JPH03503168A - Polymerizable surfactant - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Polymerizable surfactant Description of the invention In emulsion polymerization (suspension polymerization) of ethylenically unsaturated monomers, the reacting monomers and to emulsify the polymer product latex and the resulting polymer product latex. Surfactants (or emulsifiers) are used. Such surfactants are Not chemically bonded to product molecules by carbon-carbon bonds (physical mixing or (e.g., adsorbed onto the polymer product). Therefore, this port A small amount of surfactant remains in the remer product latex, so Performance of products prepared from such latex, such as paints and adhesives can be inhibited. U.S. Pat. No. 3,941,857 describes a vinyl chloride/olefin A coating prepared from a copolymer is disclosed. This paint is hot water resistant. It exhibits unstable properties, especially after the coating has been exposed to boiling water for a long time. hair becomes sensitive to water, and hair length and "fogging" (whitening) may occur sporadically. Ru.

Such performance characteristics are detrimental to final products using these copolymers. So End products such as, for example, container and paper coatings, interior and exterior coatings, These include industrial paints, automotive paints, and certain adhesives.

These reported results are due to surfactant residues in emulsion polymerized polymers. Various proposals have been made to avoid this problem.

U.S. Pat. No. 3,941,857 teaches that before casting films from these resins, Then, a small amount of epoxy resin is added to the vinyl chloride/olefin copolymer resin. It is stated that. U.S. Pat. No. 4,049,608 describes vinyl and other In the emulsion polymerization of ethylenically unsaturated monomers, hydroxyalkanesulfone Acids selected from the group consisting of cinnamic acids and alkenoic acids of 4 to 18 carbon atoms. The use of esters of selected alkenoic acids is described. These esters are milk It has the functions of both a polymerizing agent and a copolymerization monomer. U.S. Patent No. 4.224.45 No. 5 includes cyclic, sulfonated, maleic anhydride and alkoxylated alkyl Herfestel's class with Luariroll is described. These beauty salons is an anionic emulsifier (surfactant) and also under emulsion polymerization conditions. It is reported to be a reactive functional monomer that can be copolymerized. U.S. Patent No. 4.33 No. 7.185 describes the use of reactive polymeric surfactants. This port Remer surfactants are polymeric backbones composed of one or more ethylenically unsaturated monomers. a substantially linear synthetic water-soluble surfactant derived from about 500 to about 4 It has a number average molecular I of 0.000 and has various functional groups.

The present invention exhibits surfactant ability, that is, it exhibits surfactant properties in the emulsion (suspension) polymerization process. αβ ethylenically unsaturated poly(alkyleneoxy) that functions as a sexing agent (emulsifier) A novel group of compounds is provided. Furthermore, they are based on the reactions present in compound molecules. vinyl, of the type commonly used in emulsion polymerization processes due to its double bonds. It is possible to copolymerize with ethylenically unsaturated monomers, including monomers. Book According to the invention, a hydrophobic moiety containing αβ ethylenic unsaturation and a poly(alkylene oxide) c) Segments and ionicity (anionic, nonionic, or cationic) A novel group of compounds having a hydrophilic portion comprising a segment is provided.

Detailed description of the invention The polymerizable surfactant compound of the present invention is represented by the following formula: R-0-(R'0) , -(EO) a-1<H2CH, -X, (I) Here, R is It is a monovalent organic group with αβ olefinic (ethylenic) unsaturation. even better Preferably, R is C2-C11 alkenyl, (e.g. vinyl and allyl) , acrylyl, acrylyl (C+~C1゜)alkyl, methacrydyl, methacrylic Zyl (C+~C8°) alkyl, vinylphenyl, and vinylphenylene (C + to CS) alkyl. For more details, see C8-C1a The alkenyl group is represented by the formula: CH2=CH(knee To-(II) Here, a is a number between 0 and 16. When a is O, this alkenyl group is (i.e., CH, =CH-). When a is 1, this alkenyl group is allyl (i.e., CH2=CH-CHz-).

Acrylyl, acrylyl (C1-C1°) alkyl, methacrydyl, and meth Crisyl (C+~C1゜)alkyl is 2R,0 represented by the following formula a CHs<(l(:bHz-(III) Here, RI is hydrogen or methyl, and b is a number from 0 to 1o.

When b is 0 and R1 is hydrogen, this group is acrylyl [CB2=C1l-C (0)-]. If b is 0 and R1 is methyl, this group is methacrylic acid. ECBz=CCCHs) - one of the CCs. R, is hydrogen and b is 1. If Ru.

Bivinylphenyl and vinylphenylene (C+-Cs) alkyl groups have the following formula: Indicated by: CHI<H-Ar-CJzg-(IV) where Ar is phenylene and d is It is a number between 0 and 6. When d is 0, the group is vinylphenyl; When d is 1, the group is vinylphenylenemethyl.

In the above formula (I), -Roo- represents divalent alkyleneoxy (substituted and unsubstituted cyclic ethers other than ethylene oxide, or such cyclic Derived from a mixture of ethers. More specifically, -Roo- is -CH2C It is represented by the formula E (R”)-0-, where l?” is methyl, ethyl, phenyl. , phenyloxymethyl, -CHt-(CHz)z-CIll, -0-1 and It is a mixture of these. More specifically, -R'O- is propylene oxide , (e.g. 1,2-epoxypropane), butylene oxide, (e.g. 1, 2-epoxybutane), styrene oxide [(epoxyethyl)benzene, te trihydrofuran, phenyl glycidyl ether (l, 2-epoxy-3-phenyl) cyclic ethers selected from the group consisting of It can be a divalent group derived from Preferably -R'O- is propylene oxy butylene oxide, and mixtures of propylene oxide and butylene oxide. It is a divalent epoxy group derived from a compound. E in the above formula (I) is a divalent ether a tyrene group, m and n each vary between about 5 and about 100, preferably is about 5 or 10 and about 50.

The manO ratio is about 20:l to about 1:20. The actually used ratio of m:n is It depends on the particular polymerization system in which the polymerizable surfactant of the present invention is contained.

The ratio of 1:n is the HLB (hydrophilic-lipophilic balance) of this polymerizable surfactant compound. ) changes with changes in Hydrophobic surfactants are required in polymerization systems If m is greater than n. On the other hand, hydrophilic surfactants are required in emulsion polymerization systems. If required, m is less than n. The m:n ratio is such that the resulting compound is on the surface of water. It should be selected in such a way that the tension can be reduced. Preferably 25 The surface tension of a 0.1% by weight aqueous solution of this polymerizable surfactant at °C is 38dy below nes/centimeter. More preferably, such a solution Surface tension ranges from 30 to 35 dynes/centimeter. surface Tension was measured using a Du Nouy tensiometer. can be determined.

X in the above formula (1) is hydroxyl (-OH), chloride (-C1), Sulfonate (-SOs), Sulfate (-OSO3), Phosphate [ -〇-P (0) (OH)z], acetate (-cH, -C(0)OH) , isethionate (CF2-CH2-SOsEl), and the above-mentioned sulfonate such as nates, sulfates, phosphates, acetates, and isethionates. Alkali metal salt of anionic group, t-amino [i.e. -NCRz) (Rs) R4 (where R2, R8 and R4 are each an alkyl group and hydroxyalkyl groups, especially alkyl groups containing 1 to 5 carbon atoms. and hydroxyalkyl groups), for example trimethyl Amines, triethylamine, triethanolamine and diethylmethylamine is a tertiary amine derived from the group consisting of In general, honates, sulfates, phosphates, acetates, (and their alkaline selected from the group consisting of hydroxyl, chloride, and t-amine groups be done. As used herein, the term "alkali metals" includes sodium, potassium, ammonium, lithium, and ammonium.

The polymerizable surfactant of the present invention is a precursor alcohol ROI (where R is as already defined with respect to formula (I)) and the desired amount of the first (fi rst) cyclic ether R'O (e.g. propylene oxide, butylene oxide , or a mixture thereof) and then the resulting epoxy-containing product is obtained by reacting with the desired amount of ethylene oxide EO. this series The product obtained from the reaction is a substance in the above formula (I) in which X is hydroxyl. matches. Such substances are used as nonionic surfactants.

The preparation of polymerizable surfactants in which X is sulfate is based on the corresponding nonionic (Terminal hydroxy cap) surfactant with chlorosulfonic acid and 100% sulfuric acid , or by reacting with sulfur trioxide. For example, H, A, bull U.S. Pat. No. 2.143.759 to Bruson (11, ^), and See No. 2.106.716. Neutralization of this reaction product requires alkaline As a reagent, for example, an alkali metal hydroxide such as sodium hydroxide is used. This gives the corresponding salt, for example the sodium salt. Similarly, corresponding The nonionic surfactant to be used is polyphosphoric acid (P20s/212 0) or can react with chloroacetic acid, phosphate or acetate end caps A polymerizable surfactant is prepared.

The sulfonate-terminated polymerizable surfactant of formula (I) is first prepared using a corresponding nonionic substance. reaction with thionyl chloride or with carbonyl chloride ( decarboxylate the chloride) to the corresponding chloride. and prepared by reacting this chloride derivative with sodium sulfite. can be manufactured.

When carrying out the sulfonation reaction, the preformed sulfonate-terminated surfactant compositions can be used as reaction media to promote conversion. Therefore, 0 to 20 Weight % (based on total amount of reactants) of preformed sulfonate product may be added to the reaction vessel.

This chloride-capped surfactant can itself be used as a surfactant; Sometimes sulfonate products, isethionate products, or quaternary ammonium powder Precursor for preparing edge surfactants. This isethionate derivative is The loride-capped surfactant and isethionic acid are combined, for example, with sodium hydroxide. It can be prepared by reacting in the presence of such a base. 4th grade ammonium The compound derivative is prepared by combining the corresponding chloride and the tertiary amine N(R2XR3)R4 (where R 7, R3 and R4 are the same as defined in relation to X in formula (I); ) can be prepared by reacting them. This nonionic polymerizable surfactant Contains sex agents such as chloride, sulfate, sulfonate, phosphate, acetate, The process of converting to sethionate or quaternary ammonium derivatives can be carried out by a person skilled in the art. By (known to) scholars.

The precursor αβ ester used to prepare the polymerizable surfactant material of formula (1) Thyrenic unsaturated alcohols can be prepared by well known methods. allyl alcohol Some, such as, are commercially available. Specific embodiments of the invention In some cases, this precursor alcohol is charged into a suitable autoclave and heated to about 11 hours. Heat to a temperature ranging from 0 to about 130°C. propylene oxide and/or 1 , 2-epoxybutane were weighed and added to the autoclave, and these were mixed with sodium hydroxide. Reacts with the above unsaturated alcohol in the presence of an alkaline reagent such as let After the desired degree of propoxylation and/or butoxylation has taken place. ethylene oxide in place of propylene oxide and/or 1,2-ethoxybutane. oxide is metered into the reaction vessel and the desired degree of ethoxylation takes place. . The internal pressure of the reaction vessel is typically 100 pounds per square inch during these reactions. Do not exceed the gauge (pounds per 5 square 1 nch gauge) maintain it as it is.

The resulting poly(alkyleneoxy) material is removed from the reaction vessel and an alkaline reagent is added. The product is recovered by neutralization with acid and reduction. This nonionic substance The quality of sulfates, sulfonates, phosphate esters, and acetates was determined by the method described above. tart, or isethionate (or their salts), or chloride, or can be converted into quaternary ammonium derivatives.

Epoxy groups present in polymerizable surfactant materials (e.g., alkyleneoxy, etc.) ) may vary as explained with respect to formula (I). Surfactant of formula (I) the number of epoxy units present per mole of (i.e. r+aJ and "n") is the average number of moles of cyclic ether present per mole of surfactant, and Therefore, the values of m and n are fractional numbers between 5 and 100. mber).

In the polymerizable surfactant material of the present invention, emulsion (or suspension) polymerization or solution This can be done using polymerization. Such polymerizations can be circular, continuous, or controlled. Using a monomer loading process with known stirring times and temperature conditions, and starting Using known additives such as agents, surfactants, electrolytes, pH adjusters, buffers, etc. It is carried out by free radical initiated polymerization. Generally, emulsion polymerization or solution polymerization is carried out at a temperature between about 20°C and about 120°C (e.g., about 50°C and about 80°C) .

Batch polymerization times vary depending on the polymerization method and the monomers being polymerized. child Such times may vary from about 2 to about 10 hours. Polymerizable surfactant of the present invention The materials are particularly useful in liquid phase emulsion polymerization processes. In that case, the water is continuous A phase is formed, and the monomer exists substantially as a dispersed phase at the start of polymerization.

The polymerization medium contains a stable, small particle size, dispersed monomer emulsion or fraction. Contain the minimum amount of the polymerizable surfactant of the present invention necessary to generate a dispersion. Ru. The polymerizable surfactant of the present invention is added to the polymerizable reaction mixture either batchwise or semi-continuously. , or may be added continuously.

The amount of polymerizable surfactant used in the polymerization of ethylenically unsaturated monomers is Especially when used alone as an emulsion polymerization surfactant, the emulsion polymerization system from about 1.0 to about 10% by weight based on the total reactant monomers used in the process. obtain. Preferably, the amount of polymerizable surfactant material used is similar to the total monomer from about 3.0 to about 6% by weight, based on the amount.

The polymerizable surfactant material of the present invention is a conventional non-reactive emulsion polymerizable surfactant (i.e. (i.e., it does not copolymerize with a polymerizable monomer) and can be used in an emulsion polymerization reaction. Both When selecting surfactant materials for use, consider anionic and cationic materials. Should not be used together.

Anionic surfactant substances and nonionic surfactant substances, or cationic Surfactant materials and nonionic surfactant materials may be used in combination. Main departure Akira's reactive surfactant itself creates stable emulsions in emulsion polymerization. It shows excellent performance in forming. Such conventional surfactants are It is contemplated that amounts of 3 to 6% by weight, based on volume, may be used.

In another embodiment of the invention, the polymerizable surfactants of the invention are Used as a comonomer of ethylenically unsaturated monomers to modify physical properties It is thought that you can get it. The amount of polymerizable surfactant used in this manner may be, for example, about may vary from 1 to about 25% by weight, but generally based on total reacted monomer content. It may range from about 1 to about 10% by weight, such as from 3 to 6%. In this embodiment Conventional emulsion polymerization surfactants can also be used as polymerization additives, e.g. It is used in an amount of about 3-6% by weight, based on the total weight of the combined monomers.

In other embodiments of the invention, ethylenically unsaturated monomers and 1 to 25% by weight of the polymerizable reactive compound of formula (I) is added to the solution polymerization. more copolymerized. All conventional organic solvents (this includes both monomers and polymers) or only the monomer) can be used.

Organic free radical initiation to initiate solution polymerization as described here agent is used.

A sufficient amount of polymerization initiator (such as a conventional free radical initiator) is added to the polymerization medium. The polymerization of the monomers is initiated at a predetermined temperature. For emulsion polymerization process The initiator used in the process is of a type that generates free radicals and is preferably It is a peroxide. For example, inorganic peroxides such as hydrogen peroxide and persulfate Inorganic persulfate compounds such as monium, sodium persulfate, and potassium persulfate such as cumene hydroperoxide, and t-butyl hydroperoxide Organic hydroperoxides; benzoyl peroxide, acetyl peroxide, lauroy peroxide Organic peroxides such as Oxydicarbonate esters, peracetic acid and perbenzoic acid (iron(II) compounds, Water soluble such as sodium bisulfate or hydroxylamine hydrochloride ), and 2,2°-azobisisobutyro Other free radical generating materials such as nitriles may be mentioned.

Traditional cationic non-polymerizable surfactants include a class of salts of aliphatic amines. derived from fatty acid amines, quaternary amine salts and hydrates, disubstituted diamines, in particular fatty acid amides, aliphatic chain derivatives of pyridinium compounds, and ethyl amines of aliphatic amines. Ren oxide condensation products, sulfonium compounds, isothiopronium (isot hiouronium) compounds, and phosphonium compounds. this Specific examples of cationic surfactants such as dodecylamine acetate, salt Acid dodecylamine, tetradecylamine hydrochloride, hexadecylamine acetate, Lauryl dimethylamine citrate, octadecylamine sulfate, dode lactate Cylamine, cetyltrimethylammonium bromide, cetylpyridinium chloride Lido, ethanolated alkylguanidine amine complex, stearyldimethylbenzi ammonium chloride, cetyldimethylamine oxide, cetyldimethylben Dylammonium chloride, tetradecylpyridinium bromide, diisobutyl Phenoxyethoxyethyldimethylbenzylammonium chloride, 1-(2 -hydroxyethyl)-2-(mixed pentadecyl and heptadecyl)-2- imidacillin, resin amine ethoxylate, oleyl imidacillin, octadecy Ruethylmethylsulfonium methylsulfate, dodecyl-bis-hydroxy Ethylsulfonium acetate, dodecylbenzyl-dimethylsulfonium chloride dodecylbenzyltrimethylphosphonium chloride, and 5-p-dode Syl-benzyl-N-N-N'-N'-tetramethylisothiolonium chloride can be mentioned.

Typical examples of anionic surfactants are alkylaryl sulfonates, alkali metal Alkyl sulfates, sulfonated alkyl esters, fatty acid soaps, etc. can be lost. Specific examples of these well-known emulsifiers include dodecylbenzenesulfone Sodium acid (dodecylbenzene 5 odiurn 5 ulfon) ate), sodium butylnaphthalene sulfonate, sodium lauryl sulfate, Dodecyl diphenyl ether disulfonic acid disodium, sulfosuccinic acid n-o Examples include tadecyl disodium, and dioctyl sodium sulfosuccinate. It will be done.

Typical nonionic emulsifiers (surfactants) include ethylene oxide, propylene oxide, oxide or alkylene oxide such as butylene oxide and long chain fatty acids, alkylene oxides such as butylene oxide and Kylated phenols, long chain alkyl mercaptans, long chain alkyl primary amines (e.g. (for example, cetylamine), and the alkylene oxide is formed by reaction with the corresponding in a ratio of about 5 to 20 moles to 1 mole of reactants, or in a higher ratio. , for example, in amounts up to 50 mol. Other representative compounds are monoester For example, reaction products of polyethylene glycol and long chain fatty acids, e.g. For example, glycol monostearate, sorbitan, triole ate), and polyglycol ethers of long-chain carboxylic acids and polyhydric alcohols partial and complete esters. In the above description, "long chain" The term refers to aliphatic groups having from 6 to 20 or more carbon atoms. Taste.

Other additives that may be introduced into the polymerization reaction medium include alkyl polyhalides, Alternatively, conventional chain transfer agents such as mercaptans are used. For example, bromophor carbon tetrachloride, carbon tetrabromide, bromoethane, alkyl of 1 to 12 carbon atoms Mercaptans (e.g. dodecyl mercaptan, thiophenol, and hydro xyalkyl mercaptans (e.g. mercaptoethanol)).

Ethylenically unsaturated, which can be copolymerized with the ethylenically unsaturated polymerizable substance of formula (I) Monomers are well known to those skilled in the art, and representative examples are described here. ethylenic unsaturation Examples of monomers include mono- and polyunsaturated hydrocarbon monomers, vinyl esters, (e.g. vinyl esters of 01-c6 saturated monocarboxylic acids), vinyl esters ethers, monoethylenically unsaturated mono- and polycarboxylic acids, and their alkaline Kill esters (e.g. acrylic esters and methacrylic esters, especially their C1-C+Z alkyl esters), nitriles, vinyl halides, halo Examples include vinylidene genide, amides of unsaturated carboxylic acids, and amino monomers. but not limited to.

Representative examples of hydrocarbon monomers include, for example, styrene, carboxylated styrene, and styrenic compounds such as alpha-methylstyrene, and, for example, butadiene. , isoprene, and conjugated diene such as copolymers of butadiene and isoprene. This includes compounds such as

Typical examples of vinyl halides and vinylidene halides include vinyl chloride, Included are vinylidene, vinyl fluoride, and vinylidene fluoride.

Examples of acrylic and methacrylic esters include alkyl acrylates. and alkyl methacrylates. Typical acrylic esters and and methacrylic esters include methyl acrylate, methyl methacrylate, and acrylic esters. Ethyl acrylate, ethyl methacrylate, isopropyl acrylate, isopropyl methacrylate Lopyl, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate isobutyl methacrylate, hexyl acrylate, 2-ethylhexyl acrylate sil, 2-ethylhexyl methacrylate, t-butyl acrylate, methacrylic acid t-Butyl, 3,3"-dimethylbutyl acrylate, 3,3'-dimethyl methacrylate Includes methylbutyl, and lauryl acrylate.

Suitable vinyl esters include, for example, vinyl formate, vinyl acetate, propion vinyl acid, vinyl butyrate, vinyl isobutyrate, vinyl valerate, and vinyl caproate. aliphatic vinyl esters such as allyl acetate, allyl propionate, and allyl esters of saturated monocarboxylic acids such as allyl lactate.

Typical vinyl ethers include methyl vinyl ether, ethyl vinyl ether and and n-butyl vinyl ether. Typical vinyl ketones include methyl Includes vinyl ketone, ethyl vinyl ketone, and isobutyl vinyl ketone. Ru. Preferred dialkyl esters of monoethylenically unsaturated dicarboxylic acids include Dimethyl maleate, diethyl maleate, dibutyl maleate, dio maleate Cutyl, diisooctyl maleate, dinonyl maleate, diisode maleate Sil, ditridecyl maleate, dimethyl fumarate, diethyl fumarate, fumar Dipropyl acid, dibutyl fumarate, dioctyl fumarate, diisooctyl fumarate didecyl fumarate, dimethyl itaconate, diethyl itaconate, itaconic acid Dibutyl, and dioctyl itaconate are included.

Preferred monoethylenically unsaturated monocarboxylic acids include acrylic acid and methacrylic acid. , ethacrylic acid, and crotonic acid; maleic acid, fumaric acid, itaconic acid, and monoethylenically unsaturated dicarboxylic acids such as citraconic acid and aconite; monoethylenically unsaturated tricarboxylic acids such as substituted derivatives of these acids (e.g. alpha-tetraroacrylic acid), and anhydrides of these acids (e.g. E1f.

Maleic anhydride and citraconic anhydride are used as monomers; Included.

Acrylonitrile, α-chloroacrylonitrile, and methacrylatetrile, etc. Nitriles corresponding to these acids can also be used as monomers. This type of acid Preferred amides include unsubstituted amides such as acrylamide and methacrylamide. , and other α-substituted acinolamides, and the mono- and polycarboxylic acids mentioned above. by the conventional reaction of an amine with an aldehyde such as formaldehyde. N-substituted amides are included. Typical N-substituted amides include N-methylola Acrylamide, tomethylolmethacrylamide, alkylated N-methylolacrylamide rylamide, and N-methylolmethacrylamide (e.g. N-methoxymethacrylamide). lyacrylamide and N-methoxymethyl methacrylamide).

Typical amino monomers include substituted and unsubstituted aminoalkyl acrylates For example, β-aminoethyl acrylate, β-aminoethyl methacrylate, dimethyl acrylate, etc. Minomethyl acrylate, β-methylaminoethyl acrylate, and dimethyl aminomethyl methacrylate).

Hydroxyl group-containing monomers include β-hydroxyethyl acrylate and β-hydroxypropyropropylene. Pyracrylate, γ-hydroxypropyl acrylate, and β-hydroxyethyl acrylate Chil methacrylate is included.

The monomers mentioned above, especially acrylic esters and methacrylic esters, are may also be combined with other listed monomers (i.e., one or more addition polymerizable monomers). different monomers).

The reactive surfactant of the present invention includes vinyl acetate-acrylic monomer mixture, vinyl acetate monomer, ethylene-vinyl acetate monomer mixture, styrene, styrene-a Acrylic monomer mixture, butadiene-acrylonitrile monomer mixture, steel Ren-butadiene monomer mixture, vinyl chloride, vinylidene chloride, vinyl fluoride , vinylidene fluoride, and each of the above-mentioned vinyl halides with other monomers. Acrylic monomer-acrylonite homopolymer mixtures, such as lyle monomer mixtures, and all acrylic monomer mixtures. Contains various monomers and monomer mixtures to form remers and copolymers It is particularly used in polymerization systems where The term “acrylic” used here The term refers to one or more acrylic esters and/or methacrylic esters. With acrylic acid or methacrylic acid, acrylic acid or methacrylic acid Intended to be included whether or not together with. Such monomer mixture compounds are well known to those skilled in the art.

The polymerizable surfactant of the present invention is polymerized together with conventional reactive monomers in the polymerization process. will be combined. Therefore, virtually surfactant-free polymer particles that are insoluble in water is formed. Thus, polymer latex products contain undesirable water-soluble No contamination with surfactant residues. This polymer product exhibits improved water resistance. However, all the specific polymer products produced from conventional reaction monomers are used. Used in end application fields. Examples of these include interior and exterior coatings. materials (e.g., latex paints, container, paper, and paperboard paints, and also e.g. paints, adhesives, fillers, industrial paints, vehicle paints, textile coatings and binders, floor finishes, water-based inks, films, and carpet backing materials. binders for nonwoven materials such as

Polymer products prepared using the polymerizable surfactant of the present invention include paints, adhesives, etc. resin compositions to prepare fillers, binders, inks, floor finishes, etc. or as a minor component of a resin mixture. This frame The film-forming composition, when used in the end applications described above, may also include Also, various fillers (e.g., pigments, colorants, etc.), solvents, e.g., aqueous or Mechanical solvent, plasticizer, antioxidant, hardening agent, thickening agent, surfactant, preservative, wet strength imparting agents), and other auxiliary materials may be added.

The process of the invention is explained in further detail in the following examples. These are just examples It will be obvious to those skilled in the art that various modifications can be made.

Example 1 11 autoclave with magnetic stirrer ζ2 5g, Ig allia It was charged with alcohol and 0.92 g of sodium hydroxide. This autoclave was sealed and the air inside was replaced with nitrogen. This autoclave was heated with nitrogen for 10 vol. Pressurize 4 square inch gauges (psig) and heat the contents to 120℃. It was hot. 1,2-epoxybutane was gradually and continuously introduced into this autoclave. Ta. During this time, the contents of the reactor were kept between 110 and 130°C. 1,2-epo The maximum pressure during the xybutane introduction step did not exceed 1100 psi. 600g After introducing 1,2-epoxybutane into the autoclave, the reaction was slowed down. O The contents of the autoclave were cooled to approximately 15°C, the autoclave was opened, and the alkoxy An additional 0.66 g of sodium hydroxide was introduced to speed up the reaction.

Close the autoclave, replace the air inside with nitrogen, and flush the autoclave with nitrogen. Pressure was applied to 10 psig and the contents were heated to 120°C. 1,2-epoxybutane was reintroduced into the autoclave, and the total amount of epoxybutane added was approximately 865 g. And so. When the pressure inside the autoclave reached a certain value, the autoclave was cooled down. . 886.4 g of pale yellow colored liquid product was obtained. This product is exposed to reduced pressure, Residual unreacted 1,2-epoxybutane was removed from the product. This vacuum treatment product was identified as a butoxylation product of allyl alcohol. Proton NMR spectroscopy Analysis determined that the number of butoxy groups in the product was approximately 12,3 per molecule. .

11 In an autoclave equipped with a magnetic stirrer, 332g was treated under reduced pressure as described above. butoxylated allyl alcohol. Nitrogen the air in the autoclave The butoxylated allyl alcohol was heated to 120°C. stop 240g of ethylene oxide was added to this autoclave at a reaction temperature of 120g. ℃ and keep the internal pressure from exceeding 90 psig. Add slowly over about 3 hours. added. Cool the resulting product to 30 °C to neutralize the basicity of the reaction mixture. 0.89 g of acetic acid was added to the reaction product. The final product is a pale yellow liquid Ta. The number of ethoxy units per molecule in the product was determined by proton NMR and was approximately 15. A value of 3 was obtained. This product is referred to herein as Sample 1-A. 0.1 weight of sample 1-A % aqueous solution was prepared, and the surface tension of this solution was measured using a Dunouy tensiometer at 25°C. It was measured with The surface tension of this solution is 31.6 dynes/centimeter Met.

11 Place 277 g of vacuum-treated butoxylated allyl alcohol in an autoclave. Filled and flushed with nitrogen for 30 minutes. This butoxylated allyl alcohol Heated to 120°C and added 330g of ethylene oxide, keeping the reaction temperature at about 120°C. Add slowly over approximately 3 hours, making sure the internal pressure does not exceed 90 psig. Ta. 0.74 g of acetic acid was added to the reaction product to neutralize the basicity of the product. . 614.7 g of pale yellow liquid product was obtained. As measured by proton NMR At this time, the number of ethoxy units per molecule in the product was approximately 26.1. this product is referred to herein as Sample 1-B. Surface of 0.1 wt% aqueous solution of sample 1-B product The tension was 32.2 dynes/centimeter at 25°C.

11 Put 221 g of vacuum-treated butoxylated allyl alcohol into an autoclave. Filled and flushed with nitrogen, the butoxylated allyl alcohol was heated to 120°C. Heated. 370g of ethylene oxide was added at a temperature of about 120°C. , Gradually heat the autoclave over a period of approximately 4 hours, making sure that the internal pressure does not exceed 1100 psi. Added to Bu. After adding all the ethylene oxide to the autoclave, the internal pressure is The autoclave was cooled. 0.5 to neutralize the basicity of the product 9g of acetic acid was added to the reaction product. When measured by proton NMR, it was pale yellow. The number of ethoxy units per molecule in the product was approximately 40.6. This product is Here, it is referred to as sample 1-C. Surface tension of 0.1% by weight aqueous solution of sample 1-C product was 33.6 dynes/centimeter at 25°C. Example 2 Equipped with phosgene inlet tube, dry ice cooled condenser, stirrer and dropping funnel A jacketed 21 round bottom flask was charged with 20 g of liquid phosgene. and , into a reaction flask, 477 g of the sample 1-B product described in Example 1; and 40 g of phosgene were further added.

The reaction mixture was stirred for several hours at 15-20°C, after which the reaction products were reduced. Excess phosgene was removed by applying pressure. The obtained chloroformate is 1. 120-140°C in the presence of 23g trioctylmethylammonium chloride It was converted to the corresponding chloride by heating for 4 hours. 480g of product Recovered. Is this product proton NMI? Spectroscopy and infrared spectroscopy and Compatible with total chloride analysis It was confirmed that it is a chloride.

Example 3 Example of 100.7g in an autoclave with a 0.51 magnetic cooler Chloride product of 2, 12.3g Sodium sulfite (98%), 265.1g of deionized water, and 1.2 g of a 50% aqueous solution of sodium hydroxide.

Seal this Autotra 1 knob and heat the contents to 155°C and keep this temperature overnight. Maintained. The internal pressure in the autoclave was kept constant at approximately 60 psig. Autotoku The contents of the leve were then cooled to below 5°C. The product obtained i.e., the sulfonate corresponding to the chloride product of Example 2) had a solid content of 28.3%. A pale yellow liquid containing 7.2% of anionic surfactant activity. It was the body.

Example 4 77.4 g of the sulfonate product previously prepared in Example 3 was combined with the reactants. The procedure of Example 3 was repeated, except that the mixture was added to the autoclave. 423 ．． 7 g of pale yellow clear liquid product was recovered from the autoclave. residual sulfite This product was treated with 1.00 g of hydrogen peroxide (49,5 %). This product contains approximately 30% solids and has anionic surfactants. The agent activity was determined to be approximately 14.6%.

Example 5 113.2 g of the sulfonate product previously prepared in Example 4 was added as reactant. The procedure of Example 3 was repeated except that both were added to the autoclave. anti The reaction product was a pale yellow transparent liquid. To remove residual sulfite anions, This product was treated with 1.33 g of hydrogen peroxide (49.5%). This sulfona The product from Example 4 was combined with the product from Example 4. The color mixture obtained is approximately 28.3% solids content, and anionic surfactant activity was determined to be approximately 16.2%. this The surface tension of a 0°1% aqueous solution of the product is 35.6 dynes at 25°C. /centimeter.

Example 6 Using the procedure of Example 2, 401 g of Sample 1-A was reacted with phosgene to obtain of chloroformate with 1.1 g of trioctylmethylammonium chloride. Decarboxylation by reaction gave the corresponding chloride. 77. 7 g of the resulting chloride product were dissolved in 15° 4 g of sodium sulfite, 174.3 g of deionized water and 1.54 g of a 50% aqueous solution of sodium hydroxide. It was converted to the sulfonate by the procedure of Example 3. Contains 33.3% solids , a milky white, pale yellow liquid was obtained with an anionic surfactant activity of 9.6%. .

Example 7 77.7 g of the chloride product of Example 6, 1.5.4 g of sodium sulfite, 1, 54 g of sodium hydroxide, 218.3 g of deionized water and 135. Example 3 using 9 g of the sulfonate product preformed in Example 6 The sulfonation operation was repeated. The product contains about 29.3% solids and about 1 It was determined to have 0.8% anionic surfactant activity. Leave it for about 2 weeks The product separated into two phases.

Example 8 149.8 g of the upper layer of the sulfonate product of Example 7 was added to the sulfonation reaction. Repeat the procedure of Example 7 except use the preformed sulfonate. did. This sulfonate product was treated with 1.33 g of hydrogen peroxide (49.5%). The residual sulfite anion was removed by combined with the rest of the composition.

The mixed product had an anionic surfactant activity of 11.1%. this product The surface tension of a 0.1% aqueous solution of is 35.9dynes/cen at 25°C. It was timer.

Example 9 Treat 407 g of sample 1 with phosgene according to the procedure of Example 2. Converted to chloroformate. 1.05 g trioctylmethylammonium The solution is to decarboxylate this chloroformate using chloride. The corresponding chloride was obtained. 10.8g sodium sulfite, 1.1g sodium hydroxide The procedure of Example 3 was performed using a 50% aqueous solution of 115.6 g of the resulting chloride product was converted into the corresponding sulfonate. Converted to Nato.

The product was pale yellow and transparent at 60°C. Add this to 1.9g of hydrogen peroxide (49.5%) to remove residual sulfite anions. The product is 28.8% of solids and had an anionic surfactant activity of 15.8.

Example 10 57.1 g of the sulfonate product preformed in Example 9 was combined with the reactants. The sulfonation procedure of Example 9 was repeated except that . The product is a clear pale yellow liquid that can be treated with 1.76 g of hydrogen peroxide. Residual sulfite anions were removed. This sulfonate product is approximately 31.9 % solids and an anionic surfactant activity of 18.7%.

This sulfonate product was combined with the remainder of the product from Example 9. profit The resulting mixture contains about 32.6% solids and about 16.1% anionic interface. The activator activity was determined. The surface tension of a 0.1% aqueous solution of this product is 25°C. It was 35.1 dynes/centimeter.

Example 11 Using the sulfonate product of Example 5 alone as a surfactant, vinyl acetate- A butyl acrylate copolymer was prepared. 11 resin keratle, 281g of desorbed 31.7 g of the sulfonate product of Example 5 in ionized water was charged. This melt The solution was heated to 80°C under nitrogen atmosphere. 1 g of potassium persulfate (KzSz Os) was added to the solution, followed by 202 g of vinyl acetate and 36 g of butylene acrylate. 50 ml of the mixture consisting of 50m of monomer mixture After adding 1, the degree of polymerization was maintained at 75-80°C for 30 minutes. 7 Keratol The remainder of the monomer mixture was heated for 3 to 4 hours while maintaining the polymerization temperature between 0 and 75°C. and filled it into a keratle. The contents of the resin keratle were heated to 70°C for an additional hour. Stir and then add 10 g of 2% formaldehyde sulfoxylate to the keratru. In addition, the polymerization was terminated.

Cool the contents of the keratru to room temperature and dry with cheese cloth. The latex in the keratle was recovered by concentrating it through filtration.

The aggregated polymer product was less than 1%. Turn part of this latex into a film The film was cast and dissolved in chloroform-d (CD3C1). this Proton NMR spectroscopy of chloroform solution reveals the absence of allyl hydrogen. This was confirmed. Therefore, the sulfonate product of Example 5 is It is considered that there was a complete reaction.

Cast a film of this latex onto a microscope slide and leave it for at least 24 hours. Air dried. The film was measured using an NRL contact angle goniometer, model 100-00. The contact angle of a drop of water placed on the film was measured.

The contact angle was measured within 10 seconds of placing the water on the film and obtained a value of 52°. .

Example 12 For comparison purposes, 24 g of sodium lauryl sulfate (30% active) was used alone as a surfactant. Emulsion polymerization in Example 11 was carried out using the compound as a sexing agent. Cheese cloth (cheese c) The product was recovered by concentrating through (loth).

The aggregated product was less than 1%.

A film prepared from the latex described above according to the procedure described in Example 11. The contact angle of a water droplet placed on the membrane was measured. By measuring immediately after dropping a water drop The contact angle obtained was less than 5°.

Contact angle measurements of Examples 11 and 12 revealed that the copolymerizable interface of Example 5 Latexes prepared with activators are compatible with conventional dairy products such as sodium lauryl sulfate. It was shown to be less hydrophilic than latex made from polymerizing agents.

Example 13 Vinyl acetate was prepared using the sulfonate product of Example 10 alone as a surfactant. A monopolymer was prepared. 11 resin keratle, 20 g of 238 g of deionized water A solution of the sulfonate product of Example 10 was charged. This solution was added under nitrogen atmosphere. 0.5 g of potassium persulfate (KzSzOs) was added to the solution. added. 50g of vinyl acetate was slowly added to the resin kerator. Early days of vinyl acetate After the filling was completed, the reaction temperature was maintained at 75-80°C for 30 minutes. Next, While keeping the rattle at a polymerization temperature of about 80°C, add 150g of vinyl acetate for 3 to 4 hours. and filled it into a keratle. The contents of the resin keratle were heated to 85°C for an additional 1 hour. Stir for a while, cool to room temperature, then thicken through a cheese cloth. The latex in the tank was collected. The amount of agglomerated polymer product was approximately 1% . This latex was cast into a film on a microscope slide and kept for at least 24 hours. Air dry for a while. Example 1: Measuring the contact angle of a drop of water placed on this film 1), a value of 53° was obtained.

Thus, although the invention is described in detail with respect to certain specific embodiments, Such detailed description does not limit the scope of the invention as encompassed by the claims appended hereto. It's not something you can do.

Submission of translation of written amendment (Article 184-7, Paragraph 1 of the Patent Act) December 20, 1990 11

Claims (35)

[Claims] 1. A compound represented by the following formula: R-O-(R'O)m-(EO)n-1-CH2CH2-X, where R is C 2-C18 alkenyl, acrylyl, acrylyl (C1-C10) alkyl, Methacrylyl, methacrylyl (C1-C10) alkyl, vinylphenyl, and and vinylphenylene (C1-C6) alkyl, and R'O is , divalent alkyleneoxy derived from a cyclic ether other than ethylene oxide and mixtures of such alkyleneoxy groups, is a divalent ethylene group, m and n are each a number from about 5 to about 100, The m:n ratio is about 20:1 to about 1:20, and X is hydroxyl, chloride, t-Amino, and anionic groups such as sulfonate, sulfate, and phosphatide. acetate, isethionate, (and alkali of such anionic groups) potassium metal salts). 2. The alkyleneoxy group R'O formula, -CH2CH(R'')-O- (wherein , R'' is methyl, ethyl, phenyl, phenyloxymethyl, and -CH2 -(CH2)2-CH2-O-), where m and n are each about 5 to a number of about 50, where X is chloride, hydroxyl, t-amino, and anio sulfonate, sulfate, phosphate, acetate, isethyl onates, (and alkali metal salts of such anionic groups) 2. A compound according to claim 1, selected from: 3. R is selected from the group consisting of vinyl and allyl, and R'O is propylene oxy butylene oxide, and mixtures of propylene oxide and butylene oxide. It is a divalent epoxy group derived from a compound, and m and n are each about 5 to about 5. 0 and X is chloride, hydroxyl, t-amino, and anionic The groups sulfonate, sulfate, phosphate, acetate, isethiona (and alkali metal salts of such anionic groups) A compound according to claim 1, which is selected from the group consisting of: 4. The compound according to claim 3, wherein the t-amino group is represented by the following formula: -N+(R2)(R3)R4, Here, R2, R3, and R4 are C1-C5 alkyl, and hydro selected from the group consisting of xy(C1-C5)alkyl; 5. R is allyl and R′0 is a divalent epoxy derived from butylene oxide. 4. The compound according to claim 3, which is a group. 6. sulfates in which X is chloride, hydroxyl, and anionic groups; sulfonates, phosphates, (and such anionic alkali gold 6. The compound according to claim 5, wherein the compound is selected from the group consisting of genus salts. 7. A method for free radical initiated polymerization of ethylenically unsaturated reactive monomers. and the polymerization comprises about 1% to about 25% by weight or less, based on the total amount of reacting monomers. A method carried out in the presence of a compound of the formula: R-O-(R'O)m-(EO)m-1-CH2CH2-X, where R is C 2-C18 alkenyl, acrylyl, acrylyl (C1-C10) alkyl, Methacrylyl, methacrylyl (C1-C10) alkyl, vinylphenyl, and and vinylphenylene (C1-C6) alkyl, and R'O is , divalent alkyleneoxy derived from a cyclic ether other than ethylene oxide and mixtures of such alkyleneoxy groups, is a divalent ethylene group, m and n are each a number from about 5 to about 100, The m:n ratio is about 20:1 to about 1:20, and X is hydroxyl, chloride, t-Amino, and anionic groups such as sulfonate, sulfate, and phosphatide. acetate, isethionate, (and alkali of such anionic groups) metal salts). 8. 8. The method of claim 7, wherein the polymerization is emulsion polymerization. 9. 9. The method of claim 8, wherein a non-polymerizable surfactant is present during said polymerization. 10. The ethylenically unsaturated monomer is a mono- and polyunsaturated hydrocarbon monomer. -, vinyl esters, vinyl ethers, monoethylenically unsaturated mono and polycarbonate Rubonic acids and their alkyl esters, nitriles, vinyl halides, halide vinylidene chlorides, amides of unsaturated carboxylic acids, amino monomers, and 9. The method of claim 8, wherein the monomer is selected from the group consisting of a mixture of monomers such as: 11. The monoethylenically unsaturated alkyl monocarboxylic acid is acrylic acid or tacrylic acid, and their alkyl esters are C1-C12 alkyl esters. The method according to claim 10. 12. 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, vinylide fluoride and a mixture of acrylic monomers. How to put it on. 13. A process for free radical-initiated emulsion polymerization of ethylenically unsaturated reactive monomers. in which the polymerization comprises about 1% to about 25% by weight based on the total amount of reactant monomers. Improvement carried out in the presence of a compound of the following formula: R-O-(R'O)m-(EO)n-1-CH2CH2-X, where R is C 2-C18 alkenyl, acrylyl, acrylyl (C1-C10) alkyl, Methacrylyl, methacrylyl (C1-C10) alkyl, vinylphenyl, and and vinylphenylene (C1-C6) alkyl, and R'O is Formula, -CH2CH(R'')-O- (where R'' is methyl, ethyl, phenyl phenyloxymethyl, and -CH2-(CH2)2-CH2-O-. divalent alkyleneoxy groups represented by ), and such alkyleneoxy groups selected from the group consisting of a mixture of groups, E is a divalent ethylene group, m and n are each a number from about 5 to about 50, and the m:n ratio is from about 20:1 to about 1:20. and X is chloride, hydroxyl, t-amino, and an anionic group. Ruphonate, Sulfate, Phosphate, Acetate, Isethionate, and alkali metal salts of such anionic groups). 14. Claims wherein the compound represented by the formula: is present in an amount of about 1 to about 10% by weight. Steps described in 13: R-O-(R'O)m-(EO)n-1-CH2CH2-X. 15. 15. The method of claim 14, wherein a non-polymerizable surfactant is present during the polymerization step. . 16. R is selected from the group consisting of vinyl and allyl, and R′O is propylene. butylene oxide, butylene oxide, and propylene oxide and butylene oxide is a divalent epoxy group derived from a mixture of ˜about 50, where X is chloride, hydroxyl, t-amino, and anidine. Ionic groups sulfonate sulfate, phosphate, acetate, isethyl onates, (and alkali metal salts of such anionic groups) 15. The process according to claim 14, selected from: 17. The ethylenically unsaturated monomer is a mono- and polyunsaturated hydrocarbon monomer. vinyl esters, vinyl ethers, monoethylenically unsaturated mono- and polyesters, vinyl esters, vinyl ethers, Carboxylic acids and their alkyl esters, nitriles, vinyl halides, Vinylidene halides, amides of unsaturated carboxylic acids, amino monomers, and 17. The process of claim 16, wherein the monomer is selected from the group consisting of mixtures of these monomers. 18. The monoethylenically unsaturated monocarboxylic acid is acrylic acid or methacrylic acid. acids, and their alkyl esters are C1-C12 alkyl esters, 18. The method according to claim 17. 19. The ethylenically unsaturated monomer is a vinyl acetate-acrylic monomer mixture. compound, vinyl acetate, styrene-acrylic monomer mixture, styrene-butadiene monomer mixture, vinyl chloride, vinyl fluoride, vinylidene chloride, vinyl fluoride Claim 1 selected from the group consisting of DEN, and a mixture of acrylic monomers. 6. The process described in 6. 20. R is allyl and R'O is a divalent epoxy derived from butylene oxide. 20. The process according to claim 19, which is an xy group. 21. Sulfates in which X is chloride, hydroxyl, and anionic groups , sulfonates, phosphates, (and alkalis of such anionic groups) 21. The process according to claim 20, wherein the metal salt is selected from the group consisting of: 22. From about 1 to about 25% by weight, based on the total amount of reacting monomers, represented by the formula: free radicals of ethylenically unsaturated reaction monomers carried out in the presence of compounds Polymer prepared by initiated polymerization and substantially free of water-soluble surfactants Product: R-O-(R'O)m-(EO)n-1-CH2CH2-X, where R is C2-C18 alkenyl, acrylyl, acrylyl (C1-C10) acryl alkyl, methacrylyl, methacrylyl (C1-C10) alkyl, vinylphenylene and vinylphenylene (C1-C6) alkyl, R'O is a divalent alkylene derived from a cyclic ether other than ethylene oxide. selected from the group consisting of alkyleneoxy groups, and mixtures of such alkyleneoxy groups. , E is a divalent ethylene group, and m and n are each a number from about 5 to about 50. , the m:n ratio is about 20:1 to about 1:20, and X is hydroxyl, chloro lydo, t-amino, and the anionic groups sulfonate, sulfate, and phosphatide. sphate, acetate, isethionate, (and such anionic groups) alkali metal salts). 23. 23. The polymer product of claim 22, wherein said polymer is in latex form. 24. R is selected from the group consisting of vinyl and allyl; oxide, butylene oxide, and the combination of propylene oxide and butylene oxide. is a divalent epoxy group derived from a mixture, m and n are each about 5 to about 50 and X is chloride, hydroxyl, t-amino, and anion sulfonate, sulfate, phosphate, acetate, isethio (and alkali metal salts of such anionic groups) 23. The polymer product of claim 22, wherein: 25. The ethylenically unsaturated monomer is a mono- and polyunsaturated hydrocarbon monomer. -, vinyl esters, vinyl ethers, monoethylenically unsaturated mono and polycarbonate Rubonic acids and their alkyl esters, nitriles, vinyl halides, halide vinylidene chlorides, amides of unsaturated carboxylic acids, amino monomers, and 25. The polymer product of claim 24 selected from the group consisting of a mixture of monomers of . 26. The monoethylenically unsaturated monocarboxylic acid is acrylic acid or methacrylic acid. acids, and their alkyl esters are C1-C12 alkyl esters, 26. The polymer product of claim 25. 27. 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, vinylide fluoride and a mixture of acrylic monomers. polymer products. 28. R is allyl and R'O is a divalent epoxy derived from butylene oxide. 28. The polymer product of claim 27, which is an xy group. 29. From about 1 to about 10% by weight, based on the total amount of reactant monomers, represented by the formula: free radicals of ethylenically unsaturated reaction monomers carried out in the presence of compounds Polymers prepared by initiated emulsion polymerization and containing substantially no water-soluble surfactants. mer product: R-O-(R'O)m-(EO)n-1-CH2CH2-X, where and R is C2-C18 alkenyl, acrylyl, acrylyl (C1-C10 ) alkyl, methacrylyl, methacrylyl (C1-C10) alkyl, vinylph selected from the group consisting of phenyl, and vinylphenylene (C1-C6) alkyl. and R′O has the formula -CH2CH(R″)-O- (where R″ is methyl, thyl, phenyl, phenyloxymethyl, and -CH2-(CH2)2-CH 2-O-), and such alkyloxy groups; selected from the group consisting of a mixture of xyleneoxy groups, E is a divalent ethylene group; , m and n are each a number from about 5 to about 50, and the m:n ratio is from about 20:1 to about 1:20 and X is chloride, hydroxyl, t-amino, and anion sulfonate, sulfate, phosphate, acetate, isethio (and alkali metal salts of such anionic groups) selected. 30. R is selected from the group consisting of vinyl and allyl, and R′O is propylene. oxide, butylene oxide, and propylene oxide and butylene oxide is a divalent epoxy group derived from a mixture of ˜about 50, where X is chloride, hydroxyl, t-amino, and anidine. Ionic groups sulfonate, sulfate, phosphate, acetate, ise thionates (and alkali metal salts of such anionic groups) 30. The polymeric product of claim 29, selected from: 31. The ethylenically unsaturated monomer is a mono- and polyunsaturated hydrocarbon monomer. vinyl esters, vinyl ethers, monoethylenically unsaturated mono- and polyesters, vinyl esters, vinyl ethers, Carboxylic acids and their alkyl esters, nitriles, vinyl halides, Vinylidene halides, amides of unsaturated carboxylic acids, amino monomers, and 31. The polymer product of claim 30 selected from the group consisting of mixtures of these monomers. thing. 32. The monoethylenically unsaturated monocarboxylic acid is acrylic acid or methacrylic acid. acids, and their alkyl esters are C1-C12 alkyl esters, 32. The polymer product of claim 31. 33. 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, vinylide fluoride and a mixture of acrylic monomers. polymer products. 34. R is allyl and R'O is a divalent epoxy derived from butylene oxide. 34. The polymer product of claim 33, which is an xy group. 35. 34. A coating prepared from the polymer product of claim 33, wherein the water of the coating comprises: A coating film having a contact angle of less than 5° when a water drop is placed on the coating film.