and/or methacrylic esters with and without acrylic acid or methacrylic acid. Such monomer mixtures are well known to the skilled artisan. The polymerizable surfactants of the present invention polymerize along with the conventional reactant monomer(s) in the polymerization process, thereby to form water-insoluble, substantially surfactant-free polymer particles. Thus, the polymer latex product is not contaminated with an undesirable residue of water-soluble surfactant. The polymer product has improved resistance to water and may be used in any end use application for which the particular polymer product produced from the conventional reactant monomer(s) may be used. Examples include interior and exterior coatings, e.g., latex paints, container, paper and paperboard coatings, e.g., can coatings, adhesives, such as water-borne adhesives and pressure sensitive adhesives, sealants, industrial coatings, automotive coatings, textile coatings and binders, floor finishes, water-based inks, films, and binders for non-woven materials such as carpet backing. The polymer product prepared with the polymerizable surfactants of the present invention may be used as the principle resin component or as a minor component of a resin mixture used to prepare the coatings, adhesives, sealants, binders, inks, floor finishes, etc. described herein. The remainder of the film forming composition may comprise various fillers, e.g., pigments, colorants, etc., solvents, e.g., aqueous or organic solvents, plasticizers, antioxidants, curing agents, thickeners, surfactants, preservatives, wet strength additives, and other adjuvant materials added in conventional amounts to resin compositions used in the aforedescribed end-use applications. The present process is more particularly described in the following examples, which are intended as illustrative only since numerous modifications and variations therein will be apparent to those skilled in the art. EXAMPLE 1 A one liter magnetically stirred autoclave was charged with

58.1 grams of allyl alcohol and 0.92 grams of sodium hydroxide. The autoclave was sealed and the air atmosphere therein replaced with nitrogen. The autoclave was pressurized with nitrogen to 10 pounds per square inch gage (psig) and the contents heated to 120°C.

1,2-epoxybutane was introduced slowly and continuously into the autoclave while the reactor contents vcere maintained between about 110°C. and 130°C. The maximum operating pressure during addition of the 1,2-epoxybutane was less than 100 psig. After 600 grams of

1,2-epoxybutane had been introduced into the autoclave, the reaction slowed. The contents of the autoclave were cooled to about 15°C., the autoclave opened and an additional 0.66 grams of sodium hydroxide introduced into the autoclave to enhance the rate of alkoxylation. The autoclave was closed, the air atmosphere replaced with nitrogen, the autoclave pressurized to a pressure of 10 psig with nitrogen and the contents heated to 120°C. 1,2-epoxybutane was again charged to the autoclave until the total amount of epoxybutane added reached about 865 grams. When the pressure in the autoclave reached a steady value, the autoclave was cooled. 886.4 grams of a light yellow-colored liquid product was recovered. The product was subjected to vacuum degassing . to remove any residual unreacted 1,2-epoxybutane from the product. The degassed product was identified as the butoxylated product of allyl alcohol. Proton nuclear magnetic resonance (NMR) spectroscopy indicated that the number of butoxy groups in the product was about 12.3 per molecule.

A one liter magnetically stirred autoclave was charged with 332 grams of the above-described degassed butoxylated allyl alcohol.

After replacing the air atmosphere in the autoclave with nitrogen, the butoxylated allyl alcohol was heated to 120ºC. and 240 grams of ethylene oxide added slowly to the autoclave over a period of about 3 hours so as to maintain the reaction temperature at 120°C. and the operating pressure below 90 psig. The resultant product was allowed to cool to 3°°C. and 0.89 grams of acetic acid added to the reaction product for neutralization of the basicity in the reaction mixture. The final product was a light yellow liquid. The number of ethoxy units per molecule in the product were determined by proton NMR to be about 15.3. This product will be referred to herein as Sample 1-A. A 0.1 weight percent aqueous solution of Sample 1-A was prepared and the surface tension of the solution measured at 25°C. with a Du Nouy tensiometer. The surface tension was found to be 31.6 dynes/centimeter.

The one liter autoclave was charged with 277 grams of the degassed butoxylated allyl alcohol and flushed with nitrogen for 30 minutes. The butoxylated allyl alcohol was heated to 120ºC. and 330 grams of ethylene oxide charged slowly over about 3 hours to the autoclave while maintaining the reaction temperature at about 120ºC. and the operating pressure below 90 psig. 0.74 grams of acetic acid were added to neutralize the basicity in the product. 614.7 grams of a light yellow liquid product was recovered. Proton-NMR indicated that the number of ethoxy groups per molecule in the product was about 26.1. This product will be referred to herein as Sample 1-B. The surface tension of a 0.1 weight percent aqueous solution of Sample 1-B product was 32.2 dynes/centimeter at 25°C.

The one liter autoclave was charged with 221 grams of the degassed butoxylated allyl alcohol, flushed with nitrogen, and the butoxylated allyl alcohol heated to 120°C. 370 grams of ethylene oxide were charged slowly to the autoclave over about 4 hours while maintaining the reaction temperature at about 120ºC. and the reaction pressure at less than 100 psig. When all of the ethylene oxide had been charged to the autoclave, the pressure was permitted to equilibrate and the autoclave cooled. 0.59 grams of acetic acid were added to neutralize the basicity in the reaction product. Proton-NMR indicated that the number of ethoxy units in the light yellow liquid product was about 40.6. This product will be referred to herein as Sample 1-C. The surface tension of a 0.1 weight percent aqueous solution of the Sample 1-C product was 33.6 dynes/centimeter at 25"C.

EXAMPLE 2 A two liter, jacketed round-bottom flask equipped with a phosgene inlet tube, dry ice cooled condenser, stirrer and dropping funnel was charged with 20 grams of liquid phosgene. The reaction flask was then charged simultaneously with 477 grams of product Sample 1-B described in Example 1 and 40 grams of additional phosgene. The reaction mixture was stirred at 15-20°C. for several hours before excess phosgene was removed by degassing the reaction product. The resulting chloroformate was converted to the corresponding chloride by heating it in the presence of 1.23 grams of trioctyl methyl ammonium chloride at 120-140°C. for 4 hours. 480 grams of product were recovered. The product was confirmed as the corresponding chloride by proton-NMR and infrared spectroscopy, and total chloride analysis.

EXAMPLE 3

A 0.5 liter magnetically stirred autoclave was charged with 100.7 grams of the chloride product of Example 2, 12.3 grams of sodium sulfite (98 percent), 265.1 grams of deionized water and 1.2 grams of a 50 percent aqueous solution of sodium hydroxide. The autoclave was sealed and the contents heated to 155°C. and maintained at temperature overnight. The pressure within the autoclave stabilized at about 60 psig. The contents of the autoclave were cooled subsequently to less than 5°C. The product, i.e., the corresponding sulfonate of the chloride product of Example 2, was a light yellow liquid containing 28.3 percent solids with 7.2 percent (as is) anionic surfactant activity.

EXAMPLE 4 The procedure of Example 3 was repeated except that 77.4 grams of the pre-formed sulfonate product produced in Example 3 was added to the autoclave with the reactants. 423.7 grams of a light yellow clear liquid product was recovered from the autoclave. The product was treated with 1.00 grams of hydrogen peroxide (49.5 percent) for removal of residual sulfite anion. The product contained about 30 percent solids and analyzed about 14.6 percent anionic surfactant activity.

EXAMPLE 5 The procedure of Example 3 was repeated except that 113.2 grams of the pre-formed sulfonate product from Example 4 was added to the autoclave with the reactants. The product was a light yellow clear liquid. It was treated with 1.33 grams of hydrogen peroxide (49.5 percent) for removal of residual sulfite anion. The sulfonate product was combined with the product of

Example 4. The resultant mixture had a solids content of about 28.3 percent and analyzed about 16.2 percent anionic surfactant activity. The surface tension of a 0.1 weight percent aqueous solution of the product was found to be 35.6 dynes/centimeter at 25°C.

EXAMPLE 6

Using the procedure of Example 2, 401 grams of Sample 1-A were reacted with phosgene and the resulting chloroformate decarboxylated to the corresponding chloride with 1.1 grams of trioctyl methyl ammonium chloride. 77.7 grams of the resulting chloride product were converted to the sulfonate by the procedure of Example 3 utilizing 15.4 grams of sodium sulfite, 174.3 grams of deionized water and 1.54 grams of a 50 percent aqueous solution of sodium hydroxide. A milky light yellow liquid containing 33.3 percent solids with 9.6 percent anionic surfactant activity was obtained.

EXAMPLE 7 The sulfonation procedure of Example 3 was followed using

77.7 grams of the chloride product of Example 6, 15.4 grams of sodium sulfite, 1.54 grams of sodium hydroxide, 218.3 grams of deionized water and -135.9 grams of the pre-formed sulfonate product produced in Example 6. The product contained about 29.3 percent solids and analyzed about

10.8 percent anionic surfactant activity. After standing for about two weeks, the product was observed to have separated into two layers .

EXAMPLE 8

The procedure of Example 7 was repeated except that 149.8 grams of the top layer of the sulfonate product of Example 7 was used as the pre-formed sulfonate in the sulfonation reaction. The sulfonate product was treated with 1.33 grams of hydrogen peroxide (49.5 percent) to remove residual sulfite anion, and then combined with the remainder of the sulfonate product from Example 7. The combined product had

11.1% anionic surfactant activity. The combined product had 11.1% anionic surfactant activity. The surface tension of a 0.1 weight percent aqueous solution of the product was found to be 35.9 dynes/centimeter at 25°C. EXAMPLE 9 Following the procedure of Example 2, 407 grams of Sample 1-C were converted to the corresponding chloroformate with phosgene. The chloroformate was decarboxylated to the corresponding chloride with

1.05 grams of trioctyl methyl ammonium chloride. 115.6 grams of the resulting chloride product were converted to the corresponding sulfonate by the procedure of Example 3 utilizing 10.8 grams of sodium sulfite, 1.1 grams of a 50 percent aqueous solution of sodium hydroxide and 296.2 grams of deionized water. The product was a light yellow clear solution at 60"C. It was treated with 1.9 grams of hydrogen peroxide (49.5 percent) to remove any residual sulfite anion. The product contained 28.8 percent solids with 15.8 anionic surfactant activity.

EXAMPLE 10 The sulfonation procedure of Example 9 was repeated except that 57.1 grams of the pre-formed sulfonate product of Example 9 was added to the autoclave with the reactants. The product was a clear light yellow liquid which was treated with 1.76 grams of hydrogen peroxide to remove residual sulfite anion. The sulfonate product contained about 31.9 percent solids and analyzed 18.7 percent anionic surfactant activity.

The sulfonate product was combined with the remainder of the product from Example 9. The resulting mixture contained about 32.6 percent solids and analyzed about 16.1 percent anionic surfactant activity. The surface tension of a 0.1 weight percent aqueous solution of the product was found to be 35.1 dynes/centimeter at 25°C.

EXAMPLE 11 A vinyl acetate-butyl acrylate copolymer was prepared utilizing the sulfonate product of Example 5 as the sole surfactant. A one liter resin kettle was charged with a solution of 31.7 grams of the sulfonate product of Example 5 in 281 grams of deionized water. The solution was heated to 80°C. under a nitrogen atmosphere. One gram of potassium persulfate (K₂S₂O₈) was added to the solution followed by the slow addition of 50 milliliters of a mixture comprising 202 grams of vinyl acetate and 36 grams of butyl acrylate. The polymerization temperature was maintained at 75-80°C. for 30 minutes after the addition of the 50 milliliter portion of the monomer mixture. The remainder of the monomer mixture was charged to the kettle over a 3-4 hour period while maintaining the polymerization temperature at between

70°C. and 75°C. The contents of the resin kettle were post stirred at 70°C. for 1 hour and then 10 grams of 2 percent formaldehyde sulfoxylate added to the kettle to complete the polymerization. The kettle contents were allowed to cool to ambient temperature and the latex in the kettle recovered by filtration through a cheese cloth. Less than 1 percent of the polymer product had coagulated. A portion of the latex was cast into a film and the film dissolved in chloroform-d (CD₃CI). Proton-NMR spectroscopy of the chloroform solution did not reveal the presence of any allylic hydrogens, which indicated that the sulfonate product of Example 5 had reacted completely during the polymerization. A film of the latex was cast onto a microscope slide and air dried for at least 24 hours. A NRL contact angle goniometer, Model 100-00, was employed to measure the contact angle of a drop of deionized water placed onto the film. The contact angle was determined within 10 seconds of the water being placed upon the film and was found to be 52°.

EXAMPLE 12 For purposes of comparison, the emulsion polymerization of

Example 11 was performed using 24 grams of sodium lauryl sulfate, (30 percent active) as the sole surfactant. The product was recovered by filtration through a cheese cloth and less than 1 percent of the product was found to have coagulated.

In accordance with the procedure described in Example 11, the contact angle for a drop of water placed on a film prepared from the aforesaid latex was measured. The water droplet was observed to spread immediately with a resulting contact angle of less than 5°.

The contact angle measurements of Examples 11 and 12 show that the latex prepared with the copolymerizable surfactant of Example

5 was less water sensitive than those made from conventional emulsifiers, i.e., sodium lauryl sulfate. EXAMPLE 13

A vinyl acetate homopolymer was prepared utilizing the sulfonate product of Example 10 as the sole surfactant. A one liter resin kettle was charged with a solution of 20.0 grams of the sulfonate product of Example 10 in 238 grams of deionized water. The solution was heated to 80°C. under a nitrogen atmosphere and 0.5 grams of potassium persulfate (K₂S₂O₈) added to the solution. 50 grams of vinyl acetate was added slowly to the resin kettle. The reaction temperature was maintained at 75-80°C. for 30 minutes after completing the initial charge of vinyl acetate. Subsequently, 150 grams of vinyl acetate was added to the kettle over 3-4 hours while maintaining the polymerization temperature at about 80°C. The contents of the resin kettle were post stirred for one hour at 85°C, cooled to ambient temperature, and filtered through a cheese cloth. The amount of coagulation found was about one percent. A film of the latex was cast onto a microscope slide and air dried for at least 24 hours. The contact angle for a drop of water placed on the film was measured (as per Example 11) and found to be 53°. Although the present invention has been described with reference to specific details of certain embodiments thereof, it is not intended that such detail should be regarded as limitations upon the scope of the invention, except as and to the extent that they are included in the accompanying claims.

PCT WORLD INTELLECTUAL PROPERTYORGANIZATION

International Bureau

INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PC

(51) International Patent Classification ⁴ (11)International Publication Number: WO 89/ C07C 43/16, 43/17, 43/156 C07C43/174, 59/42, 59/48 Al C07C93/08, 93/04, 141/10 (43)International Publication Date: 28 December 1989 (28. C07C 141/16, C07F9/40 t

(21)InternationalApplication Number: PCT/US89/02647 (81)Designated States: AT (European patent), AU, BE pean patent), CH (European patent), DE (Europe

(22)InternationalFiling Date: 16June 1989(16.06.89) tent), FR (European patent), GB (European pate (European patent), JP, KR, LU (European paten (European patent), SE (European patent).

(30)Priority data:

209,249 20June 1988 (20.06.88) US

Published

With internationalsearch report.

(71)Applicant: PPG INDUSTRIES, INC. [US/US]; One PPG With amended claims andstatement.

Place, Pittsburgh, PA 15272 (US).

(72)Inventors: TANG, Robert, H. ; 3008 Wilbanks Drive, Norton, OH 44203 (US). CHAKRABARTI, Paritosh, M. ; 1361 Redfern Drive, Pittsburgh, PA 15241 (US).

(74)Agents: STEIN, Irwin, M. et al.; PPG Industries, Inc., One PPG Place, Pittsburgh, PA 15272 (US).

(54)Title: POLYMERIZABLE SURFACTANT

(57)Abstract

Describes alpha-beta ethylenically unsaturated poly(alkyleneoxy) compounds that display surfactant activity and tha lymerize when used in the emulsion polymerization of ethylenically unsaturated monomers, including vinyl monomers.

FOR THE PURPOSES OF INFORMATION ONLY

Codes used to identify States party to the PCT on the front pages of pamphlets publishing international applications under the PCT.

AT Austria Fl Finland ML Mali

AU Australia FR France MR Mauritania

BB Barbados Gλ Gabon MW Malawi

BE Belgium GB United Kingdom NL Netherlands

BF Burkina Fasso HU Hungary NO Norway

BG Bulgaria IT Italy RO Romania

BJ Benin JP Japan SO Sudan

BR Brazil KP Democratic People's Republic SE Sweden

CF Central African Republic ofKorea SN Senegal

CG Congo KR Republic ofKorea SU Soviet Union

CH Switzerland U Liechtenstein TD Chad

CM Cameroon LK Sri Lanka TG Togo

DE Germany, Federal Republicof LU Luxembourg US United States of America

DK Denmark MC Monaco

ES Spain MG Madagascar

POLYMERIZABLE SURFACTANT

DESCRIPTION OF THE INVENTION

In the emulsion (suspension) polymerization of ethylenically unsaturated monomers, one or more surfactants (or emulsifiers) are employed conventionally to emulsify the monomer reactant(s) and the resulting polymer product latex. Such surfactants do not become chemically bonded to the polymer product molecule by carbon to carbon bonding (as distinct from a physical mixture, being adsorbed on the polymer product or the like). It has been suggested that the small amount of surfactant which remains in the polymer product latex may interfere with performance of products, e.g., coatings and adhesives, prepared from such latex. U.S. Patent 3,941,857 reports that coatings prepared from vinyl chloride/olefin copolymers show inconsistent performance in hot water resistance and tend to be sensitive to water in that pitting or "blushing" (a whitening effect) may sporadically occur, particularly after exposure of the coating to boiling water for extended periods. Such a performance characteristic is detrimental to certain end uses for such copolymers, e.g., container and paper coatings, interior and exterior coatings, industrial coatings, automotive coatings and certain adhesives. Various proposals have been made for avoiding the reported adverse effects of surfactant residues in emulsion polymerized polymers. U.S. Patent 3,941,857 describes incorporating a small amount of an epoxy resin with a vinyl chloride/olefin copolymer resin before casting a film from the resin. U.S. Patent 4,049,608 describes the use of esters of an alkenoic acid selected from the group consisting of cinnamic acid and alkenoic acids of from 4 to 18 carbon atoms with a hydroxyalkane sulfonic acid in the emulsion polymerization of vinyl and other ethylenically unsaturated monomers. These esters serve the dual function of emulsifier and co-monomer. U.S. Patent 4,224,455 describes a class of ringed sulfonated half esters of maleic anhydride and alkoxylated alkyl arylols. These esters are reported to be anionic emulsifiers (surfactants) and reactive functional monomers that are copolymerizable under emulsion polymerization conditions. U.S. Patent 4,337,185 describes use of a reactive polymeric surfactant which is a substantially linear synthetic water-soluble surfactant whose polymeric backbone is derived from the polymerization of one or more ethylenically unsaturated monomers and which polymeric surfactant has a number average molecular weight of from about 500 to about 40,000 and contains various functional groups. The present invention provides a novel group of alpha-beta ethylenically unsaturated poly(alkyleneoxy) compounds that display surfactant activity, i.e., they function as surfactants (emulsifiers) in emulsion (suspension) polymerization processes. Moreover, they are copolymerizable with ethylenically unsaturated monomers, including vinyl monomers, of the type commonly employed in emulsion polymerization processes by virtue of the reactive double bond present in the compounds. In accordance with the present invention, there is provided a novel group of compounds having a hydrophobic portion containing alpha-beta ethylenic unsaturation, and a hydrophilic portion containing a poly(alkyleneoxy) segment and an ionic (anionic, nonionic, or cationic) segment.

DETAILED DESCRIPTION OF THE INVENTION The polymerizable surfactant compounds of the present invention may be represented by the following graphic formula:

wherein R is an organic monovalent radical having alpha-beta olefinic (ethylenic) unsaturation. More particularly, R is an organic radical selected from the group consisting of C₂-C₁₈ alkenyl, e.g., vinyl and allyl, acrylyl, acrylyl (C₁-C₁₀) alkyl, methacrylyl, methacrylyl

(C₁-C₁₀) alkyl, vinylphenyl and vinylphenylene (C₁-C₆) alkyl. More particularly, the C₂-C₁₈ alkenyl group may be represented by the following graphic formula: CH₂=CH-C_aH_2a- (II) wherein a is a number between 0 and 16. When a is 0, the alkenyl group is vinyl, i.e., CH₂=CH-. When a is 1, the alkenyl group is allyl, i.e., CH₂=CH-CH₂-. The acrylyl, acrylyl (C₁-C₁₀) alkyl, methacrylyl and methacrylyl (C₁-C₁₀) alkyl groups may be represented by the following graphic formula:

wherein R₁ is hydrogen or methyl and b is a number from 0 to 10. When b is 0 and R₁ is hydrogen, the group is acrylyl [CH₂=CH-C(O)-]. When b is 0 and R₁ is methyl, the group is methacrylyl [CH₂=C(CH₃)-C(O)-]. When R₁ is hydrogen and b is 1, the group is acrylyl methyl [CH₂=CH-C(O)-CH₂-]. The vinylphenylene and vinylphenylene (C₁-C₆) alkyl groups may be represented by the following graphic formula: CH₂=CH-Ar-C_dH_2d- (IV) wherein Ar is phenylene and d is a number between 0 and 6. When d is 0, the group is vinylphenyl and when d is 1, the group is vinylphenylene methyl. In graphic formula I, -R'O- is a bivalent alkyleneoxy

(substituted and unsubstituted) group derived from a cyclic ether other than ethylene oxide or mixture of such cyclic ethers. More particularly, -R'O- may be represented by the graphic formula -CH₂CH(R")-O-, wherein R" is methyl, ethyl, phenyl, phenyloxymethyl,

-CH₂-(CH₂)₂-CH₂-O-, and mixtures thereof. Still more particularly, -R'O- may be described as the bivalent radical derived from cyclic ethers selected from the group consisting of propylene oxide, (e.g., 1,2-epoxypropane), butylene oxide (e.g., 1,2-epoxybutane), styrene oxide [(epoxyethyl) benzene], tetrahydrofuran, phenyl glycidyl ether (1,2-epoxy-3-phenoxypropane) and mixtures thereof. Preferably, -R'O- is the bivalent epoxy group derived from propylene oxide, butylene oxide and mixtures of propylene oxide and butylene oxide. The letter E in graphic formula I is the bivalent ethylene radical, and m and n are each numbers which may vary from about 5 to about 100, preferably between about 5 or 10 and about 50. The ratio of m:n may vary from about 20:1 to about 1:20. The specific ratio of m:n used will depend on the particular polymerization system in which the polymerizable surfactant of the present invention is incorporated. Varying the ratio of m:n will vary the HLB (Hydrophilic-Lipophilic Balance) of the polymerizable surfactant compound. If the polymerization system requires a hydrophobic surfactant, m will be greater than n. Conversely, if the emulsion polymerization system requires a hydrophilic surfactant, then m will be less than n. The ratio of m:n should be chosen so that the resulting compound is capable of reducing the surface tension of water.

Preferably, the surface tension of a 0.1 weight percent aqueous solution of the polymerizable surfactant compound at 25°C is less than

38 dynes per centimeter. More preferably, the surface tension of such a solution is in the range of 30 to 35 dynes per centimeter. Surface tension may be measured by a Du Nouy tensiometer. X in graphic formula I is selected from the group consisting of hydroxyl (-OH), chloride (-C1), sulfonate (-SO₃), sulfate (-OSO₃), phosphate [-O-P(O)(OH)₂], acetate (-CH₂-C(O)OH), isethionate

(-CH₂-CH₂-SO₃H), and the alkali metal salts of the aforedescribed sulfonate, sulfate, phosphate, acetate and isethionate anionic groups, tertiary amino, i.e., -N(R₂)(R₃)R₄, wherein R₂, R₃ and R₄ are each selected from the group consisting of alkyl and hydroxyalkyl groups, particularly groups containing from 1 to 5 carbon atoms, e.g., a tertiary amine derived from trimethylamine, triethylamine, triethanolamine and diethylmethylamine. Commonly, X will be selected from the group consisting of sulfonate, sulfate, phosphate, acetate

(and alkali metal salts thereof), hydroxyl, chloride and tertiaryamino. As used herein, the term "alkali metal" includes sodium, potassium, lithium and ammonium. The polymerizable surfactant of the present invention may be prepared by reacting the precursor alcohol, ROH, wherein R is as heretofore defined with respect to graphic formula I, with the desired amount of first cyclic ether (R'O), e.g., propylene oxide, butylene oxide or mixtures thereof, and subsequently reacting the resulting epoxy-containing product with the desired amounts of ethylene oxide (EO). The product resulting from this reaction sequence is a material corresponding to graphic formula I wherein X is hydroxyl. Such a material may be used as a non-ionic surfactant.

Preparation of the polymerizable surfactant wherein X is sulfate may be accomplished by reacting the corresponding non-ionic

(hydroxy end-capped) surfactant with chlorosulfonic acid, 100% sulfuric acid or with sulfur trioxide. See, for example, U.S. Patents 2,143,759 and 2,106,716 of H. A. Bruson. Neutralization of the reaction product with an alkaline reagent, e.g., an alkali metal hydroxide such as sodium hydroxide, yields the corresponding salt, e.g., the sodium salt. Similarly, the corresponding non-ionic surfactant may be reacted with polyphosphoric acid (P₂O₅ ● 2H₂O) or chloroacetic acid by known procedures to prepare the phosphate or acetate end-capped polymerizable surfactant.

Sulfonate terminated polymerizable surfactants of graphic formula I may be prepared by first converting the corresponding non-ionic material to the corresponding chloride by reaction with thionyl chloride or carbonyl chloride (followed by subsequent decarboxylation to the chloride) and then reacting the chloride derivative with sodium sulfite. In conducting the sulfonation reaction, the pre-formed sulfonate terminated surfactant product may be used as the reaction medium to improve conversions. Thus, from 0 to 20 weight percent (based on the total amount of reactants) of pre-formed sulfonate product may be added to the reactor.

The chloride capped surfactant may be used itself as a surfactant as well as a precursor for preparing the sulfonate, isethionate or quaternary ammonium terminated surfactant. The isethionate derivative may be prepared by reacting the chloride-capped surfactant with isethionic acid in the presence of a base, e.g., sodium hydroxide. Quaternary ammonium derivatives may be prepared by reacting the corresponding chloride with the tertiary amine, N(R₂)(R₃)R₄, wherein R₂, R3 _and R₄ are the same as defined with respect to X in graphic formula I. Processes for converting the non-ionic polymerizable surfactant to the chloride, sulfate, sulfonate, phosphate ester, acetate, isethionate or quaternary ammonium derivative are well known to the skilled chemist.

The precursor alpha-beta ethylenically unsaturated alcohols used to prepare the polymerizable surfactant materials of graphic formula I may be prepared by methods known in the art. Some, such as allyl alcohol, are readily commercially available. In accordance with a particular embodiment of the present invention, the precursor alcohol is charged to a suitable autoclave and heated to a temperature in the range of from about 110°C. to about 130°C. Propylene oxide and/or 1,2-epoxybutane are metered into the autoclave and reacted with the unsaturated alcohol in the presence of an alkaline reagent such as sodium hydroxide. After the desired amount of propoxylation and/or butoxylation is achieved, ethylene oxide is substituted for the propylene oxide and/or 1,2-epoxybutane reactant(s) and metered into the reactor until the desired level of ethoxylation is achieved. Pressures in the reactor will usually remain at less than 100 pounds per square inch gage during these reactions. The resulting poly(alkyleneoxy) material is removed from the reactor, the alkaline reagent neutralized with acid, and the product recovered by filtration. This non-ionic material maybe converted to the sulfate, sulfonate, phosphate ester, acetate, or isethionate (or their salts), or the chloride or quaternary ammonium derivative by the methods heretofore described. The number of epoxy, e.g., alkyleneoxy, groups present in the polymerizable surfactant material will vary as described with respect to graphic formula I. The number of epoxy units present per mole of surfactant of graphic formula I, i.e., the letters "m" and "n", is the average number of moles of cyclic ether present per mole of surfactant and hence the value of m and n may be a fractional number between 5 and 100.

Polymerizable surfactant materials of the present invention may be used in emulsion (or suspension) or solution polymerizations.

Such polymerizations may be carried out by free radical initiated polymerization using batch, continuous, or controlled monomer feed processes, known conditions of stirring time and temperature, and known kinds of additives such as initiators, surfactants, electrolytes, pH adjusting agents, buffering agents and the like. In general, the emulsion or solution polymerization will be carried out from about

20°C. to about 120°C, e.g., between about 50°C. and about 80°C. Batch polymerization times may vary depending on the method of polymerization and the monomers being polymerized. Such times may vary from about 2 to about 10 hours. The polymerizable surfactant materials of the present invention are particularly useful in emulsion polymerization processes of the liquid phase type wherein water comprises the continuous phase and the monomer(s) is present substantially as a dispersed phase at the initiation of polymerization. The polymerization medium has incorporated therein at a minimum a sufficient amount of the polymerizable surfactant of the present invention to produce a stable, small particle size, dispersed monomer emulsion or suspension. The polymerizable surfactant of the present invention may be added batchwise, semicontinuously or continuously to the polymerizable reaction mixture. The quantity of polymerizable surfactant used in the polymerization of ethylenically unsaturated monomers, particularly when used as the sole emulsion polymerization surfactant, may range from about 1.0 to about 10 weight percent based on the total reactant monomer content employed in the given emulsion polymerization system. Preferably the amount of such polymerizable surfactant material employed ranges from about 3.0 to about 6 weight percent, similarly based on total monomer. The polymerizable surfactant materials of the present invention may be used in an emulsion polymerization reaction in combination with conventional emulsion polymerization surfactants that are not reactive, i.e., non-copolymerizable with the polymerizable monomers. In selecting cosurfactant materials to be used, anionic and cationic materials should not be used together. Anionic and non-ionic surfactant materials or cationic and non-ionic surfactant materials may be used in combination. The reactive surfactants of the present invention themselves characteristically display excellent capacity for producing emulsion stability characteristics in the emulsion polymerization. It is contemplated that such conventional surfactants will be used in amounts of from 3 to 6 weight percent, based on the total amount of monomer(s).

In another embodiment of the present invention, it is contemplated that polymerizable surfactants of the present invention may be used as comonomers with the ethylenically unsaturated monomer(s) to modify the physical properties of the resulting polymer. The amount of polymerizable surfactant that may be so used may vary, e.g., from about 1 to about 25 weight percent, but will commonly be in the range of from about 1 to about 10, e.g., 3 to 6, weight percent, based on the total reactant monomer content. In this embodiment, conventional emulsion polymerization surfactants also may be used as additives to the polymerization, e.g., in amounts of from about 3 to 6 weight percent, based on the total amount of monomeric reactants to be polymerized. In a further embodiment of the present invention, ethylenically unsaturated monomer(s) and from 1-25 weight percent (as described hereinbefore) of the polymerizable reactive compounds represented by graphic formula I are copolymerized by solution polymerization. Any conventional organic solvent, which may be a solvent for both the monomer(s) and polymer, or just the monomer(s) may be used. Organic free-radical initiators, as described herein, may be used to initiate the solution polymerization. A sufficient quantity of a polymerization initiator (such as a conventional free radical initiator) is introduced into the polymerization medium to cause polymerization of the monomer(s) at the particular temperatures employed. Initiators used in emulsion polymerization processes are of the type which produce free radicals and conveniently are peroxygen compounds, for example: inorganic peroxides such as hydrogen peroxide and inorganic persulfate compounds such as ammonium persulfate, sodium persulfate and potassium persulfate; organic hydroperoxides such as cumene hydroperoxide and tertiary butyl hydroperoxide; organic peroxides such as benzoyl peroxide, acetyl peroxide, lauroyl peroxide, peroxydicarbonate esters such as diisopropyl peroxydicarbonate, peracetic acid and perbenzoic acid - sometimes activated by water-soluble reducing agents such as a ferrous compound, sodium bisulfite or hydroxylamine hydrochloride - and other free radical producing materials such as 2,2'-azobisisobutyronitrile. Conventional cationic nonpolymerizable surfactants include the classes of salts of aliphatic amines, especially the fatty amines, quaternary ammonium salts and hydrates, fatty amides derived from disubstituted diamines, fatty chain derivatives of pyridinium compounds, ethylene oxide condensation products of fatty amines, sulfonium compounds, isothiouronium compounds and phosphonium compounds. Specific examples of the cationic surfactants are dodecylamine acetate, dodecylamine hydrochloride, tetradecylamine hydrochloride, hexadecylamine acetate, lauryl dimethylamine citrate, octadecylamine sulfate, dodecylamine lactate, cetyl trimethyl ammonium bromide, cetyl pyridinium chloride, an ethanolated alkyl guanidine amine complex, stearyl dimethyl benzyl ammonium chloride, cetyl dimethyl amine oxide, cetyl dimethyl benzyl ammonium chloride, tetradecylpyridinium bromide, diisobutyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride, 1-(2-hydroxyethyl)-2-(mixed pentadecyl and heptadecyl)-2-imidazoline, resin amine ethoxylate, oleyl imidazoline, octadecyl ethylmethyl sulfonium methyl sulfate, dodecyl-bis-hydroxyethylsulfonium acetate, dodecylbenzyl-dimethylsulfonium chloride, dodecylbenzyltrimethylphosphonium chloride and S-p-dodecylbenzyl-N-N-N'-N'-tetramethylisothioronium chloride.

Representative types of anionic emulsifiers are the alkyl aryl sulfonates, the alkali metal alkyl sulfates, the sulfonated alkyl esters, the fatty acid soaps and the like. Specific examples of these well known emulsifiers are dodecylbenzene sodium sulfonate, sodium butyl naphthalene sulfonate, sodium lauryl sulfate, disodium dodecyldiphenyl ether disulfonate, n-octadecyl disodium sulfosuccinate and dioctyl sodium sulfosuccinate. Typical nonionic emulsifiers (surfactants) are compounds formed by the reaction of an alkylene oxide, such as ethylene oxide, propylene oxide or butylene oxide, with long chain fatty alcohols, long chain fatty acids, alkylated phenols, long chain alkyl mercaptans, long chain alkyl primary amines, for example, cetylamine, the alkylene oxides being reacted in a ratio of from about 5 moles to 20 moles or higher, e.g., up to 50 moles, per mole of the coreactant. Other representative compounds are monoesters, e.g., the reaction products of a polyethylene glycol with a long chain fatty acid, for example, glycerol monostearate, sorbitan, trioleate and partial and complete esters of long chain carboxylic acids with polyglycol ethers of polyhydric alcohols. By "long chain" in the above description is meant an aliphatic group having from six carbon atoms to 20 carbon atoms or more. A further additive that may be introduced into the polymerization reaction media is a conventional chain transfer agent such as an alkyl polyhalide or mercaptan. Examples include: bromoform, carbon tetrachloride, carbon tetrabromide, bromoethane, alkyl mercaptans of 1 to 12 carbon atoms, e.g., dodecylmercaptan, thiophenol and hydroxyalkyl mercaptans, e.g., mercaptoethanol. Ethylenically unsaturated monomer(s) which may be copolymerized with an ethylenically unsaturated, polymerizable material of graphic formula I are well known in the art and are illustrated herein only by representative example. Ethylenically unsaturated monomers are represented by, but not restricted to, mono- and polyunsaturated hydrocarbon monomers, vinyl esters, e.g., vinyl esters of C₁-C₆ saturated monocarboxylic acids, vinyl ethers, monoethylenically unsaturated mono- and polycarboxylic acids and their alkyl esters, e.g., acrylic acid esters and methacrylic acid esters,

(particularly their C₁-C₁₂ alkyl esters), the nitriles, vinyl and vinylidene halides, amides of unsaturated carboxylic acids and amino monomers. Representative examples of hydrocarbon monomers include compounds such as the styrene compounds, e.g., styrene, carboxylated styrene, and alpha-methyl styrene, and conjugated dienes, for example, butadiene, isoprene and copolymers of butadiene and isoprene. Representative examples of vinyl and vinylidene halides include: vinyl chloride, vinylidene chloride, vinyl fluoride and vinylidene fluoride. Acrylic ester and methacrylic ester examples include alkyl acrylates and methacrylates. Typical acrylic esters and methacrylic esters include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, hexyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 3,3-dimethylbutyl acrylate, 3,3-dimethyl butyl methacrylate, and lauryl acrylate. Suitable vinyl esters include aliphatic vinyl esters, such as vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl valerate, and vinyl caproate, and allyl esters of saturated monocarboxylic acids, such as allyl acetate, allyl propionate and allyl lactate.

Typical vinyl ethers include methylvinyl ether, ethylvinyl ether and n-butylvinyl ether. Typical vinyl ketones include methylvinyl ketone, ethylvinyl ketone and isobutylvinyl ketone. Suitable dialkyl esters of monoethylenically unsaturated dicarboxylic acids include dimethyl maleate, diethyl maleate, dibutyl maleate, dioctyl maleate, diisooctyl maleate, dinonyl maleate, diisodecyl maleate, ditridecyl maleate, dimethyl fumarate, diethyl fumarate, dipropyl fumarate, dibutyl fumarate, dioctyl fumarate, diisooctyl fumarate, didecyl fumarate, dimethyl itaconate, diethyl itaconate, dibutyl itaconate and dioctyl itaconate. Suitable monoethylenically unsaturated monocarboxylic acids include acrylic acid, methacrylic acid, ethacrylic acid and crotonic acid; monoethylenically unsaturated dicarboxylic acids, such as maleic acid, fumaric acid, itaconic acid and citraconic acid; and monoethylenically unsaturated tricarboxylic acids, such as aconitic acid and the halogen-substituted derivatives, e.g., alphachloroacrylic acid, and anhydrides of these acids, such as, e.g., maleic anhydride and citraconic anhydride are suitable for use as monomers. Acrylonitrile, alpha-chloro-acrylonitrile and methacrylonitrile are among the corresponding nitriles of such acids which can be used as monomers. Suitable amides of such acids include unsubstituted amides such as acrylamide, methacrylamide and other alpha-substituted acrylamides and N-substituted amides obtained by conventional reaction of the amides of the aforementioned mono- and poly-carboxylic acids with an aldehyde, such as formaldehyde. Typical

N-substituted amides include N-methylolacrylamide, N-methylolmethacrylamide, alkylated N-methylolacrylamides and N-methylolmethacrylamides, such as N-methoxymethylacrylamide and N-methoxymethylmethacrylamide.

Typical amino monomers include substituted and unsubstituted aminoalkyl acrylates, hydrochloride salts of amino monomers and methacrylates, such as beta-aminoethylacrylate, beta-aminoethylmethacrylate, dimethylamino-methylacrylate, beta-methylaminoethylacrylate, and dimethylaminomethylmethacrylate. Hydroxy-containing monomers include beta-hydroxyethylacrylate, beta-hydroxypropylacrylate, gamma-hydroxypropylacrylate and beta-hydroxyethylmethacrylate.

The aforesaid monomers, particularly the acrylic esters and methacrylic esters, may be homopolymerized or copolymerized with other of the described monomers, i.e., one or more different monomers capable of addition type polymerization.

The reactive surfactants of the present invention may find particular use in polymerization systems including various monomer and monomer mixtures to form homopolymers and copolymers, such as vinyl acetate-acrylic monomer mixtures, vinyl acetate monomer, ethylene-vinyl acetate monomer mixtures, styrene, styrene-acrylic monomer mixtures, butadiene-acrylonitrile monomer mixtures, styrene-butadiene monomer mixtures, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, and mixtures of other monomers with each of said vinyl and vinylidene halides, acrylic monomer-acrylonitrile monomer mixtures, and all acrylic monomer mixtures. The term "acrylic" as used herein is intended to mean and include one or more acrylic esters and/or methacrylic esters with and without acrylic acid or methacrylic acid. Such monomer mixtures are well known to the skilled artisan. The polymerizable surfactants of the present invention polymerize along with the conventional reactant monomer(s) in the polymerization process, thereby to form water-insoluble, substantially surfactant-free polymer particles. Thus, the polymer latex product is not contaminated with an undesirable residue of water-soluble surfactant. The polymer product has improved resistance to water and may be used in any end use application for which the particular polymer product produced from the conventional reactant monomer(s) may be used. Examples include interior and exterior coatings, e.g., latex paints, container, paper and paperboard coatings, e.g., can coatings, adhesives, such as water-borne adhesives and pressure sensitive adhesives, sealants, industrial coatings, automotive coatings, textile coatings and binders, floor finishes, water-based inks, films, and binders for non-woven materials such as carpet backing. The polymer product prepared with the polymerizable surfactants of the present invention may be used as the principle resin component or as a minor component of a resin mixture used to prepare the coatings, adhesives, sealants, binders, inks, floor finishes, etc. described herein. The remainder of the film forming composition may comprise various fillers, e.g., pigments, colorants, etc., solvents, e.g., aqueous or organic solvents, plasticizers, antioxidants, curing agents, thickeners, surfactants, preservatives, wet strength additives, and other adjuvant materials added in conventional amounts to resin compositions used in the aforedescribed end-use applications. The present process is more particularly described in the following examples, which are intended as illustrative only since numerous modifications and variations therein will be apparent to those skilled in the art. EXAMPLE 1 A one liter magnetically stirred autoclave was charged with

58.1 grams of allyl alcohol and 0.92 grams of sodium hydroxide. The autoclave was sealed and the air atmosphere therein replaced with nitrogen. The autoclave was pressurized with nitrogen to 10 pounds per square inch gage (psig) and the contents heated to 120°C.

1,2-epoxybutane was introduced slowly and continuously into the autoclave while the reactor contents were maintained between about 110°C. and 130°C. The maximum operating pressure during addition of the 1,2-epoxybutane was less than 100 psig. After 600 grams of

1,2-epoxybutane had been introduced into the autoclave, the reaction slowed. The contents of the autoclave were cooled to about 15°C, the autoclave opened and an additional 0.66 grams of sodium hydroxide introduced into the autoclave to enhance the rate of alkoxylation. The autoclave was closed, the air atmosphere replaced with nitrogen, the autoclave pressurized to a pressure of 10 psig with nitrogen and the contents heated to 120°C. 1,2-epoxybutane was again charged to the autoclave until the total amount of epoxybutane added reached about 865 grams. When the pressure in the autoclave reached a steady value, the autoclave was cooled. 886.4 grams of a light yellow-colored liquid product was recovered. The product was subjected to vacuum degassing to remove any residual unreacted 1,2epoxybutane from the product. The degassed product was identified as the butoxylated product of allyl alcohol. Proton nuclear magnetic resonance (NMR) spectroscopy indicated that the number of butoxy groups in the product was about 12.3 per molecule.

A one liter magnetically stirred autoclave was charged with 332 grams of the above-described degassed butoxylated allyl alcohol.

After replacing the air atmosphere in the autoclave with nitrogen, the butoxylated allyl alcohol was heated to 120ºC. and 240 grams of ethylene oxide added slowly to the autoclave over a period of about 3 hours so as to maintain the reaction temperature at 120°C. and the operating pressure below 90 psig. The resultant product was allowed to cool to 30°C. and 0.89 grams of acetic acid added to the reaction product for neutralization of the basicity in the reaction mixture. The final product was a light yellow liquid. The number of ethoxy units per molecule in the product were determined by proton NMR to be about 15.3. This product will be referred to herein as Sample 1-A. A 0.1 weight percent aqueous solution of Sample 1-A was prepared and the surface tension of the solution measured at 25°C. with a Du Nouy tensiometer. The surface tension was found to be 31.6 dynes/centimeter.

The one liter autoclave was charged with 277 grams of the degassed butoxylated allyl alcohol and flushed with nitrogen for 30 minutes. The butoxylated allyl alcohol was heated to 120°C. and 330 grams of ethylene oxide charged slowly over about 3 hours to the autoclave while maintaining the reaction temperature at about 120°C. and the operating pressure below 90 psig. 0.74 grams of acetic acid were added to neutralize the basicity in the product. 614.7 grams of a light yellow liquid product was recovered. Proton-NMR indicated that the number of ethoxy groups per molecule in the product was about 26.1. This product will be referred to herein as Sample 1-B. The surface tension of a 0.1 weight percent aqueous solution of Sample 1-B product was 32.2 dynes/centimeter at 25°C.

The one liter autoclave was charged with 221 grams of the degassed butoxylated allyl alcohol, flushed with nitrogen, and the butoxylated allyl alcohol heated to 120ºC. 370 grams of ethylene oxide were charged slowly to the autoclave over about 4 hours while maintaining the reaction temperature at about 120°C. and the reaction pressure at less than 100 psig. When all of the ethylene oxide had been charged to the autoclave, the pressure was permitted to equilibrate and the autoclave cooled. 0.59 grams of acetic acid were added to neutralize the basicity in the reaction product. Proton-NMR indicated that the number of ethoxy units in the light yellow liquid product was about 40.6. This product will be referred to herein as Sample 1-C. The surface tension of a 0.1 weight percent aqueous solution of the Sample 1-C product was 33.6 dynes/centimeter at 25°C.

EXAMPLE 2 A two liter, jacketed round-bottom flask equipped with a phosgene inlet tube, dry ice cooled condenser, stirrer and dropping funnel was charged with 20 grams of liquid phosgene. The reaction flask was then charged simultaneously with 477 grams of product Sample 1-B described in Example 1 and 40 grams of additional phosgene. The reaction mixture was stirred at 15-20°C. for several hours before excess phosgene was removed by degassing the reaction product. The resulting chloroformate was converted to the corresponding chloride by heating it in the presence of 1.23 grams of trioctyl methyl ammonium chloride at 120-140°C. for 4 hours. 480 grams of product were recovered. The product was confirmed as the corresponding chloride by proton-NMR and infrared spectroscopy, and total chloride analysis.

EXAMPLE 3

A 0.5 liter magnetically stirred autoclave was charged with 100.7 grams of the chloride product of Example 2, 12.3 grams of sodium sulfite (98 percent), 265.1 grams of deionized water and 1.2 grams of a 50 percent aqueous solution of sodium hydroxide. The autoclave was sealed and the contents heated to 155°C. and maintained at temperature overnight. The pressure within the autoclave stabilized at about 60 psig. The contents of the autoclave were cooled subsequently to less than 5°C. The product, i.e., the corresponding sulfonate of the chloride product of Example 2, was a light yellow liquid containing 28.3 percent solids with 7.2 percent (as is) anionic surfactant activity.

EXAMPLE 4 The procedure of Example 3 was repeated except that 77.4 grams of the pre-formed sulfonate product produced in Example 3 was added to the autoclave with the reactants. 423.7 grams of a light yellow clear liquid product was recovered from the autoclave. The product was treated with 1.00 grams of hydrogen peroxide (49.5 percent) for removal of residual sulfite anion. The product contained about 30 percent solids and analyzed about 14.6 percent anionic surfactant activity.

EXAMPLE 5 The procedure of Example 3 was repeated except that 113.2 grams of the pre-formed sulfonate product from Example 4 was added to the autoclave with the reactants. The product was a light yellow clear liquid. It was treated with 1.33 grams of hydrogen peroxide (49.5 percent) for removal of residual sulfite anion. The sulfonate product was combined with the product of

Example 4. The resultant mixture had a solids content of about 28.3 percent and analyzed about 16.2 percent anionic surfactant activity. The surface tension of a 0.1 weight percent aqueous solution of the product was found to be 35.6 dynes/centimeter at 25°C.

EXAMPLE 6

Using the procedure of Example 2, 401 grams of Sample 1-A were reacted with phosgene and the resulting chloroformate decarboxylated to the corresponding chloride with 1.1 grams of trioctyl methyl ammonium chloride. 77.7 grams of the resulting chloride product were converted to the sulfonate by the procedure of Example 3 utilizing 15.4 grams of sodium sulfite, 174.3 grams of deionized water and 1.54 grams of a 50 percent aqueous solution of sodium hydroxide. A milky light yellow liquid containing 33.3 percent solids with 9.6 percent anionic surfactant activity was obtained.

EXAMPLE 7 The sulfonation procedure of Example 3 was followed using

77.7 grams of the chloride product of Example 6, 15.4 grams of sodium sulfite, 1.54 grams of sodium hydroxide, 218.3 grams of deionized water and 135.9 grams of the pre-formed sulfonate product produced in Example 6. The product contained about 29.3 percent solids and analyzed about

10.8 percent anionic surfactant activity. After standing for about two weeks, the product was observed to have separated into two layers.

EXAMPLE 8

The procedure of Example 7 was repeated except that 149.8 grams of the top layer of the sulfonate product of Example 7 was used as the pre-formed sulfonate in the sulfonation reaction. The sulfonate product was treated with 1.33 grams of hydrogen peroxide (49.5 percent) to remove residual sulfite anion, and then combined with the remainder of the sulfonate product from Example 7. The combined product had

11.1% anionic surfactant activity. The combined product had 11.1% anionic surfactant activity. The surface tension of a 0.1 weight percent aqueous solution of the product was found to be 35.9 dynes/centimeter at 25°C. EXAMPLE 9 Following the procedure of Example 2, 407 grams of Sample 1-C were converted to the corresponding chloroformate with phosgene. The chloroformate was decarboxylated to the corresponding chloride with

1.05 grams of trioctyl methyl ammonium chloride. 115.6 grams of the resulting chloride product were converted to the corresponding sulfonate by the procedure of Example 3 utilizing 10.8 grams of sodium sulfite, 1.1 grams of a 50 percent aqueous solution of sodium hydroxide and 296.2 grams of deionized water. The product was a light yellow clear solution at 60°C. It was treated with 1.9 grams of hydrogen peroxide (49.5 percent) to remove any residual sulfite anion. The product contained 28.8 percent solids with 15.8 anionic surfactant activity.

EXAMPLE 10 The sulfonation procedure of Example 9 was repeated except that 57.1 grams of the pre-formed sulfonate product of Example 9 was added to the autoclave with the reactants. The product was a clear light yellow liquid which was treated with 1.76 grams of hydrogen peroxide to remove residual sulfite anion. The sulfonate product contained about 31.9 percent solids and analyzed 18.7 percent anionic surfactant activity.

The sulfonate product was combined with the remainder of the product from Example 9. The resulting mixture contained about 32.6 percent solids and analyzed about 16.1 percent anionic surfactant activity. The surface tension of a 0.1 weight percent aqueous solution of the product was found to be 35.1 dynes/centimeter at 25°C.

EXAMPLE 11 A vinyl acetate-butyl acrylate copolymer was prepared utilizing the sulfonate product of Example 5 as the sole surfactant. A one liter resin kettle was charged with a solution of 31.7 grams of the sulfonate product of Example 5 in 281 grams of deionized water. The solution was heated to 80°C. under a nitrogen atmosphere. One gram of potassium persulfate (K₂S₂O₈) was added to the solution followed by the slow addition of 50 milliliters of a mixture comprising 202 grams of vinyl acetate and 36 grams of butyl acrylate. The polymerization temperature was maintained at 75-80°C. for 30 minutes after the addition of the 50 milliliter portion of the monomer mixture. The remainder of the monomer mixture was charged to the kettle over a 3-4 hour period while maintaining the polymerization temperature at between

70°C. and 75°C. The contents of the resin kettle were post stirred at 70°C. for 1 hour and then 10 grams of 2 percent formaldehyde sulfoxylate added to the kettle to complete the polymerization. The kettle contents were allowed to cool to ambient temperature and the latex in the kettle recovered by filtration through a cheese cloth. Less than 1 percent of the polymer product had coagulated. A portion of the latex was cast into a film and the film dissolved in chloroform-d (CD₃CI). Proton-NMR spectroscopy of the chloroform solution did not reveal the presence of any allylic hydrogens, which indicated that the sulfonate product of Example 5 had reacted completely during the polymerization. A film of the latex was cast onto a microscope slide and air dried for at least 24 hours. A NRL contact angle goniometer, Model 100-00, was employed to measure the contact angle of a drop of deionized water placed onto the film. The contact angle was determined within 10 seconds of the water being placed upon the film and was found to be 52°.

EXAMPLE 12 For purposes of comparison, the emulsion polymerization of

Example 11 was performed using 24 grams of sodium lauryl sulfate, (30 percent active) as the sole surfactant. The product was recovered by filtration through a cheese cloth and less than 1 percent of the product was found to have coagulated.

In accordance with the procedure described in Example 11, the contact angle for a drop of water placed on a film prepared from the aforesaid latex was measured. The water droplet was observed to spread immediately with a resulting contact angle of less than 5°.

The contact angle measurements of Examples 11 and 12 show that the latex prepared with the copolymerizable surfactant of Example

5 was less water sensitive than those made from conventional emulsifiers, i.e., sodium lauryl sulfate. EXAMPLE 13

A vinyl acetate homopolymer was prepared utilizing the sulfonate product of Example 10 as the sole surfactant. A one liter resin kettle was charged with a solution of 20.0 grams of the sulfonate product of Example 10 in 238 grams of deionized water. The solution was heated to 80°C. under a nitrogen atmosphere and 0.5 grams of potassium persulfate (K₂S₂O₈) added to the solution. 50 grams of vinyl acetate was added slowly to the resin kettle. The reaction temperature was maintained at 75-80°C. for 30 minutes after completing the initial charge of vinyl acetate. Subsequently, 150 grams of vinyl acetate was added to the kettle over 3-4 hours while maintaining the polymerization temperature at about 80°C. The contents of the resin kettle were post stirred for one hour at 85°C, cooled to ambient temperature, and filtered through a cheese cloth. The amount of coagulation found was about one percent. A film of the latex was cast onto a microscope slide and air dried for at least 24 hours. The contact angle for a drop of water placed on the film was measured (as per Example 11) and found to be 53°. Although the present invention has been described with reference to specific details of certain embodiments thereof, it is not intended that such detail should be regarded as limitations upon the scope of the invention, except as and to the extent that they are included in the accompanying claims.

Claims

What Is Claimed Is:

1. A compound represented by the following graphic formula: %

wherein R is selected from the group consisting of C₂-C₁₈ alkenyl, acrylyl, acrylyl(C₁-C₁₀)alkyl, methacrylyl, methacrylyl (C₁-C₁₀) alkyl, vinylphenyl and vinylphenylene (C₁-C₆) alkyl, R'O is selected from the group consisting of bivalent alkyleneoxy groups derived from cyclic ethers other than ethylene oxide and mixtures of such alkyleneoxy groups, E is the bivalent ethylene radical, m and n are each numbers from about 5 to about 100, the ratio of m:n being from about 20:1 to about 1:20, and X is a member selected from the group consisting of hydroxyl, chloride, tertiaryamino, and the anionic groups sulfonate, sulfate, phosphate, acetate, isethionate (and alkali metal salts of such anionic groups).

2. The compound of claim 1 wherein the alkyleneoxy group, R'O, is represented by the graphic formula, -CH₂CH(R")-O-; wherein R" is methyl, ethyl, phenyl, phenyloxymethyl, and -CH₂-(CH₂)₂-CH₂-O-, m and n are each numbers of from about 5 to about 50, and X is selected from the group consisting of chloride, hydroxyl, tertiaryamino and the anionic groups sulfonate, sulfate, phosphate, acetate, isethionate (and alkali metal salts of such anionic groups).

3. The compound of claim 1 wherein R is selected from the group consisting of vinyl and allyl, R'O is the bivalent epoxy group derived from propylene oxide, butylene oxide and mixtures of propylene oxide and butylene oxide, m and n are each numbers of from about 5 to about 50, and X is selected from the group consisting of chloride, hydroxyl, tertiaryamino, and the anionic groups sulfonate, sulfate, phosphate, acetate, isethionate (and alkali metal salts of such anionic groups).

4. The compound of claim 3 wherein the tertiaryamino group is represented by the graphic formula, -N⁺(R₂)(R₃)R₄, wherein R₂, R₃ and R₄ are each selected from the group consisting of C₁-C₅ alkyl and hydroxy (C₁-C₅)alkyl.

5. The compound of claim 3 wherein R is allyl, and R'O is the bivalent epoxy group derived from butylene oxide.

6. The compound of claim 5 wherein X is selected from the group consisting of chloride, hydroxyl and the anionic groups sulfate, sulfonate, phosphate (and alkali metal salts of such anionic groups).

7. In the method of conducting a free-radical initiated polymerization of ethylenically unsaturated reactant monomer, the improvement wherein said polymerization is conducted in the presence of from about 1 to about 25 weight percent, based on the total amount of reactant monomer, of a compound represented by the following graphic formula:

wherein R is selected from the group consisting of C₂-C₁₈ alkenyl, acrylyl, acrylyl(C₁-C₁₀)alkyl, methacrylyl, methacrylyl (C₁-C₁₀) alkyl, vinylphenyl and vinylphenylene (C₁-C₆) alkyl, R'O is selected from the group consisting of bivalent alkyleneoxy groups derived from cyclic ethers other than ethylene oxide and mixtures of such alkyleneoxy groups, E is the bivalent ethylene radical, m and n are each numbers from about 5 to about 100, the ratio of m:n being from about 20:1 to about 1:20, and X is a number selected from the group consisting of hydroxyl, chloride, tertiaryamino, and the anionic groups sulfonate, sulfate, phosphate, acetate, isethionate (and alkali metal salts of such anionic groups).

8. The method of claim 7 wherein the polymerization is an emulsion polymerization.

9. The method of claim 8 wherein non-polymerizable surfactants are present during said polymerization.

10. The method of claim 8 wherein the ethylenically unsaturated monomer is selected from the group consisting of mono- and polyunsaturated hydrocarbon monomers, vinyl esters, vinyl ethers, monoethylenically unsaturated mono- and polycarboxylic acids and their alkyl esters, nitriles, vinyl halides, vinylidene halides, amides of unsaturated carboxylic acids, amino monomers, and mixtures of said monomers.

11. The method of claim 10 wherein the monoethylenically unsaturated alkyl monocarboxylic acid is acrylic acid or methacrylic acid, and their alkyl ester is a C₁-C₁₂ alkyl ester.

12. The method of claim 8 wherein the ethylenically unsaturated monomer is selected from the group consisting of vinyl acetate-acrylic monomer mixtures, vinyl acetate, styrene-acrylic monomer mixtures, styrene-butadiene monomer mixtures, vinyl chloride, vinyl fluoride, vinylidene chloride, vinylidene fluoride, and acrylic monomer mixtures.

13. In the process of conducting a free-radical initiated emulsion polymerization of ethylenically unsaturated reactant monomer, the improvement wherein said polymerization is conducted in the presence of from about 1 to about 25 weight percent, based on the total amount of reactant monomer, of a compound represented by the following graphic formula, wherein R is selected, from the group consisting of C₂-C₁₈ alkenyl, acrylyl, acrylyl (C₁-C₁₀) alkyl, methacrylyl, methacrylyl (C₁-C₁₀) alkyl, vinylphenyl, and vinylphenylene (C₁-C₆) alkyl, R'O is selected from the group consisting of bivalent alkyleneoxy groups represented by the graphic formula, -CH₂CH(R")-O-, wherein R" is methyl, ethyl, phenyl, phenyloxymethyl, and -CH₂-(CH₂)₂-CH₂-O-, and mixtures of such alkyleneoxy groups, E is the bivalent ethylene radical, m and n are each numbers of from about 5 to about 50, the ratio of m:n being from about 20:1 to about 1:20, and X is selected from the group consisting of chloride, hydroxyl, tertiaryamino, and the anionic groups sulfonate, sulfate, phosphate, acetate isethionate (and alkali metal salts of such anionic groups).

14. The process of claim 13 wherein compounds represented by the graphic formula, 4 4

are present in amounts of from about 1 to about 10 weight percent.

15. The process of claim 14 wherein non-polymerizable surfactants are present during said polymerization process.

16. The process of claim 14 wherein R is selected from the group consisting of vinyl and allyl, R'O is the bivalent epoxy group derived from propylene oxide, butylene oxide and mixtures of propylene oxide and butylene oxide, m and n are each numbers of from about 5 to about 50, and X is selected from the group consisting of chloride, hydroxyl, tertiaryamino, and the anionic groups sulfonate, sulfate, phosphate, acetate, isethionate (and alkali metal salts of such anionic groups ).

17. The process of claim 16 wherein the ethylenically unsaturated monomer is selected from the group consisting of mono- and polyunsaturated hydrocarbon monomers, vinyl esters, vinyl ethers, monoethylenically unsaturated mono- and polycarboxylic acids and their alkyl esters, nitriles, vinyl halides, vinylidene halides, amides of unsaturated carboxylic acids, amino monomers, and mixtures of said monomers.

18. The method of claim 17 wherein the monoethylenically unsaturated monocarboxylic acid is acrylic acid or methacrylic acid, and their alkyl ester is a C₁-C₁₂ alkyl ester.

19. The process of claim 16 wherein the ethylenically unsaturated monomer is selected from the group consisting of vinyl acetate-acrylic monomer mixtures, vinyl acetate, styrene-acrylic monomer mixtures, styrene-butadiene monomer mixtures, vinyl chloride, vinyl fluoride, vinylidene chloride, vinylidene fluoride, and acrylic monomer mixtures.

20. The process of claim 19 wherein R is allyl, and R'O is the bivalent epoxy group derived from butylene oxide.

21. The process of claim 20 wherein X is selected from the group consisting of chloride, hydroxyl and the anionic groups sulfate, sulfonate, phosphate (and alkali metal salts of such anionic groups).

22. A polymer product that is prepared by the free-radical initiated polymerization of ethylenically unsaturated reactant monomer in the presence of from about 1 to about 25 weight percent, based on the total amount of reactant monomer, of a compound represented by the graphic formula:

wherein R is selected from the group consisting of C₂-C₁₈ alkenyl, acrylyl, acrylyl (C₁-C₁₀)alkyl, methacrylyl, methacrylyl (C₁-C₁₀) alkyl, vinylphenyl and vinylphenylene (C₁-C₆) alkyl, R'O is selected form the group consisting of bivalent alkyleneoxy groups derived from cyclic ethers other than ethylene oxide and mixtures of such alkyleneoxy groups, E is the bivalent ethylene radical, m and n are each numbers of from about 5 to about 50, the ratio of m:n being from about 20:1 to about 1:20, and X is selected from the group consisting of hydroxyl, chloride, tertiaryamino, and the anionic groups sulfonate, sulfate, phosphate, acetate, isethionate (and alkali metal salts of such anionic groups), said polymer product being substantially free of water-soluble surfactant.

23. The polymer product of claim 22 wherein the polymer is in the form of a latex.

24. The polymer product of claim 22 wherein R is selected from the group consisting of vinyl and allyl, R'O is the bivalent epoxy group derived from propylene oxide, butylene oxide and mixtures of propylene oxide and butylene oxide, m and n are each numbers of from about 5 to about 50, and X is selected from the group consisting of chloride, hydroxyl, tertiaryamino, and the anionic groups sulfonate, sulfate, phosphate, acetate, isethionate (and alkali metal salts of such anionic groups).

25. The polymer product of claim 24 wherein the ethylenically unsaturated monomer is selected from the group consisting of mono- and polyunsaturated hydrocarbon monomers, vinyl esters, vinyl ethers, monoethylenically unsaturated mono- and polycarboxylic acids and their alkyl esters, nitriles, vinyl halides, vinylidene halides, amides of unsaturated carboxylic acids, amino monomers, and mixtures of said monomers.

26. The polymer product of claim 25 wherein the monoethylenically unsaturated monocarboxylic acid is acrylic acid or methacrylic acid and their alkyl esters are C₁-C₁₂ alkyl esters.

27. The polymer product of claim 24 wherein the ethylenically unsaturated monomer is selected from the group consisting of vinyl acetate-acrylic monomer mixtures, vinyl acetate, styrene-acrylic monomer mixtures, styrene-butadiene monomer mixtures, vinyl chloride, vinyl fluoride, vinylidene chloride, vinylidene fluoride, and acrylic monomer mixtures.

28. The polymer product of claim 27 wherein R is allyl, and R'O is the bivalent epoxy group derived from butylene oxide.

29. A polymer product that is prepared by the free-radical initiated emulsion polymerization of ethylenically unsaturated reactant monomer in the presence of from about 1 to about 10 weight percent, based on the total amount of reactant monomer, of a compound represented by the graphic formula: 4 f

wherein R is selected from the group consisting of C₂-C₁₈ alkenyl, acrylyl, acrylyl (C₁-C₁₀) alkyl, methacrylyl, methacrylyl (C₁-C₁₀) alkyl, vinylphenyl, and vinylphenylene (C₁-C₆) alkyl, R'O is selected from the group consisting of bivalent alkyleneoxy groups represented by the graphic formula, -CH₂CH(R")-O-, wherein R" is methyl, ethyl, phenyl, phenyloxymethyl, and -CH₂-(CH₂)₂-CH₂-O-, and mixtures of such alkyleneoxy groups, E is the bivalent ethylene radical, m and n are each numbers of from about 5 to about 50, the ratio of m:n being from about 20:1 to about 1:20, and X is selected from the group consisting of chloride, hydroxyl, tertiaryamino, and the anionic groups sulfonate, sulfate, phosphate, acetate, isethionate (and alkali metal salts of such anionic groups), said polymer product being substantially free of water-soluble surfactant.

30. The polymer product of claim 29 wherein R is selected from the group consisting of vinyl and allyl, R'O is the bivalent epoxy group derived from propylene oxide, butylene oxide and mixtures of propylene oxide and butylene oxide, m and n are each numbers of from about 5 to about 50, and X is selected from the group consisting of chloride, hydroxyl, tertiaryamino, and the anionic groups sulfonate, sulfate, phosphate, acetate, isethionate (and alkali metal salts of such anionic groups).

31. The polymer product of claim 30 wherein the ethylenically unsaturated monomer is selected from the group consisting of mono- and polyunsaturated hydrocarbon monomers, vinyl esters, vinyl ethers, monoethylenically unsaturated mono- and polycarboxylic acids and their alkyl esters , nitriles , vinyl halides , vinylidene halides , amides of unsaturated carboxylic acids, amino monomers, and mixtures of said monomers.

32. The polymer product of claim 31 wherein the monoethylenically unsaturated monocarboxylic acid is acrylic acid or methacrylic acid and their alkyl esters are C₁-C₁₂ alkyl esters.

33. The polymer product of claim 31 wherein the ethylenically unsaturated monomer is selected from the group consisting of vinyl acetate-acrylic monomer mixtures, vinyl acetate, styrene-acrylic monomer mixtures, styrene-butadiene monomer mixtures, vinyl chloride, vinyl fluoride, vinylidene chloride, vinylidene fluoride, and acrylic monomer mixtures.

34. The polymer product of claim 33 wherein R is allyl, and

R'O is the bivalent epoxy group derived from butylene oxide.

35. A coating prepared from the polymer product of claim 33, the water sensitivity of said coating being such that the contact angle of a droplet of water placed on said coating is less than 5°.