KR920003118B1 - Polymerizable surfactant - Google Patents

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Description

[Name of invention]

Polymerizable Surfactants

Detailed description of the invention

[Initiation of invention]

In emulsion (suspension) polymerization of ethylenically unsaturated monomers, one or more surfactants (or emulsifiers) are typically used to emulsify the monomer reactant (s) and the product latex. Such surfactants are not chemically bound to the polymer product molecule by a carbon to carbon bond (as distinguished from the natural mixture adsorbed on the polymer product or the like). Until now it has been suggested that small amounts of surfactant remaining in polymer product latexes can impair the performance of products made from such latexes, such as coatings and adhesives.

U.S. Patent No. 3,941,857 shows that coatings made from vinyl chloride / olefin copolymers exhibit inconsistent performance in hydrothermal resistance, especially after exposing the coating to boiling water for extended periods of time. It has been documented that it tends to be sensitive to water in that blushing may occur sporadically. These performance properties are detrimental to certain end uses for such copolymers, such as container and paper coatings, interior and exterior coatings, industrial coatings, automotive coatings and certain adhesives.

Many methods have been proposed to avoid the reported adverse effects of surfactant residues on emulsion polymerized polymers. US Patent No. 3,941,857 describes mixing a small amount of epoxy resin with vinyl chloride / olefin copolymer resin before casting the film from the resin. U.S. Patent No. 4,049,608 discloses the use of esters of alkeno acids selected from the group consisting of cinnamic acid and alkeno acids having 4 to 18 residues with hydroxyalkane sulfonic acid in the emulsion polymerization of vinyl and other ethylenically unsaturated monomers. It is. These esters provide the dual function of emulsifiers and comonomers.

US Pat. No. 4,224,455 describes a series of mixed sulfonated half esters and alkoxylated alkyl arylols of maleic anhydride. These esters are reported to be anionic emulsifiers (surfactants) and reactive functional monomers which can be copolymerized under emulsion polymerization conditions. US 4,337,185 discloses a substantially linear synthesis in which a polymeric backbone is derived from the polymerization of one or more ethylenically unsaturated monomers and the polymeric surfactant contains a number average molecular weight of about 500 to about 40,000 and various functional groups. The use of reactive polymeric surfactants that are water soluble surfactants is described.

The present invention provides a novel group of alpha-beta ethylenically unsaturated poly (alkyleneoxy) compounds which exhibit surfactant activity, ie act as surfactants (emulsifiers) in the emulsion (suspension) polymerization process. Moreover, these novel groups are copolymerizable with ethylenically unsaturated monomers (eg, vinyl monomers) in the form commonly used in emulsion polymerization processes through reactive double bonds present in the compounds. According to the invention, a novel group of compounds in which the hydrophobic part contains alpha-beta ethylenic unsaturation and the hydrophilic part contains poly (alkyleneoxy) segments and ionic (anionic, nonionic or cationic) segments Is provided.

The polymerizable surfactant compound of the present invention can be represented by the following general formula (I):

RO- (R'O) _m- (EO) _n-1 -CH ₂ CH ₂ -X (Ⅰ)

Wherein R is a divalent organic radical having alpha-beta olefin type (ethylen type) unsaturation.

More particularly, R is C ₂ SC ₁₈ alkenyl (eg vinyl and allyl), acrylyl, acrylyl (C ₁ -C ₁₀ ) alkyl, methacrylyl, methacrylyl (C ₁ -C ₁₀ ) alkyl, vinyl Organic radicals selected from the group consisting of phenyl and vinylphenylene (C ₁ -C ₆₎ alkyl. More particularly, the C ₂ -C ₁₈ alkenyl group can be represented by the following general formula (II):

CH ₂ = CH-C _a h _2a- (II)

Wherein a is a number from 0 to 16.

If a is 0, the alkenyl group is vinyl, ie CH ₂ = CH-. When a is 1, the alkenyl group is allyl, ie CH ₂ = CH-CH _2- . :

Wherein R ₁ is hydrogen or methyl and b is a number from 0 to 10.

When b is 0 and R ₁ is hydrogen, the general formula (III) group is acyrylyl [CH ₂ = CH-C (O)-]. When b is 0 and R ₁ is methyl, the general formula (III) group is methacrylyl [CH ₂ = C (CH ₃ ) —C (O) —]. When R ₁ is hydrogen and b is 1, the general formula (III) group is acrylyl methyl [CH ₂ = CH-C (O) -CH _2- ].

Vinylphenylene and vinylphenylene (C ₁ -C ₆ ) alkyl groups can be represented by the following general formula (IV):

CH ₂ = CH-Ar-C _d H _2d- (IV)

Wherein Ar is phenylene and d is a number from 0 to 6.

When d is 0, the general formula (IV) group is vinylphenyl; when d is 1, the general formula (IV) group is vinylphenylene methyl.

In general formula (I), -R'O- is a divalent alkyleneoxy (substituted and unsubstituted) group derived from a cyclic ether except ethylene oxide or a mixture of such cyclic ethers. More particularly, -R'O- is of the formula -CH ₂ CH (R ')-O-, wherein R' is methyl, ethyl, phenyl, phenyloxymethyl, -CH _2- (CH ₂ ) ₂ -CH ₂ -O- and mixtures thereof). Very particularly, -R'O- is propylene oxide (e.g. 1, 2-epoxypropane), butylene oxide (e.g. 1, 2-epoxybutane), styrene oxide [(epoxyethyl) benzene], tetrahydrofuran, It can be described as a divalent radical derived from a cyclic ether selected from the group consisting of phenyl glycidyl ether (1, 2-epoxy-3-phenoxypropane) and mixtures thereof. Preferably, -R'O- is a divalent epoxy group derived from pyrophyllene oxide, butylene oxide and a mixture of propylene oxide and butylene oxide. The letter E in formula (I) is a divalent ethylene radical and m and n are each a number that can vary between about 5 and 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 incorporating the polymerizable surfactant of the present invention. Changing the m: n ratio will change the HLB (hydrophilic-lipophilic equilibrium) of the polymerizable surfactant compound. If the polymerization system requires a hydrophobic surfactant, m will be greater than n. In contrast, if the emulsion polymerization system requires a hydrophilic surfactant, m will be less than n. The ratio of m: n must be chosen so that the resulting compound can reduce the surface tension of the water. Preferably, the surface tension at 25 ° C. of a 0.1 wt% aqueous solution of polymerizable surfactant compound is less than 38 dyne / cm. More preferably the surface tension of such solutions is in the range of 30 to 35 dyne / cm. Surface tension can be measured with a Du Nouy tension meter.

X in the general formula (Ⅰ) are hydroxy (-OH): chloride (-Cl): sulfonate (-SO _3): sulphate (-OSO _3): phosphate [-OP (O) (OH) 2]: acetate (-CH ₂ -C (O) OH): isethionate (-CH ₂ -CH ₂ -SO ₃ H): alkali metal salts of the sulfonates, sulfates, phosphates, acetates and isethionate anionic groups described above; and Tertiary amino, i.e., -N (R ₂ ) (R ₃ ) R ₄ , wherein R _2, R _{3 and} R ₄ are each particularly selected from the group consisting of alkyl and hydroxyalkyl groups containing 1 to 5 carbon atoms Selected from the group consisting of tertiary amines derived from, for example, trimethylamine, triethylamine, triethanolamine and diethylmethylamine. Typically, X will be selected from the group consisting of sulfonates, sulfates, phosphates, acetates (and their alkali metal salts), hydroxyls, chlorides and tertiary aminos. The term “alkalimetal”, as used herein, includes sodium, potassium, lithium and ammonium.

The polymerizable surfactants of the present invention comprise a precursor alcohol ROH, wherein R is as defined in formula (I) above, in the first desired amount of cyclic ether (R'O) (e.g. propylene oxide, butylene oxide). Or a mixture thereof) and then react the resulting epoxy-containing product with the desired amount of ethylene oxide (EO). The product resulting from this reaction is a substance corresponding to formula (I) wherein X is hydroxyl. Such materials can be used as nonionic surfactants.

Polymerizable surfactants wherein X is a sulfate can be prepared by reacting the corresponding nonionic (hydroxy end-capped) surfactant with chlorosulfonic acid, 100% sulfuric acid or sulfur trioxide. See, for example, US Pat. Nos. 2,143,759 and 2,106,716 to HA Bruson. The reaction product is neutralized with an alkali reagent, for example an alkali metal hydroxide such as sodium hydroxide, to give the corresponding salt, for example sodium salt. Similarly, corresponding nonionic surfactants can be reacted with polyphosphoric acid (P ₂ O ₅ .2H ₂ O) or chloroacetic acid by known methods to produce phosphate or acetate end-capped polymerizable surfactants.

The sulfonate terminated polymerizable surfactant of formula (I) first reacts the corresponding nonionic material with thionyl chloride or carbonyl chloride (followed by decarboxylation with chloride) to convert to the corresponding chloride , Chloride derivatives can be prepared by reacting with sodium sulfite. When the sulfonation reaction is carried out, the preformed sulfonate terminated surfactant product can be used as the reaction medium to improve conversion. Thus, 0-20% by weight (based on the total amount of reactants) of the pre-formed sulfonate product can be added to the reactor.

The chloride-capped surfactants can be used not only as surfactants themselves but also as precursors for preparing sulfonates, isethionates or quaternary ammonium terminated surfactants. Isethionate derivatives can be prepared by reacting a chloride-tapped surfactant with isethionic acid in the presence of a base such as sodium hydroxide. The quaternary ammonium derivatives react the corresponding chlorides with tertiary amines N (R ₂ ) (R ₃ ) R ₄ , where R ₂ , R ₃ and R ₄ are as defined for X in general formula (I). Can be prepared. Processes for converting nonionic polymerizable surfactants to chlorides, sulfates, sulfonates, phosphate esters, acetates, isethionates or quaternary ammonium derivatives are well known to the skilled chemist.

The precursor alpha-beta ethylenically unsaturated alcohols used to prepare the polymerizable surfactant materials of general formula (I) can be prepared by methods known in the art. Some of these (eg allyl alcohol) are readily commercially available. According to certain embodiments of the invention, the precursor alcohol is fed to a suitable autoclave and then heated to a temperature in the range of about 110 ° C to about 130 ° C. Propylene oxide and / or 1,2-epoxybutane are metered and introduced into the occlave to react with unsaturated alcohols in the presence of alkaline reagents (e.g. sodium hydroxide). After the desired amount of propoxylation and / or butoxylation reaction, the propylene oxide and / or 1,2-epoxybutane reactant (s) are replaced with ethylene oxide and then weighed until the desired level of ethoxylation is achieved. Introduced into the reactor. The pressure in the reactor will generally remain below 100 lb / in ² .gage during these reactions. The resulting poly (alkyleneoxy) material is removed from the reactor, the alkaline reagent is neutralized with acid and the product is recovered by filtration. Such nonionic materials can be converted to sulfates, sulfonates, poststate esters, acetates or isethionates (or salts thereof), or chlorides or quaternary ammonium derivatives by the methods described above.

The number of epoxy groups (eg alkyleneoxy groups) present in the polymerizable surfactant material will vary as described for general formula (I). The number of epoxy units present per mole of surfactant of formula (I), i.e., the letters ＂m＂ and ＂n＂ are the average moles of cyclic ethers present per mole of surfactant, so the values of m and n range from 5 to It can be a fraction between 100.

The polymerizable surfactant materials of the present invention can be used for emulsion (or suspension) polymerization or solution polymerization. Such polymerization can be carried out using free radicals using batch, continuous or controlled monomer feed processes: known agitation times and temperature conditions: and known types of additives (eg, initiators, surfactants, electrolytes, pH regulators, buffers, etc.). It can be carried out by starting polymerization. Generally, emulsification or solution polymerization will be carried out at about 20 ° C. to about 120 ° C., such as about 50 ° C. to about 80 ° C. The batch polymerization time may vary depending on the polymerization method and the monomers to be polymerized. Such polymerization time may vary from about 2 hours to about 10 hours. The polymerizable surfactant materials of the present invention are particularly useful for the emulsion polymerization process in liquid form in which water comprises a continuous phase and monomer (s) are present substantially as a dispersed phase at the start of the polymerization. In order to prepare suitable small particle size dispersed monomer emulsions or suspensions, the polymerization medium is incorporated to a degree that minimizes a sufficient amount of the polymerizable surfactant of the present invention. The polymerizable surfactants of the present invention can be added to a batch, semicontinuous or continuously polymerizable reaction mixture.

The amount of surfactant used for the polymerization of ethylenically unsaturated monomers, in particular when used as a single emulsion polymerization surfactant, is the amount of surfactant used in a given emulsion polymerization system, especially when used as a sole emulsion polymerization surfactant. It may range from about 1.0 to about 10 weight percent based on the total content of reactant monomers used in a given emulsion polymerization system. Preferably, the amount of such polymerizable surfactant is similarly used in about 3.0 to about 6 weight percent based on total monomers.

The polymerizable surfactant materials of the present invention can be used in emulsion polymerization reactions with conventional emulsion polymerization surfactants which do not react with the polymerizable monomer, ie, cannot copolymerize with the polymerizable monomer. When selecting the auxiliary surfactant to be used, the anionic and cationic materials should not be used together. The anionic surfactant material and the nonionic surfactant material may be used together, or the cationic surfactant material and the nonionic surfactant material may be used together. The reactive surfactants of the present invention characteristically exhibit excellent ability to provide emulsion stability properties during emulsion polymerization. Such conventional surfactants are expected to be used in amounts of 3 to 6 weight percent based on the total amount of monomer (s).

In another aspect of the invention, it is contemplated that the polymerizable surfactants of the invention may be used as comonomers together with ethylenically unsaturated monomer (s) to modify the physical properties of the resulting polymer. The amount of polymerizable surfactant that can be used may vary from about 1 to about 25 weight percent based on the total amount of reactant monomers, but typically from about 1 to about 10 weight percent, such as from 3 to 6 weight percent It will be a range. In this embodiment, conventional emulsion polymerization surfactants may also be used as additives for polymerization, for example in amounts of about 3 to 6% by weight, based on the total amount of monomeric reactants to be polymerized.

In another embodiment of the present invention, ethylenically unsaturated monomer (s) and polymerizable reactive compounds represented by general formula (I) of 1 to 25% by weight (as described above) are copolymerized by solution polymerization. Conventional organic solvents can be used, which can be solvents for both monomer (s) and polymers or just solvents for monomer (s). Solution polymerization can be initiated using organic free-radical initiators as described herein.

A sufficient amount of 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 temperature used. The initiators used in the emulsion polymerization process are initiators in the form of generating free radicals and are conveniently used for peroxygen compounds such as inorganic peroxides such as hydrogen peroxide and inorganic persulfate compounds such as ammonium persulfate and sodium persulfate. And potassium persulfate): organic hydroperoxides (eg cumene hydroperoxide and tertiary butyl hydroperoxide): organic peroxides (eg benzoyl peroxide, acetylperoxide, lauroyl peroxide), sometimes iron compounds, Peroxydicarbonate esters activated by water-soluble reducing agents such as sodium sulfate or hydroxylamine hydrochloride (e.g. diisopropyl peroxydicarbonate, peracetic acid and perbenzoic acid); and other free radical-producing materials (e.g. 2, 2 Azobisisobutyronitrile).

Typical cationic nonpolymerizable surfactants include salts of aliphatic amines (particularly 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 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, ethanolated alkyl guanidine amine complex, stearyl dimethyl benzyl ammonium chloride, cetyl dimethyl amine oxide, cetyl dimethyl benzyl ammonium chloride, tetradecylpyridinium bromide, diisobutyl phenoxy ethoxy ethyldimethyl benzyl Ammonium Tolide, 1- (2-hydroxyethyl) -2- (mixed pentadecyl and heptadecyl) -2-imidazoline, resin amine ethoxylate, oleyl imidazoline, octadecyl ethylmethyl sulfonium Methyl Sulfate, Dodecyl-bis-hydroxyethylsulfonium Acetate , Dodecyl-benzyl-dimethyl set to phosphonium chloride, dodecyl trimethyl benzyl phosphonium chloride and tetramethyl isothiocyanate of S-p- dodecyl benzyl -N-N-N'-N'- chloride.

Representative forms of anionic emulsifiers are alkyl aryl sulfonates, alkali metal alkyl sulfates, sulfonated alkyl esters, fatty acid soaps and the like. Specific examples of these well known emulsifiers are dodecylbenzene sodium sulfonate, sodium butyl naphthalene sulfonate, sodium lauryl sulfate, yttrium dodecyldiphenyl ether disulfonate, n-octadecyl disodium sulfosuccinate and dioctyl Sodium sulfosuccinate.

Typical nonionic emulsifiers (surfactants) convert alkyneene oxides (such as ethylene oxide, propylene oxide or butylene oxide) to long-chain fatty alcohols, long-chain fatty acids, alkylated phenols, long-chain alkyl merchitanes or long-chain alkyl primary amines (eg cetyl). Amine) and a compound formed by reacting at a ratio of about 5 to 20 moles or more (eg, 50 moles or less) of alkylene oxide per mole of co-reactant. Other representative compounds are, for example, partial and complete monoesters, which are reaction products of polyethylene glycol and long chain fatty acids, such as glycerol monostearate, sorbitan, trioleate and long-chain carboxylic acids with polyglycol ethers of polyhydric alcohols. Ester. The term “long chain” described above means an aliphatic group having 6 to 20 or more carbon atoms.

Further additives which can be introduced into the polymerization reaction medium are conventional chain transfer agents such as alkyl polyhalides or mercaptans. Examples of these include bromoform, carbon tetrachloride, carbon tetrabromide, bromoethane, alkyl mercaptans with 1 to 12 carbon atoms (e.g. dodecyl merbabtan), thiophenols and hydroxyalkyl mercaptans (e.g. mercaptoethanol) Include.

Ethylenically unsaturated monomers (s) which can be copolymerized with ethylenically unsaturated polymerizable materials of general formula (I) are well known in the art and illustrate only representative examples herein. Ethylenically unsaturated monomers include, but are not limited to, mono- and polyunsaturated hydrocarbon monomers, vinyl esters (such as vinyl esters of C ₁ -C ₆ saturated monocarboxylic acids), vinyl ethers, monoethylenically unsaturated mono- and polycarboxylic acids, and Their alkyl esters such as acrylic acid esters and methacrylic esters (particularly their C ₁ -C ₁₂ alkyl esters), nitriles, vinyl and vinylidene halides, amides of unsaturated carboxylic acids and amino monomers.

Representative examples of hydrocarbon monomers include compounds such as styrene compounds (such as styrene, carboxylated sutyrene and alpha-methyl styrene) and conjugated dienes (such as 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.

Examples of acrylic esters and methacrylic esters are alkyl acrylates and methacrylates, ethyl acrylates, ethyl methacrylates, isopropyl acrylates, isopropyl methacrylates, n-butyl acrylates, n-butyl methacrylates. Latex, isobutyl acrylate, isobutyl methacrylate, hexyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 3, 3-dimethyl Butyl acrylate, 3, 3-dimethylbutyl methacrylate and lyryl 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 acetate, allyl propionate and allyl lactate. Allyl esters of saturated monocarboxylic acids.

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 are dimethyl maleate, diethyl maleate, dibutyl maleate, dioctyl maleate, diisooctyl maleate, dinonyl maleate, diisodecyl maleate, ditri Decyl 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 halogen-substituted derivatives such as alphachloroacrylic acid, and anhydrides of these acids such as maleic martial arts and citraconic anhydride for use as monomers. Suitable.

Among the corresponding nitriles of these acids, acrylonitrile, alpha-chloro-acrylonitrile and methacrylonitrile can be used as monomers. Suitable imides of these acids are unsubstituted amides (eg acrylamides), methacrylamides, and others obtained by the conventional reaction of amides of the mono- and poly-carboxylic acids mentioned above with aldehydes (eg formaldehydes). Alpha-substituted acrylamides and N-substituted amides. Typical N-substituted amides include N-methylolacrylamide, N-methylolmethacrylamide, and alkylated N-methylolacrylamide and N-methylolmethacrylamide (e.g., N-methoxymethylacrylamide and N-methoxymethylmethacrylamide).

Typical amino monomers include substituted and unsubstituted amino alkyl acrylates, chlorates and methacrylates of amino monomers such as beta-aminoethyl acrylate, beta-aminoethyl methacrylate, dimethylamino-methyl acrylate, beta -Methylamino-ethylacrylate and dimethylaminomethylmethacrylate.

Hydroxy-containing monomers include beta-hydroxyethyl acrylate, beta-hydroxypropyl acrylate, gamma-hydroxypropyl acrylate and beta-hydroxyethyl methacrylate.

The monomers described above, in particular acrylic esters and methacrylic esters, may be homopolymerized or copolymerized with other monomers, ie one or more different monomers capable of addition polymerization.

The reactive surfactants of the present invention are especially used in polymerization systems comprising various monomers and monomer mixtures, such as vinyl acetate-acrylic monomer mixtures, vinyl acetate monomers, 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 the respective vinyl and vinylidene halides with other monomers, acrylic monomers It has been found that an acrylonitrile monomer mixture and all acrylic monomer mixtures can be formed. 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 those skilled in the art.

The polymerizable surfactant of the present invention is polymerized with conventional reactant monomer (s) in the polymerization process to form substantially surfactant free water insoluble polymer particles. Thus, the polymer latex product is not degraded into unwanted residues of the water soluble surfactant. The polymer product has improved water resistance and can be used in any end use for which a particular polymer product made from conventional reactant monomer (s) can be used. Examples include interior and exterior coatings (e.g. latex paint): containers, paper and cardboard coatings (e.g. can coatings): waterborne adhesives and adhesives such as pressure sensitive adhesives: sealants: industrial coatings: Automotive coatings: textile coatings and binders: flooring paints: aqueous inks: films: and binders for nonwoven materials such as carpet substrates.

The polymer product prepared using the polymerizable surfactant of the present invention is an important resin component in the resin mixture used to prepare coatings, adhesives, sealants, binders, inks, floor coatings, etc. as described above, or It can be used as a trace component. The remainder of the film-forming composition may be a variety of fillers (e.g. pigments, colorants, etc.), solvents (e.g. aqueous or organic solvents), plasticizers, antioxidants, curing agents, thickeners, surfactants, preservatives, wet strength enhancers and the aforementioned And other adjuvants added to conventional resin amounts in the resin composition used for the end use.

The method of the present invention is described in more detail in the following examples. These embodiments are merely exemplary, and those skilled in the art will appreciate that many changes and modifications are possible.

Example 1

To a 1 L magnetically stirred autoclave, 58.1 g of allyl alcohol and 0.92 g of sodium hydroxide are fed. After sealing the autoclave, the internal air atmosphere is replaced with nitrogen. The autoclave is pressurized with nitrogen to 10 lb / in ² gage (10 psig) and then the contents are heated to 120 ° C. 1,2-Epoxybutane is introduced into the autoclave slowly and continuously while maintaining the reactor contents between about 110 ° C and 130 ° C. The maximum working pressure for 1, 2-epoxybutane addition is less than 100 psig. After 600 g of 1,2-epoxybutane are introduced into the autoclave, the reaction slows down. The contents of the autoclave are cooled to about 15 ° C., the autoclave is opened, and then 0.66 g of sodium hydroxide is further introduced into the autoclave to enhance the rate of the alkoxylation reaction. The autoclave is sealed and air is replaced by nitrogen, then the autoclave is pressurized with nitrogen to a pressure of 10 psig and the contents are heated to 120 ° C. 1,2-Epoxybutane is fed back to the autoclave until the total amount of epoxy butane reaches about 865 g. When the pressure in the autoclave reaches a constant value, the autoclave is cooled. Recover 886.4 g of the pale yellow liquid product. The product was identified as the passivation product of allyl alcohol. Quantum nuclear magnetic resonance (NMR) spectroscopy shows that the number of butoxy groups in the product is about 12.3 per molecule.

One liter of a magnetically stirred autoclave was fed with 332 g of the degassed butoxylated allyl alcohol described above. After replacing the air atmosphere in the autoclave with nitrogen, the butoxylated allyl alcohol was heated to 120 ° C. and then 240 g of ethylene oxide was autoclaved over about 3 hours to maintain a reaction temperature of 120 ° C. and a working pressure of 90 psig or less. Slowly add to. The resulting product is cooled to 30 ° C., and then 0.89 g of acetic acid is added to the reaction product to neutralize the basicity of the reaction mixture. The final product is a pale yellow liquid. Quantum NMR measurements of the number of ethoxy units per molecule in the product showed about 15.3. This product will be referred to herein as Sample 1-A. A 0.1 wt% aqueous solution of Sample 1-A was prepared and measured using a Dunoy Noiometer, but at 25 ° C. to measure the surface tension. Surface tension was found to be 31.6 dyne / cm.

A 1 liter autoclave was fed with 277 g of degassed butoxylated allyl alcohol and flushed with nitrogen for 30 minutes. The butoxylated allyl alcohol is heated to 120 ° C. and 330 g of ethylene oxide is slowly fed to the autoclave over about 3 hours while maintaining a reaction temperature of about 120 ° C. and a working pressure of 90 psig or less. 0.74 g of acetic acid is added to neutralize the basicity of the product. Recover 614.7 g of pale yellow liquid product. The number of ethoxy groups per product molecule by quantum-NMR is about 26.1. This product will be referred to herein as Sample 1-B. The surface tension of the 0.1 wt% aqueous solution of Sample 1-B is 32.2 dyne / cm at 25 ° C.

221 g of degassed butoxylated allyl alcohol is fed to a 1 L autoclave, flushed with nitrogen, and the butoxylated allyl alcohol is heated to 120 ° C. 370 g of ethylene oxide is slowly fed to the autoclave over about 4 hours while maintaining a reaction temperature of about 120 ° C. and a reaction pressure of less than 100 psig. When all of the ethylene oxide is fed to the autoclave, the pressure is kept at equilibrium and the autoclave is cooled. 0.59 g of acetic acid is added to neutralize the basicity in the reaction product. The number of ethoxy units in the pale yellow liquid product by quantum-NMR is about 40.6. This product will be referred to herein as Sample 1-C. The surface tension of the 0.1 wt% aqueous solution of Sample 1-C is 33.6 dyne / cm at 25 ° C.

Example 2

20 g of liquid phosgene is fed into a 2 l jacketed round bottom flask equipped with a phosgene inlet tube, a dry ice cooled condenser, a stirrer and a dropping funnel. The reaction flask was then fed simultaneously with 477 g of product sample 1-B described in Example 1 and an additional 40 g of phosgene. The reaction mixture is stirred at 15-20 ° C. for several hours, then the reaction product is degassed to remove excess phosgene. The resulting chloroformate is converted to the corresponding chloride by heating at 120-140 ° C. for 4 hours in the presence of 1.23 g of trioctylmethylammonium chloride. Recover 480 g of product. The product was identified by proton-NMR and IR spectroscopy and overall chloride analysis to find the corresponding chloride.

Example 3

To a 0.5 L magnetically stirred autoclave, 100.7 g of the chloride product of Example 2, 12.3 g of sodium sulfite (98%), 265.1 g of deionized water and 1.2 g of 50% aqueous sodium hydroxide solution were fed. The autoclave is sealed and the contents heated to 155 ° C. and held at that temperature overnight. Stabilize the pressure in the autoclave to about 60 psig. The contents of the autoclave are cooled to below 5 ° C. The corresponding sulfonate of the product, ie the chloride product of Example 2, is a pale yellow liquid containing 28.3% solids with an anionic surfactant activity of 7.2% (as it is).

Example 4

The procedure of Example 3 is repeated except that 77.4 g of the pre-formed sulfonate product prepared in Example 3 is added to the autoclave with the reaction. 423. g of a pale yellow, clear liquid product is recovered from the autoclave. The product is treated with 1.00 g of hydrogen peroxide (49.5%) to remove residual sulfite anions. The product contained about 30% solids and was analyzed to have about 14.6% anionic surfactant activity.

Example 5

The procedure of Example 3 is repeated except that 113.2 g of the preformed sulfonate product of Example 4 is added to the autoclave with the reaction. The product is a pale yellow, named liquid. This was treated with 1.33 g of hydrogen peroxide (49.5%) to remove residual sulfite anions.

The sulfonate product is combined with the product of Example 4. Solids content of the resulting mixture was about 28.3%, it was analyzed to have about 16.2% anionic surfactant activity. The surface tension of the 0.1 wt% aqueous solution of the product was found to be 35.6 dyne / cm at 25 ° C.

Example 6

Using the procedure of Example 2, 401 g of Sample 1-A are reacted with phosgene and the resulting chloroformate is subjected to the corresponding chloride decarboxylation with 1.1 g of trioctylmethylammonium chloride. 77.7 g of the resulting chloride product is converted to sulfonate using 15.4 g of sodium sulfite, 174.3 g of deionized water and 1.54 g of 50% aqueous sodium hydroxide solution according to the procedure of Example 3. A milky pale yellow liquid containing 33.3% solids having 9.6% anionic surfactant activity is obtained.

Example 7

The sulfonation procedure of Example 3 is carried out using 77.7 g of chloride product of Example 6, 15.4 g of sodium sulfite, 1.54 g of sodium hydroxide, 218.3 g of deionized water and 135.9 g of the preformed sulfonate product prepared in Example 6. . The product contained 29.3% solids and was analyzed to have about 10.8% anionic surfactant activity. After standing for about 2 weeks, the product was observed and separated into two layers.

Example 8

The procedure of Example 7 is repeated except that 149.8 g of the top layer of the sulfonate product of Example 7 is used as the preformed sulfonate in the sulfonation reaction. The sulfonate product is treated with 1.33 g of hydrogen peroxide (49.5%) to remove residual sulfite anions and then combined with the remaining sulfonate product of Example 7. The combined products have 11.1% anionic surfactant activity. The surface tension of the 0.1 wt% aqueous solution of the product was found to be 35.9 dyne / cm at 25 ° C.

Example 9

Following the procedure of Example 2, phosgene is used to convert 407 g of Sample 1-C to the corresponding chloroformate. Chloroformate is decarboxylated with the corresponding chloride using 1.05 g of trioctylmethylammonium chloride. 115.6 g of the resulting chloride product is converted to the corresponding sulfonate using 10.8 g of sodium sulfite, 1.1 g of 50% aqueous sodium hydroxide solution and 296.2 g of deionized water according to the procedure of Example 3. The product is a pale yellow clear solution at 60 ° C. This is treated with 1.9 g of hydrogen peroxide (49.5%) to remove residual sulfite anions. The product contains 28.8% solids with 15.8% anionic surfactant activity.

Example 10

The sulfonation procedure of Example 9 is repeated except that 57.1 g of the preformed sulfonate product of Example 9 is added to the autoclave with the reaction. The clear pale yellow liquid is treated with 1.76 g of hydrogen peroxide to remove residual sulfite anions. The sulfonate product contained about 31.9% solids and was analyzed to have 18.7% anionic surfactant activity.

The sulfonate product is combined with the remaining product of Example 9. The resulting mixture contained about 32.6% solids and was analyzed to have about 16.1% anionic surfactant activity. The surface tension of the 0.1 wt% aqueous solution of the product was found to be 35.1 dyne / cm at 25 ° C.

Example 11

The vinyl acetate-butyl acrylate copolymer is prepared using the sulfonate product of Example 5 as the sole surfactant. To a 1 liter resin kettle was supplied a solution of 31.7 g of the sulfonate product of Example 5 in 281 g of deionized water. The solution is kept at 80 ° C. for 30 minutes under nitrogen atmosphere. The remaining monomer mixture is fed to the kettle over 3 to 4 hours while maintaining the polymerization temperature at 70 to 75 ° C. The contents of the resin kettle were post-stirred at 70 ° C. for 1 hour, then 10 g of 2% formaldehyde sulfoxylate was added to the kettle to complete the polymerization.

The kettle contents are cooled to ambient temperature and the latex in the kettle is recovered by filtration through a cloth. Less than 1% of the polymer product solidifies. A portion of the latex is cast into a film and the film is dissolved in chloroform-d (CD ₃ Cl). Chloroform solution was analyzed by quantum-NMR spectroscopy to show no presence of specific allyl hydrogen. This suggests that the sulfonate product of Example 5 reacted completely during the polymerization.

The latex film is placed on a microscope slide and then air dried for at least 24 hours. NRL contact angle goniometer Model 100-00 is used to measure the contact angle of deionized water drops placed on the film. The contact angle was measured within 10 seconds after water was placed on the film and was found to be 52 °.

Example 12

For comparison, the emulsion polymerization of Example 11 is carried out using 24 g of sodium lyryl sulfate (30% active) as the sole surfactant. It was found that the product was recovered by filtration through cotton and less than 1% of the product solidified.

According to the procedure described in Example 11, the contact angle for water droplets placed on a film made from the latex is measured. Immediately after dropping the droplet, the resulting contact angle was less than 5 °.

The contact angle measurements of Examples 11 and 12 show that the latex made with the copolymerizable surfactant of Example 5 is less sensitive to water than the latex made from conventional emulsifiers such as sodium lyryl sulfate.

Example 13

The vinyl acetate homopolymer is prepared using the sulfonate product of Example 10 as the sole surfactant. To a 1 L resin kettle was supplied a solution of 20.0 g of the sulfonate product of Example 10 in 238 g of deionized water. The solution is heated to 80 ° C. under nitrogen atmosphere and then 0.5 G of potassium persulfate (K ₂ S ₂ O ₈ ) is added to the solution. Vinyl acetate 50G is slowly added to the resin kettle. After the initial feed of vinyl acetate is complete, the reaction temperature is maintained at 75-80 ° C. for 30 minutes. The vinyl acetate 150G is then added to the kettle over 3-4 hours while maintaining the polymerization temperature at about 80 ° C. The contents of the resin kettle are post-stirred at 85 ° C. for 1 hour, cooled to ambient temperature and filtered through cotton. The amount of coagulation found is about 1%. The latex film is placed on a microscope slide and then air dried for at least 24 hours. The contact angle for the droplets placed on the film (as in Example 11) was measured and found to be 53 °.

Although the present invention has been described with reference to the specific details thereof, these details are not to be regarded as a limitation on the scope of the invention, except as included in the appended claims.

Claims (35)

The compound represented by the following general formula. RO- (R'O) _m- (ED) _N-1 -CH ₂ CH ₂ -X Wherein, R is C ₂ -C ₁₀ alkenyl, acryloyl, acryloyl, acryloyl (C _1- C ₁₀₎ alkyl, methacryloyl, methacryloyl (C ₁ -C ₁₀₎ alkyl, vinylphenyl and vinyl Is selected from the group consisting of phenylene (C ₁ -C ₆ ) alkyl, R'O is selected from the group consisting of divalent alkyleneoxy groups derived from cyclic ethers other than ethylene oxide and mixtures of these alkyleneoxy groups , E is a divalent ethylene radical, m and n are each a number from about 5 to about 100, the ratio of m: n is from about 20: 1 to about 1:20, and X is hydroxyl, chloride, tertiary amino And an anionic group sulfonate, sulfate, phosphate, acetate, isethionate (and an alkali metal salt of such anionic group). The compound of claim 1, wherein the alkyleneoxy group R′O is of the formula —CH ₂ CH (R ′) — O—, wherein R ′ is methyl, ethyl, phenyl, phenyloxymethyl and —CH ₂ — (CH ₂ ) Is ₂ -CH ₂ -O-, wherein m and n are each a number from about 5 to about 50, and X is a chloride, hydroxyl, tertiary amino, and an anionic group sulfonate, sulfate, phosphate , Acetates, isethionates (and alkali metal salts of these anionic groups). The compound of claim 1 wherein R is selected from the group consisting of vinyl and allyl, and R'O is a divalent epoxy group derived from propylene oxide, butylene oxide and a mixture of propylene oxide and butylene oxide, m and n Are each a number from about 5 to about 50, X is chloride, hydroxyl, tertiary amino, and anionic groups such as sulfonates, sulfates, phosphates, acetates, isethionates (and alkali metal salts of these anionic groups) A compound selected from the group consisting of. The compound of claim 3, wherein the tertiary amino group is of the formula -N ⁺ (R ₂ ) (R ₃ ) R ₄ , wherein R ₂ , R ₃ and R ₄ are each C ₁ -C ₅ alkyl and hydroxy (C _Is selected from the group consisting of ₁ -C ₅ ) alkyl. 4. The compound of claim 3, wherein R is allyl and R'O is a divalent epoxy group derived from butylene oxide. 6. A compound according to claim 5, wherein X is selected from the group consisting of sulfates, sulfonates, phosphates (and alkali metal salts of these anionic groups), wherein X is chloride, hydroxyl, and an anionic group. A process for carrying out free-radical initiated polymerization of ethylenically unsaturated reactant monomers, wherein the polymerization is carried out in the presence of about 1 to about 25 weight percent of a compound represented by the following general formula based on the total amount of reactant monomers: . RO- (R'O) _m- (EO) _n-1 -CH ₂ CH ₂ -X Wherein R is C ₂ -C ₁₈ alkenyl, acrylyl, acrylyl (C ₁ -C ₁₀ ) alkyl, methacrylyl, methacrylyl (C ₁ -C ₁₀ ) alkyl, vinylphenyl and vinylphenylene ( C ₁ -C ₆ ) alkyl, R'O is selected from the group consisting of divalent alkyleneoxy groups derived from cyclic ethers other than ethylene oxide and mixtures of these alkyleneoxy groups, E is Divalent ethylene radical, m and n are each a number from about 5 to about 100, the ratio of m: n is from about 20: 1 to about 1:20, and X is hydroxyl, chloride, tertiary amino, and an anion And a group selected from the group consisting of sulfonates, sulfates, phosphates, acetates, isethionates (and alkali metal salts of these anionic groups). 8. The method of claim 7, wherein said polymerization is emulsion polymerization. The method of claim 8, wherein a nonpolymerizable surfactant is present during the polymerization. The method of claim 8, wherein the ethylenically unsaturated monomers are mono- and polyunsaturated hydrocarbon monomers, vinyl esters, vinyl ethers, monoethylenically unsaturated mono- and polycarboxylic acids and their alkyl esters, nitriles, vinyl fluorides, vinylridanis. Chloride, vinylidene fluoride and acrylic monomer mixture. The method of claim 10 wherein said monoethylenically unsaturated monocarboxylic acid is acrylic acid or methacrylic acid and their alkyl esters are C ₁ -C ₁₂ alkyl esters. The method of claim 8, wherein the ethylenically unsaturated monomer is a vinyl acetate-acrylic monomer mixture, vinyl acetate, styrene-acrylic monomer mixture, styrene-butadiene monomer mixture, vinyl chloride, vinyl fluoride, vinylidene chloride, vinylidene Fluoride and acrylic monomer mixture. A process for carrying out free-radical initiated emulsion polymerization of an ethylenically unsaturated reactant monomer, wherein the polymerization is carried out in the presence of about 1 to about 25 weight percent of a compound represented by the following general formula based on the total amount of reactant monomer: Way. RO- (R'O) _m- (EO) _n-1 -CH ₂ CH ₂ -X Wherein R is C ₂ -C ₁₈ alkenyl, acrylyl, acrylyl (C ₁ -C ₁₀ ) alkyl, methacrylyl, methacrylyl (C ₁ -C ₁₀ ) alkyl, vinylphenyl and vinylphenylene ( C ₁ -C ₆ ) alkyl, R'O is selected from the group: -CH ₂ CH (R ＂)-O-, wherein R 'is methyl, ethyl, phenyl, phenyloxymethyl and -CH ₂ Divalent alkyleneoxy group represented by-(CH ₂ ) ₂ -CH ₂ -O-) and a mixture of such alkyleneoxy groups, E is a divalent ethylene radical, m and n are Each having a number from about 5 to about 50, the ratio of m: n is from about 20: 1 to about 1:20, and X is a chloride, hydroxyl, tertiary amino, and anionic groups sulfonates, sulfates, phosphates, Acetates, isethionates (and alkali metal salts of these anionic groups). The method of claim 13, wherein the compound represented by the general formula RO— (R′O) _m — (EO) _n-1 —CH ₂ CH ₂ —X is present in an amount from about 1 to about 10 weight percent. The method of claim 14, wherein a nonpolymerizable surfactant is present during the polymerization process. 15. The compound of claim 14, wherein R is selected from the group consisting of vinyl and allyl, and R'O is a divalent epoxy group derived from propylene oxide, butylene oxide and a mixture of propylene oxide and butylene oxide, m and n Are each a number from about 5 to about 50, X is chloride, hydroxyl, tertiary amino, and anionic groups such as sulfonates, sulfates, phosphates, acetates, isethionates (and alkali metal salts of these anionic groups) Method selected from the group consisting of: 17. The process of claim 16 wherein the ethylenically unsaturated monomers are 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 said monoethylenically unsaturated monocarboxylic acid is acrylic acid or methacrylic acid and their alkyl esters are C ₁ -C ₁₂ alkyl esters. The method of claim 16, wherein the ethylenically unsaturated monomer is a vinyl acetate-acrylic monomer mixture, vinyl acetate, styrene-acrylic monomer mixture, styrene-butadiene monomer mixture, vinyl chloride, vinyl fluoride, vinylidene chloride, vinylidene fluorine. Lide and an acrylic monomer mixture. 20. The process of claim 19, wherein R is allyl and R'O is a divalent epoxy group derived from butylene oxide. The method of claim 20, wherein X is selected from the group consisting of sulfates, sulfonates, phosphates (and alkali metal salts of these anionic groups) wherein X is chloride, hydroxyl, and an anionic group. A substantially water-soluble surfactant free polymer prepared by polymerizing an ethylenically unsaturated reactant monomer in the presence of about 1 to about 25 weight percent of the reactant monomer, based on the total amount of reactant monomer, in the presence of about 1 to about 25 weight percent of a compound represented by the following general formula: product. RO- (R'O) _m- (EO) _n-1 -CH ₂ CH _2- X Wherein R is C ₂ -C ₁₈ alkenyl, acrylyl, acrylyl (C ₁ -C ₁₀ ) alkyl, methacrylyl, methacrylyl (C ₁ -C ₁₀ ) alkyl, vinylphenyl and vinylphenylene ( C ₁ -C ₆ ) alkyl, R'O is selected from the group consisting of divalent alkyleneoxy groups derived from cyclic ethers other than ethylene oxide and mixtures of these alkyleneoxy groups, E is Divalent ethylene radical, m and n are each a number from about 5 to about 50, the ratio of m: n is from about 20: 1 to about 1:20, and X is hydroxyl, chloride, tertiary amino, and an anion Sex group is selected from the group consisting of sulfonates, sulfates, phosphates, acetates, isethionates (and alkali metal salts of these anionic groups). The polymer product of claim 22 wherein the polymer is in the form of a latex. 23. The compound of claim 22, wherein R is selected from vinyl and allyl groups, and R'O is a divalent epoxy group derived from a mixture of pyrophylene oxide, butylene oxide and propylene oxide and butylene oxide, m And n are each a number from about 5 to about 50, and X is a chloride, hydroxyl, tertiary amino, and anionic groups sulfonates, sulfates, phosphates, acetates, isethionates (and alkali metal salts of these anionic groups). Hapmeric product selected from the group consisting of: The method of claim 24, wherein the ethylenically unsaturated monomers are 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. 27. The polymer product of claim 25, wherein said monoethylenically unsaturated monocarboxylic acid is acrylic acid or methacrylic acid and their alkyl esters are C ₁ -C ₁₂ alkyl esters. The method of claim 24, wherein the ethylenically unsaturated monomer is a vinyl acetate-acrylic monomer mixture, vinyl acetate, a styrene-acrylic monomer mixture, a styrene-butadiene monomer mixture, vinyl chloride, vinyl fluoride, vinyldiene chloride, vinyldiene fluorine. A polymer product selected from the group consisting of a lide and an acrylic monomer mixture. The polymer product according to claim 27, wherein R is allyl and R'O is a divalent epoxy group derived from butylene oxide. A substantially water free surfactant polymer product prepared by free-radical initiated emulsion polymerization of an ethylenically unsaturated reactant monomer in the presence of about 1 to about 10 weight percent of a compound represented by the following general formula based on the total amount of reactant monomers. RO- (R'O) _m- (EO) _n-1 -CH ₂ CH ₂ -X Wherein, R is C ₂ -C ₁₈ alkenyl, acryloyl, acryloyl (C ₁ -C ₁₀₎ alkyl, methacryloyl, methacryloyl (C ₁ - _C10) alkyl, vinylphenyl and vinyl phenylene (C _It is selected from the group consisting of ₁ -C ₆ ) alkyl, wherein R'O is the general formula -CH ₂ CH (R ')-O-, wherein R' is methyl, ethyl, phenyl, phenyloxymethyl and -CH _2- Divalent alkyleneoxy group represented by (CH ₂ ) ₂ -CH ₂ -O-) and a mixture of such alkyleneoxy groups, E is a divalent ethylene radical, m and n are each A number from about 5 to about 50, the ratio of m: n is from about 20: 1 to about 1:20, and X is a chloride, hydroxyl, tertiary amino, and anionic groups sulfonate, sulfate, phosphate, acetate , Isethionate (and alkali metal salts of these anionic groups). 30. The compound of claim 29, wherein R is selected from the group consisting of vinyl and allyl, and R'O is a divalent epoxy group derived from propylene oxide, butylene oxide and a mixture of propylene oxide and butylene oxide, m and n Are each a number from about 5 to about 50, and are the chloride, hydroxyl, tertiary amino, and anionic groups of X, sulfonates, sulfates, phosphates, acetates, isethionates (and alkali metal salts of these anionic groups). A polymer product selected from the group consisting of: The monomer of claim 30 wherein the ethylenically unsaturated monomers are mono- and polyunsaturated hydrocarbon monomers, vinyl esters, vinyl ethers, monoethylenically unsaturated mononu- and polycarboxylic acids and their alkyl esters, nitriles, vinyl halides, vinylidene halides, A polymer product selected from the group consisting of amides of unsaturated carboxylic acids, amino monomers and mixtures of said monomers and said monomers. 32. The polymer product of claim 31, wherein said monoethylenically unsaturated monocarboxylic acid is acrylic acid or methacrylic acid and their alkyl esters are C ₁ -C ₁₂ alkyl esters. 32. The method of claim 31 wherein the ethylenically unsaturated monomer is selected from the group consisting of vinyl acetate-acrylic monomer mixture, vinyl acetate, styrene-acrylic monomer mixture, sutyrene-butadiene monomer mixture, vinyl chloride, vinyl fluoride, vinylidene chloride, vinyl A polymer product selected from the group consisting of lidene fluoride and acrylic monomer mixture. 34. The polymer product of claim 33, wherein R is allyl and R'O is a divalent epoxy group derived from butylene oxide. A coating prepared from the polymer product of claim 33 having a water sensitivity such that the contact angle of water droplets placed on the coating is less than 5 °.