MXPA99007014A

MXPA99007014A - Novel ethylenically unsaturated amine salts of sulfonic, phosphoric and carboxylic acids

Info

Publication number: MXPA99007014A
Application number: MXPA/A/1999/007014A
Authority: MX
Inventors: K Schultz Alfred
Original assignee: K Schultz Alfred; Stepan Company
Priority date: 1997-01-28
Filing date: 1999-07-28
Publication date: 2000-01-01

Abstract

Disclosed are ethylenically unsaturated amine salts of sulfonic, phosphoric and carboxylic acids. The salts are surface active agents which are especially useful in emulsion polymerization reactions.

Description

NEW AMINO SALTS ETHICALLY INSATURED FROM SULPHONIC, PHOSPHORIC AND CARBOXYLIC ACIDS BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to the novel ethylenically unsaturated amine salts of sulfonic, phosphoric and carboxylic acids. More specifically, the invention relates to the ethylenically unsaturated amine salts of alkylbenzenesulfonic acids, alkyl olefin sulphonic acids, alkyl alcohol sulfuric acid esters and alkoxylated alkyl alcohol sulfuric acid esters, and mixtures thereof. Furthermore, the invention relates to the ethylenically unsaturated amine salts of the alkylcarboxylic acids and alkyl phosphoric acids. Salts are polymerizable surface active agents that are useful in a variety of applications, especially in detergent formulations and in emulsion polymerization processes. REF .: 30967 Description of Related Art A variety of surface active agents are known in the art, including, for example, anionic, nonionic, amphoteric and / or cationic surfactants. The anionic surfactants are typically in the form of alkali metal (lithium, sodium, potassium), alkaline earth metal (calcium, magnesium), ammonium and / or alkanolamine salts of the corresponding anionic acid. Surface active agents are useful in a variety of applications, for example, emulsion polymerization reactions. For example, in a conventional emulsion polymerization of ethylenically unsaturated monomers, one or more surfactants are used to emulsify the resulting monomers and polymer products, for example latex. The monomers used in the emulsion polymerization reactions are generally insoluble in water, but can also be soluble in water. During the polymerization, the small portions of the monomer are suspended in a continuous aqueous phase. Typically, a water-soluble surfactant is present within the aqueous phase to aid in the suspension of the monomer, with subsequent polymerization via a free radical polymerization. Water-soluble surface active agents, for example surfactants, used in emulsion polymerization reactions are typically anionic, non-ionic, cationic, or amphoteric surfactants or mixtures thereof. In a traditional emulsion polymerization reaction, discrete solid polymer particles are formed during the course of the reaction to form a latex of polymer product. Typically, the surfactant employed in such a traditional emulsion polymerization reaction does not react with, for example, chemically bound via the carbon-carbon bond formation to the discrete polymer particles. More • well, the surfactant remains unreacted in the polymeric product latex after the emulsion polymerization reaction is terminated. Unreacted surfactant can interfere with the operation of such polymerization products in coating, adhesive, sealant and elastomer (CASE) applications. Unreacted surfactant can, for example, cause delamination of the latex paint coating, and decreased resistance against moisture and resistance against rubbing or scouring in various CASE applications. In addition, the residual surfactant can cause "loss of brightness" which leads to surface irregularities in a resulting CASE, which is applied to a substrate Various proposals have been made in the prior art for employing a polymerizable surfactant as a surface active agent. during an emulsion polymerization reaction US Patent No. 5,478,883 (hereby incorporated by reference, in its entirety) describes the use of water soluble, polymerizable, ethylenically unsaturated nonionic surfactants, formed by the reaction of a diallylamine compound with ethylene oxide, propylene oxide or butylene oxide, in emulsion polymerization reactions. Similarly, U.S. Patent No. 5,162,475 (incorporated herein by reference) provides polymerizable, poly (alkyleneoxy), alpha-beta-ethylenic unsaturated surface active compounds for use in emulsion polymerization. For further examples of the polymerizable surfactants for use in emulsion polymerization processes, see U.S. Patent Nos. 4,377,185 and 4,049,608.

BRIEF DESCRIPTION OF THE INVENTION The present invention provides the ethylenically unsaturated amine salts of sulfonic, phosphoric or carboxylic acids, or mixtures thereof. The amine salts of the present invention are polymerizable surface active agents suitable for use as primary or secondary surfactants in emulsion polymerization reactions. The active surface agents of the present invention are especially useful in emulsion polymerization reactions and are generally capable of polymerizing with themselves, and / or of copolymerizing with other ethylenically unsaturated monomers of the type that are commonly employed in polymerization reactions in emulsion. The surface active agents of the present invention are prepared from inexpensive, readily available raw materials, and in general, their preparation does not require any special handling or equipment. The polymerizable surface active agents can be prepared in a batchwise or "continuous mode", these can be prepared by contacting the ethylenically unsaturated amine with the acid, or contacting the acid with the ethylenically unsaturated amine. contacting means that the acid (s) are added to the ethylenically unsaturated amines (s) and the components are mixed, or the ethylenically unsaturated amines (s) are added to the acid (s) and the components are mixed, typically, after mixing , the acid and the base combine to form an amine salt.As is known to those of skill in the art, after mixing the acid and the nitrogenous base together, the nitrogenous base becomes a conjugate acid and the acid It becomes a conjugate base The polymerizable surface active agents can be alternatively prepared by contacting the amine eti typically unsaturated with an alkaline earth metal or ammonium salt of the acid (for example, the sodium, potassium, magnesium, calcium, ammonium or ethoxylated ammonium salts of the acid), whereby the polymerizable surface active agent is formed in if you Surface active agents and mixtures of surface active agents can be prepared in a variety of ways, including but not limited to liquids, solutions, solids, powders, flakes, semisolids, gels, "ringed" gels, liquids of phase G, hexagonal phase solids, or thick pastes. The surface active agents can be spray dried, flaked, extruded and the like. Although not critical to the present invention, polymerizable surface active agents can be prepared "pure" or in a conventional solvent such as water, alcohol or low molecular weight hydrocarbon, or a mixture thereof, to produce a solution of the same. Surface Active Agent The present invention encompasses surface active agents such as salts in anhydrous form or as aqueous solutions.The salts of surface active agents can be isolated by drying a solution of surface active agents; of the surface active agents can be prepared by dissolving the surface active agent salt in water, in hydrocarbon or low molecular weight alcohol, or a mixture thereof The individual surface active agents of the present invention can be be prepared and mixed together to produce an active surface mixture comprising the active agents of surface trouble "or an aqueous surfactant mixture. In addition, pure or aqueous mixtures of surface active agents can be prepared by contacting a mixture of two or more ethylenically unsaturated amines with an acid, or by contacting a mixture of two or more ethylenically amines. unsaturated with a mixture of two or more acids. Conversely, mixtures of the surface active agents can be prepared by contacting a mixture of two or more acids with an ethylenically unsaturated amine, or by contacting a mixture of two or more acids with one or more acids. mixture of two or more ethylenically unsaturated amines. These and other advantages of the present invention will be apparent from the following description of the invention.

DETAILED DESCRIPTION OF THE INVENTION The present invention encompasses polymerizable surface active agents, which are amine salts comprising: a) at least one acid, wherein the acid is a sulfonic acid, a carboxylic acid, or a phosphoric acid, or mixtures thereof; and b) at least one nitrogenous base, wherein the nitrogenous base contains at least one nitrogen atom and at least one ethylenically unsaturated portion. The acids useful in the present invention are in general sulphonic acids, polysulfonic acids, sulfonic acid oils, paraffin sulphonic acids, lignin sulphonic acids, petroleum sulfonic acids, liquid resin acids, olefin sulfonic acids, hydroxyolefin sulphonic acids , polyolefin sulphonic acids, polyhydroxypolyolefin sulphonic acids, carboxylic acids, perfluorinated carboxylic acids, carboxylic acid sulfonates, alkoxylated carboxylic acid sulphonic acids, polycarboxylic acids, polycarboxylic acid polysulphonic acids, alkoxylated polycarboxylic acid polysulphonic acids, phosphoric acids, acids alkoxylated phosphorics, polyphosphoric acids, and alkoxylated polyphosphoric acids, fluorinated phosphoric acids, phosphoric acid esters of oils, phosphinic acids, alkylphosphinic acids, aminophosphinic acids, polyphosphinic acids, acids vinylphosphinics, phosphonic acids, polyphosphonic acids, alkyl esters of phosphonic acid, a-phosphono fatty acids, organoamino polymethylphosphonic acids, dialkylene phosphonic acids of organoamino, phosphonic acids of alkanolamine, phosphonic acids of trialkylidene, phosphonic acids of acylamidomethane, diphosphonic acids of alkyliminodimethylene, polymethylene-bis (nitrilodimethylene) tetraphosphonic acids, alkyl-bis (phosphonoalkylidene) amine oxide acids, substituted to methylphosphonic acid esters, phosphonamide acids, acylated amino acids (eg, amino acids that are reacted with alkylalkyl chlorides) , alkyl esters or carboxylic acids to produce N-acylamino acids), N-alkylacylamino acids, and acylated protein hydrolysates, and mixtures thereof.

Other acids that are useful in the present invention are selected from gumpo comprising straight or branched alkylbenzene sulphonic acids, alkylsulfuric acid esters, alkoxylated alkylsulfuric acid esters, alkylated sulfonated ester acids, a-sulfonated ester diacids, ester acids alkoxylated alkylsulfonated alkylsulfonates, di-alkylsulfonated diester acids, di-a-sulfonated dialkyl diester acids, alkylsulfonated alkyl acetate acids, primary and secondary alkylsulfonic acids, perfluorinated alkylsulfonic acids, mono- and diester acids sulfosuccinic, polysulfosuccinic polyester acids, sulfoitaconic diester acids, sulfosuccinic acids, sulfosuccinic amide acids, sulfosuccinic imide acids, italic acids, sulphophthalic acids, sulfoisophthalic acids, phthalamic acids, sulfophthalamic acids, alkyl-ketone sulfonic acids, hydroxyalkan-1-sulphonic acids cos, lactone sulphonic acids, sulfonic acid amides, sulfonic acid diamides, alkylphenolsulfuric acid esters, alkoxylated alkylphenolsulfuric acid esters, alkylated cycloalkylsulfuric acid esters, alkylated and alkylated cycloalkylsulfuric acid esters, dendritic polysulphonic acids, polycarboxylic acids dendritic, dendritic polyphosphoric acids, sarcosinic acids, isethionic acids, and tauric acids, liquid resin fatty acids, and mixtures thereof. Further, in accordance with the present invention, suitable acids of the present invention include fluorinated carboxylic acids, fluorinated sulfonic acids, fluorinated sulfate acids, fluorinated phosphonic and phosphonic acids, phosphenic acids, and mixtures thereof. Due to its inherent hydrolytic instability, the sulfuric acid esters are preferably immediately converted to the ethylenically unsaturated amine salts. For example, linear dodecyl alcohol is sulfated with S03 to produce an intermediate, hydrolytically unstable, dodecyl alcohol sulfate acid, as shown in Scheme I below. The intermediate acid is neutralized with a nitrogenous ethylenically unsaturated base, such as allylamine, to produce an ethylenically unsaturated amine salt of dodecyl sulfate.

Scheme I: Formation of the Ethylenically Unsaturated Amine Salt of Dodecyl Sulfate CH3 (CH2) nOH + S03? [CH3 (CH2) 11OSO3H] + H2NCH2CH = CH2? [CH3 (CH2) 11OS03] "[NH3CH2CH = CH2] + In addition, for example, methyl laurate is sulphonated with SO 3 to produce an intermediate-sulfonated laurylmethyl ester acid, intermediate, as shown in Scheme II below. This acid is neutralized with an ethylenically unsaturated nitrogenous base, such as allylamine, to produce an ethylenically unsaturated amine salt of the α-sulfonated laurylmethyl ester. In addition, an ethylenically unsaturated amine di-salt of the α-sulfonated laurylmethyl ester can be produced as shown in Scheme III below. The ethylenically unsaturated amine salt of the α-sulfonated laurylmethyl ester and the ethylenically unsaturated amine di-salt of α-sulfonated fatty lauryl acid can be formed as a mixture depending on the sulfonation conditions employed. The ratio of the unsaturated amine salt to the unsaturated amine di-salt is easily controlled by the sulfonation conditions, well known to those skilled in the art.

Scheme II; Formation of the ethylenically unsaturated amine salt of the sulfonated laurylmethyl ester Scheme III: Formation of Di-Salt of Ethylenically Unsaturated Amine of Ester Laurylmethyl a-sulfonated H, N (-HS03OMe) The ethylenically unsaturated amine salts of the sulfosuccinate ester acids are typically produced by sulphiting an alkyl diester of succinic acid, with sodium bisulfite, followed by, for example, ion exchange with an ethylenically unsaturated nitrogenous base, such as allylamine , as shown in Scheme IV below.

Scheme IV: Formation of an Ethylenically Unsaturated Amine Salt of Sulfosuccinate Ester The ethylenically unsaturated amine salts of sarcosinic acid are prepared by the amidation of a fatty acid, an alkyl fatty acid ester or a fatty acid chloride with sarcosine, followed by the addition of an ethylenically unsaturated nitrogenous base, such as allylamine, as is shown in Scheme V below. Optionally, and somewhat less preferably, the ethylenically unsaturated nitrogenous base is combined with sarcosine to produce the corresponding sarcosine salt, which is then used to amidate the fatty acid, the fatty acid alkyl ester or the fatty acid chloride.

Scheme V: Formation of an Ethylenically Unsaturated Amine Salt of Fat Sarcosinate Acid The ethylenically unsaturated amine salts of isethionic acid can be prepared by the esterification of a fatty acid, an alkyl fatty acid ester or a fatty acid chloride with isethionic acid, followed by the addition of an ethylenically unsaturated nitrogenous base, such as allylamine, as shown in Scheme VI below. In addition, the ethylenically unsaturated amine salts of isethionic acid can be prepared by esterification of a fatty acid, an alkyl fatty acid ester or a fatty acid chloride with the sodium salt of isethionic acid, followed by ion exchange with the ethylenically unsaturated nitrogenous base, such as allylamine. Optionally, isethionic acid, or its sodium salt, can be combined with the ethylenically unsaturated nitrogenous base, such as allylamine, to produce the allylamine salt of isethionic acid, which can then be esterified with a fatty acid, an alkyl ester. of fatty acid or a fatty acid chloride.

Scheme VI: Formation of an Ethylenically Sodium Salt * Unsaturated Isethionic Acid Preferred acids of the present invention are linear or branched alkylbenzene sulphonic acids, esters of alkylsulfuric acid, esters of alkoxylated alkylsufuric acid, acids of the alkylated a-sulfonated ester, esters of carboxylic fatty acids and phosphoric acid, and mixtures thereof. The most preferred acids of the present invention are branched or linear alkylbenzene sulphonic acids, alkylsulfuric acid esters, alkylsulfuric alkylsulfuric acid esters, and mixtures thereof. Other surfactants useful in accordance with the present invention include the sulfonic acid salts of the ethylenically unsaturated amines, derived from sultone precursors, such as the cyclic alkyl ketones. Examples of these sulphonic acid salts derived from sultone (e.g., allylamine salts) include the 2-acetamidoalkyl-l-sulfonates and the alkyl sulfonates of aminocarboxylic acid, as shown in Scheme VII and Scheme VIII below.

Scheme VII: Allylamine salts of 2- acetamidoalkyl-1-sulfonic acid where R is alkyl of 4 to 24 carbon atoms.

Scheme VIII: Alkylamine Salts of Alkylsulfonic Acid of Aminocarboxylic Acid H, N where R is alkyl of 2 to 24 carbon atoms. In general, the nitrogenous bases that are useful in the present invention are any nitrogenous base containing an ethylenically unsaturated moiety, including various vinylamines. In addition to the allylamine, as shown in the above schemes, other examples of nitrogenous bases which are useful in the present invention are the ethylenically unsaturated amines selected from the group comprising vinylamine, N, N-dimethyl-N-allylamine, N-methyl -N-allylamine, (alkyl of 1 to 24 carbon atoms) -alilamine, (alkyl of 1 to 24 carbon atoms) -altolamine ethoxylated and / or propoxylated, (dialkyl of 1 to 24 carbon atoms) -alilamine, allyl ethoxylated and / or propoxylated dialkylamine, (alkyl of 1 to 24 carbon atoms) -diallylamine, ethoxylated and / or propoxylated diallylamine, tri-allylamine, 1,2-diaminoethene, aminocrotononitrile, diaminomaleonitrile, N-allyl-N -cyclopentylamine, N-allylaniline, N-allyl-N-cyclohexylamine, [1- (2-allylphenoxy) -3- (isopropylamino) -2-propanol], 3-amino-2-butentioamide, bis [4- (dimethylamino) -benzylidene ketone, bis (3-aminocrotonate) of 1,4-butanediol, vinyl ether of 3-amino-1-propanol, vinyl ether of 2- (diethylamino) ethanol, 4- (diethylamino) cinnamaldehyde, 4- (diethylamino) cinnamonitrile, 2- (diethylamino) ethyl methacrylate, (6-methyl-2-pyridylaminomethylene) diethyl maleate, 3- (dimethylamino) acrolein, 2- (dimethylamino) methacrylate ethyl, 4-dimethylaminocinnamaldehyde, 2- (dimethylamino) ethyl acrylate, 3- (dimethylamino) -2-methyl-2-propene, 9-vinylcarbazole, N-vinylcaprolactam, 1-vinylimidazole, 2-vinylpyridine, 4-vinylpyridine, allyl (diisopropylamino) dimethylsilane, 1-allyl (diisopropylamino) dimethylsilane, 1-allylimidazole, 1-vinyl-2-pyrrolidinone, N- [3- (dimethylamino) propyl] methacrylamide, 4- [4- (dimethylamino) styryl] pyridine, 2 - [4- (dimethylamino) styrylpyridine, 2- [4- (1,2-di-phenyl-1-butenyl) phenoxy] -N, N-dimethylethylamine, 2- [4-dimethylamino) styryl-benzothiozole, 5- [4 - (dimethylamino) phenyl] 2,4-pentanedienal, (dimethylaminoethylene) malononitrile, 4-dimethylaminocinonane monitrile, 4- (dimethylamino) chalcone, riboside of [6- (3, 3-dimethylallylamino-purine, 3, 7-dimethyl- 2, 6-octadien-li lamina, 2-isopropenylaniline, isopropyl 3-aminocrotonate, S-. { 2- [3- (Hexyloxy) benzoyl] -vinyl} glutathione, methyl 3-aminocrotonate, N-methylallylamine, N-methyl-1- (methylthio) -2-nitroetenamine, oleylane, tetrakis (dimethylamino) ethylene, nitrate ester of 5 - [(6,7, 8-trimethoxy -4-quinazolinyl) amino] -1-pentanol, tris (2-methylallyl) amine, N, N, N ',' -tetramethyl-2-buten-1,4-di-amine, S-. { 2 [3- (octyloxy) benzoyl] vinyl} -glutathione, 4,4'-vinylidene- (N, N-dimethylaniline), 2 ', 5'-dimethoxy-4-tylbenamine, 3- (dimethylamino) propyl acrylate, 3-dimethylamino-acrylonitrile, 4- (dimethylamino) -cinnamic, 2-amino-l-propen, 1, 1,3-tricarbonitrile, 2-amino-4-pentenoic acid, N, N'-diethyl-2-buten-l, 4-diamine, maleate of 10, ll -dihydro-N, N-dimethyl-5-methylene-5H-dibenzo [a, d] -cycloheppen-l-ethanamine, 4- (dicyanomethylene) -2-methyl-6- (4-dimethylaminostyryl) - 4H -piran, N-ethyl-2-methylalylamine, ethyl 3-aminocrotonate, ethyl-a-cyano-3-indolacrylate, ethyl-3-amino-4,4-dicyano-3-butenoate, 1,3-divinyl- 1, 1,3,3-tetramethyldisilazane, N- (4,5-dihydro-5-oxo-l-phenyl-1, p-pyrazol-3-yl) -9-octadecen-amida, and N-oleyl ethyl ester -triptophane, and mixtures thereof. The most preferred nitrogenous bases of the present invention are allylamine, diallylamine, triallylamine, N-methyl-N-allylamine, N-allyl-N, N-dimethylamine, methyl 3-aminocrotonate, 3-aminocrotononitrile, 3-amino vinyl ester -l-propanol,. N-methyl-N-allylamine, 2- (dimethylamino) ethyl acrylate, or 1,4-diamino-2-butene, and mixtures thereof. The most preferred nitrogenous bases of the present invention are allylamine, diallylamine, triallylamine, methallylamine, N-methyl-N-allylamine, and 2- (dimethylamino) ethyl acrylate, and mixtures thereof. In the methods and compositions of the invention, the amine salts are generally preferred over the quaternary ammonium compounds. Accordingly, the present invention utilizes the surface active agents of the formula: (R?) N-Ar (S03_M +) wherein Ri is a saturated or unsaturated hydrocarbon group having from about 1 to 24 carbon atoms; wherein Ar is a phenyl, polyphenyl, naphthyl, polinaphthyl, styryl, or polystyryl group, or a mixture thereof; wherein M + is a conjugate acid of the nitrogenous base; where n = 1-5 and m = 1-8; and wherein the total number of carbon atoms represented by (R?) n is at least 5. In a preferred embodiment Ri, it is a saturated or unsaturated hydrocarbon group having from about 6 to 24 carbon atoms, Ar is a phenyl M + is a conjugate acid of the nitrogenous base, the nitrogenous base is selected from the group consisting of allylamine, diallylamine, triallylamine, methallylamine, N-methyl-N-allylamine or 2- (dimethylamino) ethyl acrylate, and mixtures thereof and n = 1 and m = 1. In another preferred embodiment, the active surface agent is of the formula: where ni = 4-18; and wherein R 'is hydrogen or a saturated or unsaturated hydrocarbon group, having from about 1 to 8 carbon atoms. The present invention also uses the surface active agents of the formula (R?) M-ÍAr (S03"M +) ml.}. -0- { Ar (S03" M +) m2} - (R2) n2 wherein Ri and R2 are independently hydrogen, or saturated or unsaturated hydrocarbon groups having from about 1 to 24 carbon atoms; wherein Ar is a phenyl, polyphenyl, naphthyl, polinaphthyl, styryl, or polystyryl group, or a mixture thereof; wherein M + is a conjugate acid of the nitrogenous base; where ni and n2 are independently 0-5, with the proviso that ni and n2 are not both equal to zero; and where mi and m2 are independently 0-8, with the proviso that mi and m2 are not both equal to zero. In a preferred embodiment, Ri is hydrogen and R2 is a saturated or unsaturated hydrocarbon group having from about 6 to 24 carbon atoms, Ar is phenyl, M + is a conjugate acid of the nitrogenous base, the nitrogenous base is selected from the group consists of allylamine, diallylamine, triallylamine, methallylamine, N-methyl-N-allylamine or 2- (dimethylamino) ethyl acrylate, and mixtures thereof, ni = 4, n2 = 1, and mi and m2 are both equal to one . In another preferred embodiment, Ri and R2 are independently saturated or unsaturated hydrocarbon groups having from about 6 to 24 carbon atoms, Ar is phenyl, M + is a conjugate acid of the nitrogenous base, the nitrogenous base is selected from the group consisting of allylamine, diallylamine, triallylamine, metalylamine, N-methyl-N-allylamine, or 2- (dimethylamino) ethyl acrylate, and mixtures thereof, ni and n2 are both equal to 1., and mi and m.2 are both equal to one. In another preferred embodiment, the surface active agent is of the formula: wherein n and n 'are independently 4-18; and wherein R 'and R "are independently hydrogen, methyl, ethyl or propyl. The present invention further utilizes the surface active agents of the formula: R? -CH (S03"M +) C02R2 wherein Ri and R2 are independently saturated or unsaturated hydrocarbon groups having from about 1 to 24 carbon atoms; and where M + is a conjugate acid of the nitrogenous base. In a preferred embodiment, Ri is a saturated or unsaturated hydrocarbon group having from about 6 to 24 carbon atoms, R2 is methyl, ethyl, or propyl, or a mixture thereof, • and M + in a conjugate acid of the nitrogenous base, the nitrogenous base is selected from the group consisting of allylamine, diallylamine, triallylamine, methallylamine, N-methyl-N-allylamine or 2- (dimethylamino) ethyl acrylate, and mixtures of the same. In another preferred embodiment, the surface active agent is of the formula: where n = 3-18. The present invention further utilizes the surface active agents of the formula: R? -CH (S03"M +) C02M + wherein Ri is a saturated or unsaturated hydrocarbon group having from about 3 to 24 carbon atoms; and where M + is a conjugate acid of the nitrogenous base. In a preferred embodiment, Ri is a saturated or unsaturated hydrocarbon group having from about 6 to 24 carbon atoms, M + is a conjugate acid of the nitrogenous base, the nitrogenous base is selected from the group consisting of allylamine, diallylamine, triallylamine, metalylamine, N-methyl-N-allylamine or 2- (dimethylamino) ethyl acrylate, and mixtures thereof. In another preferred embodiment, the surface active agent is of the formula: where n = 3-18. The present invention further utilizes the surface active agents of the formula: Ri-CH (S03"M +) C (O) O (CH2CH (R ') O) nR2 wherein Ri and R2 are independently saturated or unsaturated hydrocarbon groups having from about 1 to 24 carbon atoms; wherein R 'is methyl or hydrogen; where n = 1-100; and where M + is a conjugate acid of the nitrogenous base. In a preferred embodiment, Ri is a saturated or unsaturated hydrocarbon group having from about 4 to 24 carbon atoms, R 'is methyl or hydrogen, R2 is methyl, ethyl, or propyl, and mixtures thereof, M + is an acid conjugate of the nitrogenous base, the nitrogenous base is selected from the group consisting of allylamine, diallylamine, triallylamine, methallylamine, N-methyl-N-allylamine or 2- (dimethylamino) ethyl acrylate, and mixtures thereof, and n = 1 -100. In another preferred embodiment, the surface active agent is of the formula: where ni = 2-18; and where n2 = 1-20. The present invention further utilizes the surface active agents of the formula: Ri- (SO3"M +; wherein R is a saturated or unsaturated hydrocarbon group having from about 6 to 24 carbon atoms and wherein M + is a conjugate acid of the nitrogenous base. In a preferred embodiment, Ri is a saturated or unsaturated hydrocarbon group having from about 6 to 24 carbon atoms, and M + is a conjugate acid of the nitrogenous base, the nitrogenous base is selected from the group consisting of allylamine, diallylamine, triallylamine , metalylamine, N-methyl-N-allylamine or 2- (dimethylamino) ethyl acrylate, and mixtures thereof. In another preferred embodiment, the surface active agent is of the formula: where n = 5-17. The present invention further utilizes the surface active agents of the formula: RiCOz (CH2) nCH (S03"M +) C02Rz wherein Ri and R2 are independently saturated or unsaturated hydrocarbon groups having from about 1 to 24 carbon atoms; where n = 0-10; and where M + is a conjugate acid of the nitrogenous base. In a preferred embodiment, Ri and R2 are independently saturated or unsaturated hydrocarbon groups having from about 1 to 24 carbon atoms, n = 1-6, and M + is a conjugate acid of the nitrogenous base, the nitrogenous base is selected from the group which consists of allylamine, diallylamine, triallylamine, methallylamine, N-methyl-N-allylamine or 2- (dimethylamino) ethyl acrylate, and mixtures thereof. In another preferred embodiment, the surface active agent is of the formula: where neither is zero or an integer from 1 to 17; and Xs represents S03 ~. The present invention further utilizes the surface active agents of the formula: RxC02 (CH2) nS03 ~ M " wherein Ri is a saturated or unsaturated hydrocarbon group having from about 1 to 24 carbon atoms; where n = 1-10; and where M + is a conjugate acid of the nitrogenous base. In a preferred embodiment, Ri is a saturated or unsaturated hydrocarbon group having from about 6 to 24 carbon atoms, n = 1-5, and M + is a conjugate acid of the nitrogenous base, the nitrogenous base is selected from the group consisting of essentially of allylamine, diallylamine, triallylamine, methallylamine, N-methyl-N-allylamine, or 2- (dimethylamino) ethyl acrylate, and mixtures thereof. In another preferred embodiment, the surface active agent is of the formula: where ni = 2-18. The present invention further utilizes the surface active agents of the formula: (Ri) n-Ar-0 (CH2CH (R ') O) mS03"M + wherein Ri is a saturated or unsaturated hydrocarbon group having from about 6 to 24 carbon atoms; wherein Ar is a phenyl, polyphenyl, naphthyl, polynaphthyl, styryl, or polystyryl group, and mixtures thereof; wherein Rr is methyl or hydrogen; M + is a conjugate acid of the nitrogenous base; where n = 1-4; wherein the total number of carbon atoms represented by (R?) n is at least 5; and where m = 0-100. In a preferred embodiment, Ri is a saturated or unsaturated hydrocarbon group having from about 6 to 24 carbon atoms, Ar is phenyl; M + is a conjugate acid of the nitrogenous base, the nitrogenous base is selected from the group consisting of allylamine, diallylamine, triallylamine, methallylamine, N-methyl-N-allylamine or 2- (dimethylamino) ethyl acrylate, and mixtures thereof , n = 1, and m = 0-100. In another preferred embodiment, the surface active agent is of the formula: where ni = 5-18; and where n2 = 0-20. The present invention further utilizes the surface active agents of the formula: RiO (CH2CH (R ') O) nS03"M + wherein Ri is a saturated or unsaturated hydrocarbon group having from about 1 to 24 carbon atoms; wherein R 'is methyl or hydrogen; where n = 0 to 100; and where M + is a conjugate acid of the nitrogenous base. ' In a preferred embodiment, Ri is a saturated or unsaturated hydrocarbon group having from about 6 to 24 carbon atoms, R 'is methyl or hydrogen, n = 0 to 100, and M + is a conjugate acid of the nitrogenous base, the base Nitrogen is selected from the group consisting of allylamine, diallylamine, triallylamine, methallylamine, N-methyl-N-allylamine or 2- (dimethylamino) ethyl acrylate, and mixtures thereof. In another preferred embodiment, the surface active agent is of the formula: where ni = 5-18. In another preferred embodiment, the surface active agent is of the formula: where ni = 5-18; and where n = 1-20. The present invention further utilizes the surface active agents of the formula: R? C02 ~ M + wherein Ri is a saturated or unsaturated hydrocarbon group having from 4 to 24 carbon atoms; and where M + is a conjugate acid of the nitrogenous base. In a preferred embodiment, Ri is a saturated or unsaturated hydrocarbon group having from about 6 to 24 carbon atoms, and M + is a conjugate acid of the nitrogenous base, the nitrogenous base is selected from the group consisting of allylamine, diallylamine, triallylamine , metalylamine, N-methyl-N-allylamine or 2- (dimethylamino) ethyl acrylate, and mixtures thereof. In another preferred embodiment, the surface active agent is of the formula: CH3 (CH2) nC02 ~ + NH3 where n = 5-18. The present invention further utilizes the surface active agents of the formula: R? C0N (R ') (CH2) nC02"M wherein Ri is a saturated or unsaturated hydrocarbon group having from about 1 to 24 carbon atoms, wherein R' is methyl, ethyl, propyl or hydrogen, wherein M + is a conjugate acid of the nitrogenous base, and wherein n = 1-10 In a preferred embodiment, M + is a conjugate acid of the nitrogenous base, the nitrogenous base is selected from the group consisting of allylamine, diallylamine, triallylamine, methallylamine , N-methyl-N-allylamine or 2- (dimethylamino) ethyl acrylate, and mixtures thereof, R 'is methyl, ethyl, propyl or hydrogen, and n = 2-5. In another preferred embodiment, the active agent of Surface is of the formula: where ni = 2-18. The present invention further utilizes the surface active agents of the formula: R? C0N (R ') (CH2) nS03M + wherein Ri is a saturated or unsaturated hydrocarbon group having from about 1 to 24 carbon atoms; wherein Rr is methyl, ethyl, propyl or hydrogen; wherein M + is a conjugate acid of the nitrogenous base; and where n = 1-10. In a preferred embodiment, M + is a conjugate of the nitrogenous base acid, the nitrogenous base is selected from the group consisting of allylamine, diallylamine, triallylamine, methallylamine, N-methyl-N-allylamine or methacrylate, 2- (dimethylamino) ethyl and mixtures thereof, R 'is methyl, ethyl, propyl or hydrogen, and n = 2-5. In another preferred embodiment, the surface active agent is of the formula: where ni = 2-18. The present invention further utilizes the surface active agents of the formula: Ri O (CH2CH (R ') 0) nC0CH2S 03"M + wherein Ri is a saturated or unsaturated hydrocarbon group having from about 1 to 24 carbon atoms, wherein R' is methyl or hydrogen, wherein n = 0 to 100, wherein M + is a conjugate acid of the nitrogenous base In a preferred embodiment, Ri is a saturated or unsaturated hydrocarbon group having from about 6 to 24 carbon atoms, R 'is methyl or hydrogen, M + is a conjugated acid the nitrogenous base, the nitrogenous base is selected from the group consisting of allylamine, diallylamine, triallylamine, methallylamine, N-methyl-N-allylamine acrylate or 2- (dimethylamino) ethyl, and mixtures thereof; n = 0- 100. In another embodiment, the surface active agent is of the formula: where ni = 5-17; and where n = 0-20. The present invention further utilizes the surface active agents of the formula: RiO (P03) x "M + y wherein Ri is a saturated or unsaturated hydrocarbon group having from about 1 to 24 carbon atoms, a phenyl, polyphenyl, naphthyl, polynaphthyl, styryl or polystyryl group, a phenyl substituted with alkyl / alkoxylate, a polyphenyl substituted or polysubstituted with alkyl / alkoxylate, a substituted or polysubstituted naphthyl with alkyl / alkoxylate, a substituted or polysubstituted polysubstituted with alkyl / alkoxylate, a styryl substituted or polysubstituted with alkyl / alkoxylate, or a polystyreyl substituted or polysubstituted group with alkyl / alkoxylate, and mixtures thereof, wherein M + is a conjugate acid of the nitrogenous base, wherein x = 1 or 2, and wherein y = 1 or 2. The present invention furthermore uses the surface active agents of the formula: [R? O (CH2CH (R ') 0) m] nP (0) pX ~ M + y wherein Ri is a saturated or unsaturated hydrocarbon group having from about 1 to 24 carbon atoms; wherein R 'is methyl or hydrogen; wherein M is a conjugate acid of the nitrogenous base, the nitrogenous base is selected from the group consisting of allylamine, diallylamine, triallylamine, methallylamine, N-methyl-N-allylamine, or 2- (dimethylamino) ethyl acrylate, and mixtures thereof thereof; m = 0-100; where n = 1 or 2; where p = 2 or 3; where x = 1 or 2; and wherein y = 1 or 2. The present invention further utilizes the surface active agents of the formula: [(Ri) nArO (CH2CH (R ') 0) m] qP (O) px ~ M + y wherein Ri is a saturated or unsaturated hydrocarbon group having from about 1 to 24 carbon atoms; wherein Ar is phenyl; wherein R 'is methyl or hydrogen; wherein M + is a conjugate acid of the nitrogenous base, the nitrogenous base is selected from the group consisting of allylamine, diallylamine, triallylamine, methallylamine, N-methyl-N-allylamine or, 2- (dimethylamino) ethyl acrylate, and mixtures thereof; where n = 1-4; where m = 0-100; where q = 1 or 2; where p = 2 or 3; where x = 1 or 2; and wherein y = 1 or 2. The present invention also encompasses polymerizable surface active agents which are ammonium salts of the general formula: wherein Ri, R2, R3 and R4 are independently substituted or unsubstituted hydrocarbon groups of about 1 to about 30 carbon atoms, or hydrocarbyl groups having from about 1 to about 30 carbon atoms and containing one or more aromatic portions , ether, ester, amido, or amino, present as substituents or as linkages in the radical chain, wherein at least one of the R? ~ R4 groups contains at least one or more ethenylene groups; and wherein X "is an anionic group selected from the group consisting of sulfonate, sulfate, sulfinate, sulfenate, phosphate, carboxylate, nitrate, and acetate.The polymerizable surface active agents of the present invention include those of the general formula above in the form of annular structures formed by the covalent bonding of two of the groups Ri and R4 Examples include imidazolines, imidazoliniums and unsaturated pyridines, and the like.

All documents, for example patents and journal articles cited above or below, are incorporated by reference herein in their entirety. In the following examples, all quantities are stated as a percentage by weight of the active material, unless otherwise indicated. One of skill in the art will recognize that modifications can be made to the present invention without deviating from the spirit or scope of the invention. The invention is further illustrated by the following examples, which should not be considered as limiting the invention or the scope of the specific methods or compositions described herein. As it is used in the examples that appear later, the following designations, symbols, terms and abbreviations have the meanings indicated: Material Definition Polystep® A-13 Linear dodecylbenzenesulfonic acid (commercially available from Stepan Company, Northfield Illinois) Polystep® A-16 Branched census sodium dodecylbenic acid salt (commercially available from Stepan Company, Northfield Illinois) Polystep® A-17 Acid branched dodecylbenzenesulfonic acid (commercially available from Stepan Company, Northfield Illinois) Cedephos CP-610 Nonylphenolic ester 9-EO phosphoric acid (commercially available from Stepan Company, Northfield Illinois) Procedures Due to their amphiphilic character, surfactants have a tendency to adsorb in various liquid-liquid and liquid-air interfaces, which leads to a reduction in surface or interfacial tension. After saturation of an interface, these active surface molecules begin to aggregate in the solution to form micelles at a specific surfactant concentration, known as the critical micelle concentration (CMC). The adsorption characteristics and the icing behavior of the surfactants are responsible for the technologically important properties of the surfactants, such as wetting, solubilization, emulsification and the like. Thus, the efficiency of any surface active agent refers to its ability to decrease interfacial tension, form micelles, and show favorable adsorption characteristics by providing efficient packing of active surface molecules at the interface in a very small concentration . The following test procedures were used to evaluate the ethylenically unsaturated amine salts of the present invention. A fully automated Kruss K-12 tensometer was used to measure the adsorption and micellar behavior of the polymerizable surface active agents. All measurements were made at room temperature, and distilled water was used for CMC measurements. All NMR - "- H spectra were recorded using the 270 MHz Joel Delta NMR Fourier Transform Spectrometer. The chemical shifts (d) are reported in parts per million (ppm) of low field from tetramethylsilane (TMS). ) using internal TMS or residual non-deuterated solvent as a reference.The multiplicity is indicated by the following abbreviations: singlet (s), doublet (d), triplet (t), quarteret (q), heptet (h), multiplet (m) ), broad multiplet (br m), doublet of doublets (dd), etc. All the samples were isolated in solid form by drying in an aqueous solution in vacuo of the surface active agents to eliminate substantially all the water in the sample; NMR data for all samples were acquired by dissolving the solid sample in CD30D.

Example 1 Approximately 7.5 ml of allylamine and approximately 150.0 g of deionized water were charged to a reaction vessel equipped with a means for agitation and a means for cooling. The temperature of the allylamine / water mixture was adjusted to approximately 25 ° C and approximately 32.5 g of Polystep A-13 was added to give the desired ethylenically unsaturated amine salt as an approximately 20% active aqueous solution, with a pH * of about 6.5. The pH of the resulting saline solution can be adjusted as necessary with the addition of more acid or amine; materials of higher and lower pH can be produced as desired. 1H-NMR: d 7.8 (m 2 H), 7.2 (m, 2H), 6.0 (m, 1H), 5.4 (ddt, 2H), 5.0 (broad, 3H), 3.6 (m, 2H), 1.7 (broad m, 3H), 1.3 (broad, 16H), 0.9 (m, 6H). The CMC, the Surface Tension Reduction and the Effectiveness of the Surfactant are reported in Table I.

Example 2 Approximately 7.5 ml of allylamine and approximately 150.0 g of deionized water were charged to a reaction vessel equipped with a means for agitation and a means for cooling. The temperature of the allyla / water mixture was adjusted to approximately 25 ° C and approximately 32.5 g of Polystep® A-17 was added to give the desired ethylenically unsaturated amine salt as an active aqueous solution at approximately 20% , with a pH of approximately 7.0. The pH of the resulting saline solution can be adjusted as necessary with the addition of more acid or amine; materials of higher and lower pH can be produced as desired. 1H-NMR: d 7.8 (m 2 H), 7.4 (broad t, 2H), 5.9 (ddt, 1H), 5.4 (m, 2H), 4.9 (broad, 3H), 3.5 (dd, 2H), 2.9 (m, 1H), 1.6 (m, 3H), 0.9-1.1 (m, 28H).

Example 3 Approximately 12.3 ml of allylamine and approximately 170.0 g of deionized water were charged to a reaction vessel equipped with a means for agitation and a means for cooling. The temperature of the allylamine / water mixture was adjusted to approximately 25 ° C and approximately 32.5 g of Polystep A-13 was added to give the desired ethylenically unsaturated amine salt as an approximately 20% active aqueous solution, with a pH of about 7.0. The pH of the resulting saline solution can be adjusted as necessary with the addition of more acid or amine; materials of higher and lower pH can be produced as desired. 1 H NMR: d 7.8 (m 2 H), 7.2 (m, 2 H), 6.0 (m, 2 H), 5.4 (m, 4 H), 5.0 (broad, 2 H), 3.6 (m, 4 H), 1.7 (broad m, 4H), 1.3 (broad, 15H), 0.9 (broad m, 6H).

Example 4 Approximately 12.3 ml of allylamine and approximately 170.0 g of deionized water were charged to a reaction vessel equipped with a means for agitation and a means for cooling. The temperature of the allylamine / water mixture was adjusted to approximately 25 ° C and approximately 32.5 g of Polystep® A-17 were added to give the desired ethylenically unsaturated amine salt as an approximately 20% active aqueous solution, with a pH of about 7.0. The pH of the resulting saline solution can be adjusted as necessary with the addition of more acid or amine; materials of higher and lower pH can be produced as desired. 1 H NMR: d 7.8 (m 2 H), 7.5 (m, 2 H), 5.9 (m, 2 H), 5.4 (, 4 H), 4.9 (broad s, 2 H), 3.6 (m, 4 H), 2.8 (m, 1 H) ), 1.7 (broad m, 3H), 0.9-1.1 (m, 28H).

Example 5 (Comparative Example) Approximately 13.7 ml of propylamine and about 170.0 g of deionized water were charged to a reaction vessel equipped with a means for agitation and a means for cooling. The temperature of the propylamine / water mixture was adjusted to approximately 25 ° C and approximately 32.5 g of Polystep® A-13 were added to give the saturated amine salt as an approximately 20% active aqueous solution with a pH of approximately 7.0. The pH of the resulting saline solution can be adjusted as necessary with the addition of more acid or amine; materials of higher and lower pH can be produced as desired. 1H-NMR: d 7.8 (dd, 2H) 7.23 (t, 2H), 4.9 (broad, 2H), 2.85 (t, 2H), 1.6 (m, 6H), 1.2 (m, 14H), 0.9 (, 6H) . The CMC, the Surface Tension Reduction and the Effectiveness of the Surfactant are reported in Table I.

Example 6 Approximately 30.0 ml of allylamine and approximately 408.0 g of deionized water were charged to a reaction vessel equipped with a means for agitation and a means for cooling. The temperature of the allylamine / water mixture was adjusted to approximately 25 ° C and approximately 80.0 g of lauric acid was added to give the desired ethylenically unsaturated amine salt as an approximately 20% active aqueous solution with a pH of approximately 7.0. (The carboxylic acid can be a solid at room temperature and can be pre-melted before addition to the amine / water mixture for ease of handling.) As an alternative, the carboxylic acid and water can be combined and heated to produce a uniform mixture, for example at 50-60 ° C for the lauric acid, followed by the addition of the unsaturated amine). The pH of the resulting saline solution can be adjusted as necessary with the addition of more acid or amine; materials of higher and lower pH can be produced as desired. 1H-NMR: 6.0 (m 1 H), 5.5 (ddt, 2H), 3.6 (, 2H), 2.3 (t, 2H), 1.6 (broad, 2H), 1.42 (s, 5H, residual water), 1.41 (s) , 3H), 1.4 (broad, 18H), 0.9 (t, 3H).

Example 7 (Comparative Example) Approximately 16.4 ml of propylamine and approximately 210.0 g of deionized water were charged to a reaction vessel equipped with a means for agitation and a means for cooling. The temperature of the propylamine / water mixture was adjusted to approximately 25 ° C and approximately 40.0 g of lauric acid were added., to give the saturated amine salt, as an active aqueous solution at approximately 20%, with a pH of about 7.0. (The carboxylic acid can be a solid at room temperature and can be pre-melted before addition to the amine / water mixture for ease of handling.) As an alternative, the carboxylic acid and water can be combined and heated to produce a uniform mixture, for example at 50-60 ° C for lauric acid, followed by the addition of the saturated amine). The pH of the resulting saline solution can be adjusted as necessary with the addition of more acid or amine; materials of higher and lower pH can be produced as desired. 1H-NMR: d 5.0 (s, 3H), 3.3 (p, 2H), 2.8 (dt, 2H), 2.25 (t, 2H), 1.6 (m, 2H), 1.3 (m, 17H), 1.0 (t, 3H), 0.9 (t, 3H).

Example 8 Approximately 5.1 ml of allylamine and approximately 320.0 g of deionized water were charged to a reaction vessel equipped with a means for agitation and a means for cooling. The temperature of the allylamine / water mixture was adjusted to approximately 25 ° C and approximately 75.0 g of Cedephos CP-610 was added, to give the desired unsaturated amine salt, as an approximately 20% active aqueous solution, with a pH of about 7.0. (The phosphoric acid ester can be a solid at room temperature and can be pre-melted before addition to the amine / water mixture for ease of handling.As an alternative, the phosphoric acid ester and water can be combined and heated to produce a uniform mixture, followed by the addition of the unsaturated amine). The pH of the resulting saline solution can be adjusted as necessary with the addition of more acid or amine; materials of higher and lower pH can be produced as desired. 1 H NMR: 7.2 (m 2 H), 6.8 (m, 2 H), 6.0 (m, 1 H), 5.4 (m, 2H), 4.1 (m, 2H), 3.8 (m, 2H), 3.6 (m, 32H), 0.4-1.8 (m, 19H). The CMC, the Surface Tension Reduction and the Effectiveness of the Surfactant are reported in Table I.

Example 9 (Comparative Example) Approximately 5.1 ml of propylamine and approximately 320.0 g of deionized water were charged to a reaction vessel equipped with a means for agitation and a means for cooling. The temperature of the propylamine / water mixture was adjusted to approximately 25 ° C and approximately 75.0 g of Cedephos CP-610 was added, to give the desired saturated amine salt, as an active aqueous solution approximately 20%, with a pH of about 7.0. (The phosphoric acid ester can be a solid at room temperature and can be pre-melted before addition to the amine / water mixture for ease of handling.As an alternative, the phosphoric acid ester and water can be combined and heated to produce a uniform mixture, followed by the addition of the unsaturated amine). The pH of the resulting saline solution can be adjusted as necessary with the addition of more acid or amine; materials of higher and lower pH can be produced as desired.

XH NMR: d 7.2 (m 2 H), 6.8 (m, 2 H), 4.9 (s, 3 H), 4.1 (m, 2H), 3.8 (, 2H), 3.6 (m, 32H), 3.3 (t, 2H), 2.9 (dt, 2H), 0.4-1.8 (m, 22H). The CMC, the Reduction of Surface Tension and the Effectiveness of Surfactant are reported in Table I.

Table I: Surface Tension Data for 1 as Salts of Amine I: nsaturated from Acid Esters < you Sulphonic acids, carboxylic acids, and phoric acids, Including the Comparative Axis plos Effectiveness of the Reduction of the Amine Salt Tension Ethylically Unsaturated Superficial to Surface Tension Example # CMC (mg / l) CMC (mN / m) CMC (mN / m) 1 Allylamine Salt of Acid 100.5 33.2 39.1 Dodecylbenzenesulfonic 5 * Propylamine Salt of 480.5 31.0 41.3 Dodecylbenzenesulfonic Acid Polystep® Sodium Salt of Acid 156.0 35.0 37.3 A- 16 Dodecylbenzenesulfonic 8 Ester Allylamine Salt 31.8 30.0 42.3 Nonylphenolic 9-EO from Phosphoric Acid 9 * Propylamine Salt from 74 31.5 40.8 Nonylphenolic Ester 9-EO from Phosphoric Acid * comparative example Example 10: Emulsion Polymerization with the Allylamine Salt Polystep A-17 A pot of emulsion polymerization equipped with a nitrogen inlet, a heating medium, and a stirring medium is charged with 250 g of water and 8.13 g of the alysteine salt Polystep A-17. The mixture is heated to approximately 85 ° C. Approximately 17 g of a 4% aqueous solution of ammonium persulfate (e.g., starter solution) are added and about 75 g of monomer solution are added while mixing, the monomer solution comprising 48% butyl acrylate, 49 % methyl methacrylate and 3% methacrylic acid. After mixing for 15 minutes, 298 g of the monomer solution is added over a period of 2.5 hours. After the addition of the monomer solution has begun for 30 minutes, 67 g of initiator solution (described above) and 75 g of the alysteine salt Polystep A-17 in 35 g of water are separately and concurrently added in one period. of 2 hours. The resulting mixture is stirred at 85 ° C for a further hour, cooled, the pH adjusted with dilute NhyOH, followed by reactor discharge to give an all-acrylic latex with the following properties: Viscosity: 50 centipoise; pH: 6.4; Solids: 45.6 (effective), 46.7 (theoretical); Particle Size: 115 Example 11 A copolymer of methyl methacrylate / butyl acrylate / methacrylic acid (MMA / BA / MMA) (in a weight ratio of about 48: 49: 3), in combination with the allylamine salt of laureth-3EO is prepared as follows. -sulfate (AES-3). Approximately 205 g of deionized water and approximately 1.6 g of AAES (as a 25.5% active aqueous solution) are placed in a reactor suitable for emulsion polymerization, equipped with stirring means, heating means and cooling means. With stirring, the reactor is purged with nitrogen (99% pure), and heated to approximately 77-79 ° C. Next, 75 g of the monomer mixture is added to the reactor (20% of a total of 376 g of the monomeric mixture MMA / BA / MMA in the above proportion). After 10 minutes, 15.0 g of an ammonium persulfate solution (20% of the total solution of 1.9 g of ammonium persulfate dissolved in 72.9 g of water) are added to the reactor over a period of about 4 minutes with continuous stirring, time during which there is an exotherm of approximately 12-14 ° C. After the exotherm is complete, about 301 g of the monomer mixture (the remaining 80% of the monomeric mixture MMA / BA / MMA), 59.8 g of water are charged to the reactor over a period of 2 hours with continuous stirring. the ammonium persulfate solution (the remaining 80%), and 22.0 g of AAES-3 (as the 22% active aqueous solution) while maintaining the reactor contents at a temperature of about 78-82 ° C. The temperature of the reactor is then raised to about 82-84 ° C with continuous stirring, for about 15 minutes. After this 15 minute period, the reactor is cooled to approximately 30 ° C. The resulting latex product is completely removed from the reactor and filtered by gravity using a first 420 mesh screen and then a second 250 mesh screen. The total latex clot (eg solids) from both meshes is collected, combined and weigh yourself. The resulting latex has the following characteristics: Example 12 A copolymer of methyl methacrylate / butyl acrylate / methacrylic acid (MMA / BA / MMA) (in a weight ratio of about 48: 49: 3), in combination with the salt of lauryl sulfate (AS) is prepared as follows ). about 222 g of deionized water and about 2.3 g of AS (as an active aqueous solution at 17.2%), are placed in a reactor suitable for emulsion polymerization, equipped with stirring means, heating means and cooling means. With stirring, the reactor is purged with nitrogen (99% pure), and heated to approximately 77-79 ° C. Then, 77 g of the monomer mixture is added to the reactor (20% of a total of 378 g of the monomeric mixture MMA / BA / MMA in the above proportion). After 10 minutes, 15.4 g of an ammonium persulfate solution (20% of the total solution of 1.9 g of ammonium persulfate dissolved in 75.0 g of water) are added to the reactor over a period of about 4 minutes with continuous stirring, time during which there is an exotherm of approximately 7-8 ° C. After the exotherm is complete, about 301 g of the monomer mixture (the remaining 80% of the monomeric mixture MMA / BA / MMA), 61.6 g of the mixture are charged to the reactor over a period of 2 hours with continuous stirring. ammonium persulfate solution (the remaining 80%), and 33.7 g of AS (as the active aqueous solution at 17.2%) while maintaining the reactor content at a temperature of about 78-82 ° C. The temperature of the reactor is then raised to about 82-84 ° C with continuous stirring, for about 15 minutes. After this 15 minute period, the reactor is cooled to approximately 30 ° C. The resulting latex product is completely removed from the reactor and filtered by gravity using a first 420 mesh screen and then a second 250 mesh screen. The total latex clot (eg solids) from both meshes is collected, combined and weigh yourself. The resulting latex has the following characteristics: From the foregoing, it will be appreciated that although the specific embodiments of the invention have been described herein for purposes of illustration, various embodiments may be made without deviating from the spirit or scope of the invention.

It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Claims

CLAIMS Having described the invention as above, the content of the following claims is claimed as property:

1. polymerizable surface active agent characterized in that it comprises: a) at least one acid, wherein the acid is a sulfonic acid, an ester of sulfuric acid, a carboxylic acid, or a phosphoric acid, or a mixture thereof; and b) at least one nitrogenous base, wherein the nitrogenous base contains at least one nitrogen atom and at least one ethylenically unsaturated portion; wherein the polymerizable surface active agent is an amine salt.

2. A polymerizable surface active agent according to claim 1, characterized in that it comprises: a) at least one acid, wherein the sulphonic acid is an α-sulfonated alkyl ester acid, an α-sulfonated ester diacid, or a mixture thereof, and the sulfuric acid ester is an alkoxylated alkylsulfuric acid ester, an alkoxylated alkylarylsulfuric acid ester; or a mixture thereof; and b) at least one nitrogenous base, wherein the nitrogenous base contains at least one nitrogen atom and at least one ethylenically unsaturated portion; wherein the polymerizable surface active agent is an amine salt.

3. A polymerizable surface active agent according to claim 2, characterized in the sulfonic acid is a polysulfonic acid, a sulfonic acid of an oil, a sulphonic acid of paraffin, a sulfonic acid of lignin, a sulfonic acid of petroleum, a sulfonic acid of olefin, a polyolefin sulfonic acid, a polyolefin polysulfonic acid or a mixture thereof, the carboxylic acid is a polycarboxylic acid, and the phosphoric acid is a polyphosphoric acid, a phosphinic acid, or a polyphosphinic acid, or a mixture thereof.

4. A polymerizable surface active agent according to claim 2, characterized in that the nitrogenous base is allylamine, diallylamine, triallylamine, methallylamine, N-methyl-N-allylamine, N-allyl-N, N-dimethylamine, methyl 3-aminocrotonate. , 3-aminocrotononitrile, 3-amino-1-propanol vinyl ether, 2- (dimethylamino) ethyl acrylate, or 1,4-diamino-2-b'utene or a mixture thereof.

5. A polymerizable surface active agent according to claim 4, characterized in that the nitrogenous base is allylamine, diallylamine, triallylamine, methallylamine, N-methyl-N-allylamine, or 2- (dimethylamino) ethyl acrylate or a mixture thereof .

6. A polymerizable surface active agent according to claim 2, characterized in that it is of the formula: (R?) N-Ar (S03"M +) wherein Ri is a saturated or unsaturated hydrocarbon group having from about 1 to 24 carbon atoms; wherein Ar is a phenyl, polyphenyl, naphthyl, polinaphthyl, styryl, or polystyryl group, or a mixture thereof; wherein M + is a conjugate acid of the nitrogenous base; where n represents an integer from 1 to 5 and m represents an integer from 1 to 8; and wherein the total number of carbon atoms represented by (R?) n is at least 5.

7. A polymerizable surface active agent according to claim 6, characterized in that Ri is a saturated or unsaturated hydrocarbon group having from about 6 to 24 carbon atoms; wherein where Ar is a phenyl group; wherein the nitrogenous base is selected from the group consisting of allylamine, diallylamine, triallylamine, methallylamine, N-methyl-N-allylamine, or 2- (dimethylamino) ethyl acrylate or a mixture thereof; and where n is 1 and m is 1.

8. A polymerizable surface active agent according to claim 7, characterized in that it is of the formula: where neither represents an integer from 4 to 18; and wherein R 'is hydrogen or a saturated or unsaturated hydrocarbon group having from about 1 to 8 carbon atoms.

9. A polymerizable surface active agent according to claim 2, characterized in that it is of the formula: RiCH (S03"M +) C02R2 wherein Ri and R2 are independently saturated or unsaturated hydrocarbon groups having from about 1 to 24 carbon atoms; and where M + is a conjugate acid of the nitrogenous base.

10. A polymerizable surface active agent according to claim 9, characterized in that Rx is a saturated or unsaturated hydrocarbon group having from about 6 to 24 carbon atoms; wherein R2 is methyl, ethyl, or propyl, or a mixture thereof; and wherein the nitrogenous base is selected from the group consisting of allylamine, diallylamine, triallylamine, methallylamine, N-methyl-N-allylamine, or 2- (dimethylamino) ethyl acrylate or a mixture thereof and mixtures thereof .

11. A polymerizable surface active agent according to claim 10, characterized in that it is of the formula: where n represents an integer from 3 to 18.

12. A polymerizable surface active agent according to claim 2, characterized in that it is of the formula: Ri-CH (S03"M +) C02M wherein Ri is a saturated or unsaturated hydrocarbon group having from about 3 to 24 carbon atoms, and wherein M + is a conjugate acid of the nitrogenous base.

13. A polymerizable surface active agent according to claim 11, characterized in that Ri is a saturated or unsaturated hydrocarbon group having from about 6 to 24 carbon atoms; and wherein the nitrogenous base is selected from the group consisting of allylamine, diallylamine, triallylamine, methallylamine, N-methyl-N-allylamine, or 2- (dimethylamino) ethyl acrylate or a mixture thereof.

14. A polymerizable surface active agent according to claim 13, characterized in that it is of the formula: where n represents an integer from 3 to 18.

15. A polymerizable surface active agent according to claim 2, characterized in that it is of the formula: Ri- (S03 ~ M +) wherein Ri is a saturated or unsaturated hydrocarbon group having from about 6 to 24 carbon atoms; and where M + is a conjugate acid of the nitrogenous base.

16. A polymerizable surface active agent according to the claim 15, characterized in that Ri is a saturated or unsaturated hydrocarbon group having from about 6 to 24 carbon atoms; and wherein the nitrogenous base is selected from the group consisting of allylamine, diallylamine, triallylamine, methallylamine, N-methyl-N-allylamine, or 2- (dimethylamino) ethyl acrylate or a mixture thereof.

17. A polymerizable surface active agent according to claim 16, characterized in that it is of the formula: CH3 (CH2) nS03 ~ H3 + N where n represents an integer from 5 to 17.

18. A polymerizable surface active agent according to claim 2, characterized in that it is of the formula: (Ri) nAr-0 (CH2CH (R) 0) mS03"M- ' wherein Ri is a saturated or unsaturated hydrocarbon group having from about 1 to 24 carbon atoms; wherein wherein Ar is a phenyl, polyphenyl, naphthyl, polinaphthyl, styryl, or polystyryl group, and a mixture thereof; wherein R 'is methyl or hydrogen; wherein M + is a conjugate acid of the nitrogenous base; where n represents an integer from 1 to 4; wherein the total number of carbon atoms represented by (R?) n is at least 5; and where m is zero or an integer from 1 to 100.

19. A polymerizable surface active agent according to claim 18, characterized in that Rx is a saturated or unsaturated hydrocarbon group having from about 6 to 24 carbon atoms; wherein Ar is phenyl; wherein the nitrogenous base is selected from the group consisting of allylamine, diallylamine, triallylamine, methallylamine, N-methyl-N-allylamine, or 2- (dimethylamino) ethyl acrylate or a mixture thereof; where n is 1; and where m is zero or an integer from 1 to 100.

20. A polymerizable surface active agent according to claim 19, characterized in that it is of the formula: where neither represents an integer from 5 to 18; and where n2 represents an integer from 0 to 20.

21. A polymerizable surface active agent according to claim 2, characterized in that it is of the formula: RiO (CH2CH (R ') 0) nS03"M + wherein Ri is a saturated or unsaturated hydrocarbon group having from about 1 to 24 carbon atoms; wherein R 'is methyl or hydrogen; where n is zero or an integer from 1 to 100; and where M + is a conjugate acid of the nitrogenous base.

22. A polymerizable surface active agent according to the claim 21, characterized in that Ri is a saturated or unsaturated hydrocarbon group having from about 6 to 24 carbon atoms; wherein R 'is methyl or hydrogen; wherein n is zero or an integer from 1 to 100, and wherein the hydrogenated base is selected from the group consisting of allylamine, diallylamine, triallylamine, methallylamine, N-methyl-N-allylamine, or 2- (dimethylamino) acrylate ) ethyl or a mixture thereof.

23. A polymerizable surface active agent according to claim 22, characterized in that it is of the formula: CH3 (CH2) n? OS03"H3 + N- where neither represents an integer from 5 to 18.

24. A polymerizable surface active agent according to claim 23, characterized in that it is of the formula: where neither represents an integer from 5 to 18; and where n represents an integer from 1 to 20.

25. A polymerizable surface active agent according to claim 2, characterized in that it is of the formula: (R?) Ni-. { Ar (S03"M +) ml.}. -0- { Ar (S03 ~ M +) m2> - (R2) n? Where Ri and R2 are independently hydrogen, or the saturated or unsaturated hydrocarbon groups having about 1 to 24 carbon atoms, wherein wherein Ar is a phenyl, polyphenyl, naphthyl, polynaphthyl, styryl, or polystyryl group, wherein M + is a conjugate acid of the nitrogenous base, wherein ni and n2 are independently 0 to 5, with the proviso that ni and n2 are not both equal to zero, and where mi and m2 are independently 0 to 8, with the proviso that mi and m2 are not both equal to zero.

26. A polymerizable surface active agent according to claim 25, characterized in that Ri is hydrogen and R 2 is a saturated or unsaturated hydrocarbon group having from about 6 to 24 carbon atoms, wherein Ar is phenyl; wherein the nitrogenous base is selected from the group consisting of allylamine, diallylamine, triallylamine, methallylamine, N-methyl-N-allylamine, or 2- (dimethylamino) ethyl acrylate or a mixture thereof; where ni is 4 and n2 is 1; and where MI and m.2 are both equal to one.

27. A polymerizable surface active agent according to claim 25, characterized in that Ri and R2 are independently saturated or unsaturated hydrocarbon groups having from about 6 to 24 carbon atoms, wherein Ar is phenyl, wherein the nitrogenous base is selected of the group consisting of allylamine, diallylamine, triallylamine, methallylamine, N-methyl-N-allylamine, or 2- (dimethylamino) ethyl acrylate or a mixture thereof; where ni and n2 are both equal to one; and where my and m2 are both equal to one.

28. A polymerizable surface active agent according to claim 27, characterized in that it is of the formula: wherein n and n 'are independently 4-18; and wherein R 'and R "are independently hydrogen, methyl, ethyl or propyl.

29. A polymerizable surface active agent according to claim 2, characterized in that it is of the formula. R? -CH (S03"M +) C (0) 0 (CH2CH (R ') 0) nR2 wherein Ri and R2 are independently saturated or unsaturated hydrocarbon groups having from about 1 to 24 carbon atoms; wherein R 'is methyl or hydrogen; wherein n represents an integer from 1 to 100; and where M + is a conjugate acid of the nitrogenous base.

30. A polymerizable surface active agent according to claim 29, characterized in that Ri is a saturated or unsaturated hydrocarbon group having from about 4 to 24 carbon atoms; R 'is methyl or hydrogen; R 2 is methyl, ethyl or propyl, and mixtures thereof; the nitrogenous base is selected from the group consisting of allylamine, diallylamine, triallylamine, methallylamine, N-methyl-N-allylamine, or 2- (dimethylamino) ethyl acrylate or a mixture thereof; and where n represents an integer from 1 to 100.

31. A polymerizable surface active agent according to claim 30, characterized in that it is of the formula: S ° 3 'H3 + N' where neither represents an integer from 2 to 18; .and where n2 represents an integer from 1 to 20.

32. A polymerizable surface active agent according to claim 2, characterized in that it is of the formula: R? C02 (CH2) nCH (S03 ~ M +) CO2R2 wherein Ri and R2 are saturated or unsaturated hydrocarbon groups having from about 1 to 24 carbon atoms; where n is zero or an integer from 1 to 10; and where M + is a conjugate acid of the nitrogenous base.

33. A polymerizable surface active agent according to claim 32, characterized in that Ri and R2 are saturated or unsaturated hydrocarbon groups having from about 1 to 24 carbon atoms; wherein n represents an integer from 1 to 6, and wherein the nitrogenous base is selected from the group consisting of allylamine, diallylamine, triallylamine, methallylamine, N-methyl-N-allylamine, or 2- (dimethylamino) ethyl acrylate or a mixture of them.

34. A polymerizable surface active agent according to claim 32, characterized in that it is of the formula: where ni e s zero or an integer from 1 to 1 7 35. A polymerizable surface active agent according to claim 2, characterized in that it is of the formula:

R? C02 (CH2) nS03"M + wherein Ri is a saturated or unsaturated hydrocarbon group having from about 1 to 24 carbon atoms; wherein n represents an integer from l to 10; and where M + is a conjugate acid of the nitrogenous base.

36. A polymerizable surface active agent according to claim 35, characterized in that Ri is a saturated or unsaturated hydrocarbon group having from about 6 to 24 carbon atoms; where n is an integer from 1 to 5; and wherein the nitrogenous base is selected from the group consisting of allylamine, diallylamine, triallylamine, methallylamine, N-methyl-N-allylamine, or 2- (dimethylamino) ethyl acrylate or a mixture thereof.

37 An active polyfunctional surface agent according to claim 36, characterized in that it is of the formula: where neither is an integer from 2 to 18

38. A polymerizable surface active agent according to claim 1, characterized in that it is of the formula: R? C02"M + wherein Ri is a saturated or unsaturated hydrocarbon group having from about 4 to 24 carbon atoms; and where M + is a conjugate acid of the nitrogenous base.

39. A polymerizable surface active agent according to claim 38, characterized in that Ri is a saturated or unsaturated hydrocarbon group having from about 6 to 24 carbon atoms; and wherein the nitrogenous base is selected from the group consisting of allylamine, diallylamine, triallylamine, methallylamine, N-methyl-N-allylamine, or 2- (dimethylamino) ethyl acrylate and mixtures thereof.

40. A polymerizable surface active agent according to claim 39, characterized in that it is of the formula: CH3 (CH2) nC02"H3 + N ' where n is an integer from 5 to 18.

41. A polymerizable surface active agent according to claim 1, characterized in that it is of the formula: R? CON (R ') (CH2) nC02"M wherein Ri is a saturated or unsaturated hydrocarbon group having from about 1 to 24 carbon atoms; wherein R 'is methyl, ethyl, propyl or hydrogen; wherein M + is a conjugate acid of the nitrogenous base; and where n is an integer from 1 to 10.

42. An active polymerizable surface agent according to claim 41, characterized in that the nitrogenous base is selected from the group consisting of allylamine, diallylamine, triallylamine, methallylamine, N-methyl-N-allylamine, or 2- (dimethylamino) acrylate. ethyl and mixtures thereof; wherein R 'is methyl, ethyl, propyl, or hydrogen; and where n is an integer from 2 to 5.

43. A polymerizable surface active agent according to claim 42, characterized in that it is of the formula: wherein ni is an integer from 2 to 1 44. A polymerizable surface active agent according to claim 2, characterized in that it is of the formula:

R? CON (R ') (CHainSOsM wherein i is a saturated or unsaturated hydrocarbon group having from about 1 to 24 carbon atoms; wherein R 'is methyl, ethyl, propyl or hydrogen; wherein M + is a conjugate acid of the nitrogenous base; and where n is an integer from 1 to 10.

45. A polymerizable surface active agent according to claim 44, characterized in that the nitrogenous base is selected from the group consisting of allylamine, diallylamine, triallylamine, methallylamine, N-methyl-N-allylamine, or 2- (dimethylamino) ethyl acrylate. and mixtures thereof, wherein R 'is methyl, ethyl, propyl, or hydrogen; and where n is an integer from 2 to 5.

46. A polymerizable surface active agent according to claim 45, characterized in that it is of the formula: where neither is an integer from 2 to 18.

47. A polymerizable surface active agent according to claim 2, characterized in that it is of the formula: Ri O (CH2CH (R ') O) nCOCH2S 03' go wherein Ri is a saturated or unsaturated hydrocarbon group having from about 1 to 24 carbon atoms; wherein R 'is methyl, or hydrogen; where n is zero or an integer from 1 to 100; where M + is a conjugate acid of the nitrogenous base.

48. A polymerizable surface active agent according to claim 47, characterized in that Ri is a saturated or unsaturated hydrocarbon group having from about 6 to 24 carbon atoms; wherein R 'is methyl or hydrogen; wherein the nitrogenous base is selected from the group consisting of allylamine, diallylamine, triallylamine, methallylamine, N-methyl-N-allylamine, or 2- (dimethylamino) ethyl acrylate or a mixture thereof; and where n is zero or an integer from 1 to 100.

49. A polymerizable surface active agent according to the claim 48, characterized in that it is of the formula: where neither is an integer from 5 to 17; and where n is zero or an integer from 1 to 20.

50. A polymerizable surface active agent according to claim 1, characterized in that it is of the formula: RIO (PO3; M ^ where Ri is a saturated or unsaturated hydrocarbon group having from about 1 to 24 carbon atoms, or a phenyl, polyphenyl, naphthyl, polynaphthyl, styryl or polystyryl group, a phenyl group substituted with alkyl / alkoxylate, a substituted or polysubstituted polyphenyl group with alkyl / alkoxylate, a naphthyl group substituted or polysubstituted with alkyl / alkoxylate, a polinaphthyl group substituted or polysubstituted with alkyl / alkoxylate, a styryl group substituted or polysubstituted with alkyl / alkoxylate, or a polystyreyl group substituted or polysubstituted with alkyl / alkoxylate and mixtures thereof; wherein M + is a conjugate acid of the nitrogenous base; where x is l or 2 e and is l or 2.

51. A polymerizable surface active agent according to claim 1, characterized in that it is of the formula: [R? O (CH2CH (R ') 0) m] nP (0) px_ M + y wherein Ri is a saturated or unsaturated hydrocarbon group having from about 1 to 24 carbon atoms; wherein R 'is methyl or hydrogen; wherein the nitrogenous base is selected from the group consisting of allylamine, diallylamine, triallylamine, methallylamine, N-methyl-N-allylamine, or 2- (dimethylamino) ethyl acrylate and mixtures thereof; m is zero or an integer from 1 to 100; n is 1 or 2; p is 2 or 3; x is 1 or 2; e y is 1 6 2.

52. A polymerizable surface active agent according to claim 1, characterized in that it is of the formula: [(R?) NArO (CH2CH (R ') O) m] qP (O) px ~ M + y wherein Ri is a saturated or unsaturated hydrocarbon group having from about 1 to 24 carbon atoms; where Ar is phenyl; wherein R 'is methyl or hydrogen; wherein the nitrogenous base is selected from the group consisting of allylamine, diallylamine, triallylamine, methallylamine, N-methyl-N-allylamine, or 2- (dimethylamino) ethyl acrylate and mixtures thereof; where n is an integer from 1 to 4; where m is zero or an integer from 1 to 100, where q is 1 or 2; where p is 2 or 3; where x is 1 or 2; and where y is 1 or 2.

53. An aqueous surface active solution, characterized in that it comprises: a) a surface-active agent polymerizing: i) at least one acid, wherein the acid is a sulfonic acid, an ester of sulfuric acid, a carboxylic acid, or a phosphoric acid, or a mixture thereof; and ii) at least one nitrogenous base, wherein the nitrogenous base contains at least one nitrogen atom and at least one ethylenically unsaturated portion; wherein the polymerizable surface active agent is an amine salt; and b) water.

54. An aqueous surface active solution according to claim 53, characterized in that it comprises: a) a polymerizable surface active agent comprising: 1. at least one acid wherein the acid is a sulfonic acid, an ester of sulfuric acid , an alkoxylated alkylsulfuric acid ether, an α-sulfonated alkylester acid, an α-sulfonated ester diacid, alkoxylated alkylarylsulfuric acid esters or a mixture thereof; and 2. at least one nitrogenous base, wherein the nitrogenous base contains at least one nitrogen atom and at least one ethylenically unsaturated portion; wherein the polymerizable surface active agent is an amine salt; and b) water.

55. An aqueous surface active solution according to claim 53, characterized in that it comprises: a) a polymerizable surface active agent of the formula: (R?) NAr (S03_M +) m wherein Rx is a saturated or unsaturated hydrocarbon group having from about 1 to 24 carbon atoms; wherein Ar is a phenyl, polyphenyl, naphthyl, polynaphthyl, styryl, or polystyryl group or a mixture thereof; wherein M + is a conjugate acid of the nitrogenous base; where n is an integer from 1 to 5 and m is an integer from 1 to 8; and wherein the total number of carbon atoms represented by (R?) n is at least 5; and b) water

56. An aqueous surface active solution according to claim 53, characterized in that it comprises: a) a polymerizable surface active agent of the formula: (Ri) m-. { Ar (S03"M +) m ?.}. -0- { Ar (S03" M +) m2} - (R2) n2 wherein Ri and R2 are independently hydrogen or saturated unsaturated hydrocarbon groups having from about 1 to 24 carbon atoms; wherein Ar is a phenyl, polyphenyl, naphthyl, polynaphthyl, styryl, or polystyryl group; wherein M + is a conjugate acid of the nitrogenous base; where ni and n2 are independently 0 to 5, with the proviso that ni and n2 are not both equal to zero; and where mi and m2 are independently 0 to 8, with the proviso that mi and m2 are not both equal to zero; and b) water.

57. An aqueous surface active solution according to claim 53, characterized in that it comprises: a) a polymerizable surface active agent of the formula: R1-CH (S03 ~ M +) CO2R2 wherein Ri and R2 are independently saturated or unsaturated hydrocarbon groups having from about 1 to 24 carbon atoms; and wherein M + is a conjugate acid of the nitrogenous base; b) water.

58. An aqueous surface active solution according to claim 53, characterized in that it comprises: a) a polymerizable surface active agent of the formula: R? -CH (S03"M +) C02M + wherein Rx is a saturated or unsaturated hydrocarbon group having from about 3 to 24 carbon atoms; and wherein M + is a conjugate acid of the nitrogenous base; and b) water.

59. An aqueous surface active solution according to claim 53, characterized in that it comprises: a) a polymerizable surface active agent of the formula: Ri-CH (S03"M +) C (O) O (CH2CH (R ') 0) nR2 wherein Ri and R2 are independently saturated or unsaturated hydrocarbon groups having from about 1 to 24 carbon atoms; wherein R 'is methyl or hydrogen; wherein n is an integer from 1 to 100 and wherein M + is a conjugate acid of the nitrogenous base; and b) water.

60. An aqueous surface active solution according to claim 53, characterized in that it comprises: a) a polymerizable surface active agent of the formula: Ri- (S03"M +) wherein Ri is a saturated or unsaturated hydrocarbon group having from about 6 to 24 carbon atoms; and wherein where M + is a conjugate acid of the nitrogenous base; and b) water.

61. An aqueous surface active solution according to claim 53, characterized in that it comprises: a) a polymerizable surface active agent of the formula: R C02 (CH2) nCH (S03"M +) CO2R2 wherein Ri and R2 are independently saturated or unsaturated hydrocarbon groups having from about 1 to 24 carbon atoms, wherein n is zero or an integer from 1 to 10; and where M + is a conjugate acid of the nitrogenous base, and b) water.

62. An aqueous surface active solution according to claim 53, characterized in that it comprises: a) a polymerizable surface active agent of the formula: R? C02 (CH2) nS03 ~ M + wherein Ri is a saturated or unsaturated hydrocarbon group having from about 1 to 24 carbon atoms; and wherein M + is a conjugate acid of the nitrogenous base; and b) water.

63. An aqueous surface active solution according to claim 53, characterized in that it comprises: a) a polymerizable surface active agent of the formula: (Ri) n-Ar-0 (CH2CH (R ') 0) mS03 ~ M +) wherein Ri is a saturated or unsaturated hydrocarbon group having from about 1 to 24 carbon atoms; wherein Ar is a phenyl, polyphenyl, naphthyl, polynaphthyl, styryl, or polystyryl group and mixtures thereof; wherein R 'is methyl or hydrogen: wherein M + is a conjugate acid of the nitrogenous base; where n is an integer from 1 to 4; wherein the total number of carbon atoms represented by (R?) n is at least 5; and where m is zero or an integer from 1 to 100; and b) water.

64. An aqueous surface active solution according to claim 53, characterized in that it comprises: a) a polymerizable surface active agent of the formula: RiO (CH2CH (R ') 0) n (S03 ~ M + where Ri is a saturated or unsaturated hydrocarbon group having from about 1 to 24 carbon atoms, where R' is methyl or hydrogen, where n is zero or an integer from 1 to 100, and where M + is a conjugate acid of the nitrogenous base, and b) water.

65. An aqueous surface active solution according to claim 53, characterized in that it comprises: a) a polymerizable surface active agent of the formula: R? C02"M + wherein Ri is a saturated or unsaturated hydrocarbon group having from about 4 to 24 carbon atoms; and wherein M + is a conjugate acid of the nitrogenous base; and b) water.

66. An aqueous surface active solution according to claim 53, characterized in that it comprises: a) a polymerizable surface active agent of the formula: R? CON (R ') (CH2) nC02"M + r wherein Ri is a saturated or unsaturated hydrocarbon group having from about 1 to 24 carbon atoms; wherein R 'is methyl, ethyl, propyl or hydrogen; wherein M + is a conjugate acid of the nitrogenous base; and where n is a whole number of 1 to 10; and b) water.

67. An aqueous surface active solution according to claim 53, characterized in that it comprises: a) a polymerizable surface active agent of the formula: RiCONÍR ') (CH2) nS03"M + wherein Ri is a saturated or unsaturated hydrocarbon group having from about 1 to 24 carbon atoms; wherein R 'is methyl, ethyl propyl, or hydrogen, wherein M + is a conjugate acid of the nitrogenous base, and wherein n is an integer from 1 to 10, and b) water.

68. An aqueous surface active solution according to claim 53, characterized in that it comprises: a) a polymerizable surface active agent of the formula: RiO (CH2CH (R ') O) nCOCH2S03 ~ M + wherein Ri is a saturated or unsaturated hydrocarbon group having from about 1 to 24 carbon atoms; wherein R 'is methyl or hydrogen; where n is zero or an integer from 1 to 100; wherein M + is a conjugate acid of the nitrogenous base; and b) water.

69. An aqueous surface active solution according to claim 53, characterized in that it comprises: a) a polymerizable surface active agent of the formula: R? O (P03) x "M + y wherein Ri is a saturated or unsaturated hydrocarbon group having from about 1 to 24 carbon atoms, or a phenyl, polyphenyl, naphthyl, polynaphthyl, styryl or polystyryl group, a phenyl group substituted with alkyl / alkoxylate, a substituted polyphenyl group or polysubstituted with alkyl / alkoxylate, a naphthyl group substituted or polysubstituted with alkyl / alkoxylate, a polinaphthyl group substituted or polysubstituted with alkyl / alkoxylate, a styryl group substituted or polysubstituted with alkyl / alkoxylate, or a polystyreyl group substituted or polysubstituted with alkyl / alkoxylate and mixtures thereof; wherein M + is a conjugate acid of the nitrogenous base; where x is 1 or 2 and y is 1 or 2; and b) water.

70. An aqueous surface active solution according to claim 53, characterized in that it comprises: a) a polymerizable surface active agent of the formula: [RiO (CH2CH (R ') Om] nP (O) px_M + and wherein Ri is a saturated or unsaturated hydrocarbon group having from about 1 to 24 carbon atoms; wherein R 'is methyl or hydrogen; wherein M + is a conjugate acid of the nitrogenous base, selected from the group consisting of allylamine, diallylamine, triallylamine, methallylamine, N-methyl-N-allylamine, or 2- (dimethylamino) ethyl acrylate and mixtures thereof; where m is zero or an integer from 1 to 100; where n is 1 or 2; where p is 2 or 3; where x is 1 or 2; and where y is 1 or 2; and b) water.

71. An active surface solution, according to claim 53, characterized in that it comprises:: a polymerizable surface active agent of the formula [(Ri) nArO (CH2CH (R ') 0) m] qP (0) Px "M + Y wherein Ri is a saturated or unsaturated hydrocarbon group having from about 1 to 24 carbon atoms; wherein Ar is phenyl; wherein R 'methyl or hydrogen; wherein M + is a conjugate acid of the nitrogenous base, selected from the group consisting of allylamine, diallylamine, triallylamine, methallylamine, N-methyl-N-allylamine, or 2- (dimethylamino) ethyl acrylate and mixtures thereof; where n is an integer from 1 to 4; where m is zero or an integer from 1 to 100, where q is 1 or 2; where p is 2 or 3; where x is 1 or 2; and where y is 1 or 2; and wherein the number of carbon atoms represented by (R?) n is at least about 5 when m is 0 and q is 1; and b) water.

72. A polymerizable surface active agent according to claim 1, characterized in that the nitrogenous base is a compound of the formula N R3 / \ R2 wherein Ri and R2 are independently hydrogen or organic groups containing an ethenylene group, with the proviso that at least one of the groups R1-R3 is a straight or branched chain alkyl group containing 1 to 8 carbon atoms and Etenylene functional group.