Emulsion polymerization process utilizing ethylenically unsaturated amine salts of sulfonic, phosphoric and carboxylic acids

Abstract

Disclosed is an improved method of making polymers. The method utilizes at least one ethylenically unsaturated monomer and at least one polymerizable surface active agent. The polymerizable surface active agent is capable of co-polymerization with traditional monomers and/or polymerization with itself (i.e. homopolymerization) and is preferably substantially completely consumed during the course of the polymerization. Polymers produced by the method of the present invention are well suited for use in coatings, adhesives, sealants, elastomers and the like, as they form stable films, possess excellent adhesion properties and have improved hydrolytic stability characteristics. The present invention also encompasses homopolymeric surface active agents and their use in polymerization reactions.

What is claimed:  
     
         1 . A method for forming polymers comprising: 
 a) preparing a mixture comprising: 
 i) at least one ethylenically unsaturated monomer;  
 ii) at least one polymerizable, surface active agent;  
 wherein the polymerizable, surface active agent is a salt or quatemary nitrogen compound comprising: 
 a) at least one acid, wherein the acid is a sulfonic 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 moiety; and  
 
   b) polymerizing the mixture; 
 wherein the polymerizable, surface active agent is capable of polymerization with itself, copolymerization with the ethylenically unsaturated monomer or co-polymerization with a partially polymerized polymer particle.  
   
     
     
         2 . A method according to  claim 1 , wherein a portion of the polymerizable, surface active agent is partially consumed by polymerization with itself, co-polymerization with the monomer and/or co-polymerization with a partially polymerized polymer particle.  
     
     
         3 . A method according to  claim 1 , wherein the polymerizable, surface active agent is substantially consumed by polymerization with itself, co-polymerization with the monomer and/or co-polymerization with a partially polymerized polymer particle.  
     
     
         4 . A method according to  claim 1 , wherein the polymerizable, surface active agent is substantially completely consumed by polymerization with itself, co-polymerization with the monomer and/or co-polymerization with a partially polymerized polymer particle.  
     
     
         5 . A method according to  claim 1 , wherein the nitrogenous base is a compound of the formula  
       
         
           
           
               
               
           
         
       
       wherein R 1 , R 2  and R 3  are independently hydrogen or organic groups containing an ethenylene group, provided that at least one of R 1 -R 3  is a straight or branched chain alkyl group containing 1-8 carbon atoms and an ethenylene functionality.  
     
     
         6 . A method according to  claim 1 , wherein the nitrogenous base is allyl amine, diallyl amine, triallyl amine, methallyl amine, N-methyl N-allyl amine, allyldimethyl amine, methyl 3-amino crotonate, 3-amino crotononitrile, 3-amino-1-propanol vinyl ether, 2-(dimethylamino)ethyl acrylate, or 1,4-diamino-2-butene or a mixture thereof.  
     
     
         7 . A method according to  claim 6 , wherein the nitrogenous base is allyl amine, diallyl amine, triallyl amine, methallyl amine, N-methyl N-allyl amine or 2-(dimethylamino)ethyl acrylate, or a mixture thereof.  
     
     
         8 . A method according to  claim 1 , wherein the acid is a sulfonic acid, a sulfonic acid ester, a polysulfonic acid, a sulfonic acid of an oil, a paraffin sulfonic acid, a lignin sulfonic acid, a petroleum sulfonic acid, an olefin sulfonic acid, a polyolefin sulfonic acid, a polyolefin polysulfonic acid, a carboxylic acid, a polycarboxylic acid, a phosphoric acid, a polyphosphoric acid, a phosphinic acid, or a polyphosphinic acid, or a mixture thereof.  
     
     
         9 . A method according to  claim 1 , wherein the polymerizable, surface active agent is of the formula: 
       (R 1 ) n —Ar(SO 3   − M + ) m   
       wherein R 1  is a saturated or unsaturated hydrocarbon group having from about 1-24 carbon atoms; wherein Ar is a phenyl, polyphenyl, napthyl, polynapthyl, styryl, or polystyryl group, or a mixture thereof; wherein M +  is a conjugate acid of the nitrogenous base; wherein n=1-5 and m=1-8; and wherein the total number of carbon atoms represented by (R 1 ) n  is at least 5.  
     
     
         10 . A method according to  claim 9 , wherein R 1  is a saturated or unsaturated hydrocarbon group having from about 6-24 carbon atoms; wherein Ar is a phenyl; wherein M +  is a conjugate acid of the nitrogenous base, selected from the group consisting of allyl amine, diallyl amine, triallyl amine, methallyl amine, N-methyl N-allyl amine or 2-(dimethylamino)ethyl acrylate, and mixtures thereof; and wherein n=1 and m=1.  
     
     
         11 . A method according to  claim 10 , wherein the polymerizable, surface active agent is of the formula:  
       
         
           
           
               
               
           
         
       
       wherein n1=4-18; and wherein R′ is hydrogen or saturated or unsaturated hydrocarbon group having from about 1-8 carbon atoms.  
     
     
         12 . A method according to  claim 1 , wherein the polymerizable, surface active agent is of the formula: 
       (R 1 ) n1 —{Ar(SO 3   − M + ) m1 }—O—{Ar(So 3   − M + ) m2 }—(R 2 ) n2   
       wherein R 1  and R 2  are independently hydrogen, or saturated or unsaturated hydrocarbon groups having from about 1-24 carbon atoms; wherein Ar is a phenyl, polyphenyl, napthyl, polynapthyl, styryl, or polystyryl group, or a mixture thereof; wherein M +  is a conjugate acid of the nitrogenous base; wherein n1 and n2 are independently 0-5, provided that n1 and n2 are not both equal to zero; and wherein m1 and m2 are independently 0-8, provided that m1 and m2 are not both equal to zero.  
     
     
         13 . A method according to  claim 12 , wherein R 1  is hydrogen and R 2  is a saturated or unsaturated hydrocarbon group having from about 6-24 carbon atoms; wherein Ar is phenyl; wherein M +  is a conjugate acid of the nitrogenous base, selected from the group consisting of allyl amine, diallyl amine, triallyl amine, methallyl amine, N-methyl N-allyl amine or 2-(dimethylamino)ethyl acrylate, and mixtures thereof; wherein n1-4 and n2-1; and wherein m1 and m2 both equal one.  
     
     
         14 . A method according to  claim 12 , wherein R 1  and R 2  are independently saturated or unsaturated hydrocarbon groups having from about 6-24 carbon atoms; wherein Ar is phenyl, wherein M +  is a conjugate acid of the nitrogenous base, selected from the group consisting of allyl amine, diallyl amine, triallyl amine, methallyl amine, N-methyl N-allyl amine, or 2-(dimethylamino)ethyl acrylate, and mixtures thereof; wherein n1 and n2 both equal one; and wherein m1 and m2 both equal one.  
     
     
         15 . A method according to  claim 1 , wherein the polymerizable, surface active agent is of the formula: 
       R 1 —CH(SO 3   − M + )CO 2 R 2   
       wherein R 1  and R 2  are independently saturated or unsaturated hydrocarbon groups having from about 1-24 carbon atoms; and wherein M +  is a conjugate acid of the nitrogenous base.  
     
     
         16 . A method according to  claim 15 , wherein R 1  is a saturated or unsaturated hydrocarbon group having from about 6-24 carbon atoms; wherein R 2  is methyl, ethyl, or propyl, or a mixture thereof; and wherein M +  is a conjugate acid of the nitrogenous base, selected from the group consisting of allyl amine, diallyl amine, triallyl amine, methallyl amine, N-methyl N-allyl amine, or 2-(dimethylamino)ethyl acrylate, and mixtures thereof.  
     
     
         17 . A method according to  claim 16 , wherein the polymerizable, surface active agent is of the formula:  
       
         
           
           
               
               
           
         
       
       wherein n=3-18.  
     
     
         18 . A method according to  claim 1 , wherein the polymerizable, surface active agent is of the formula: 
       R 1 —CH(SO 3   −M   + )CO 2 M +   
       wherein R 1  is a saturated or unsaturated hydrocarbon group having from about 3-24 carbon atoms; and wherein M +  is a conjugate acid of the nitrogenous base.  
     
     
         19 . A method according to  claim 18 , wherein R 1  is a saturated or unsaturated hydrocarbon group having from about 6-24 carbon atoms; and wherein M +  is a conjugate acid of the nitrogenous base, selected from the group consisting of allyl amine, diallyl amine, triallyl amine, methallyl amine, N-methyl N-allyl amine, or 2-(dimethylamino)ethyl acrylate, and mixtures thereof.  
     
     
         20 . A method according to  claim 1 , wherein the polymerizable, surface active agent is of the formula: 
       R 1 —CH(SO 3   −M   + )C(O)O(CH 2 CH(R′)O) n R 2   
       wherein R 1  and R 2  are independently saturated or unsaturated hydrocarbon groups having from about 1-24 carbon atoms; wherein R′ is methyl or hydrogen; wherein n=1-100; and wherein M +  is a conjugate acid of the nitrogenous base.  
     
     
         21 . A method according to  claim 20 , wherein R 1  is a saturated or unsaturated hydrocarbon group having from about 4-24 carbon atoms; R′ is methyl or hydrogen; R 2  is methyl, ethyl, or propyl, and mixtures thereof; M +  is the nitrogenous base, selected from the group consisting of allyl amine, diallyl amine, triallyl amine, methallyl amine, N-methyl N-allyl amine, or 2-(dimethylamino)ethyl acrylate, and mixtures thereof; and wherein n=1-100.  
     
     
         22 . A method according to  claim 1 , wherein the polymerizable, surface active agent is of the formula: 
       R 1 —(SO 3   − M + ) 
       wherein R 1  is a saturated or unsaturated hydrocarbon group having from about 6-24 carbon atoms; and wherein M +  is a conjugate acid of the nitrogenous base.  
     
     
         23 . A method according to  claim 22 , wherein R 1  is a saturated or unsaturated hydrocarbon group having from about 6-24 carbon atoms; and wherein M +  is a conjugate acid of the nitrogenous base, selected from the group consisting of allyl amine, diallyl amine, triallyl amine, methallyl amine, N-methyl N-allyl amine, or 2-(dimethylamino)ethyl acrylate, and mixtures thereof.  
     
     
         24 . A method according to  claim 1 , wherein the polymerizable, surface active agent is of the formula: 
       R 1 CO 2 (CH 2 ) n CH(SO 3   + M + )CO 2 R 2   
       wherein R 1  and R 2  are independently saturated or unsaturated hydrocarbon groups having from about 1-24 carbon atoms; wherein n=0-10; and wherein M +  is a conjugate acid of the nitrogenous base.  
     
     
         25 . A method according to  claim 24 , wherein R 1  and R 2  are independently saturated or unsaturated hydrocarbon groups having from about 1-24 carbon atoms; wherein n=1-6; and wherein M +  is a conjugate acid of the nitrogenous base, selected from the group consisting of allyl amine, diallyl amine, triallyl amine, methallyl amine, N-methyl N-allyl amine, or 2-(dimethylamino)ethyl acrylate, and mixtures thereof.  
     
     
         26 . A method according to  claim 1 , wherein the polymerizable, surface active agent is of the formula: 
       R 1 CO 2 (CH 2 ) n SO 3   − M +   
       wherein R 1  is a saturated or unsaturated hydrocarbon group having from about 1-24 carbon atoms; wherein n=1-10; and wherein M +  is a conjugate acid of the nitrogenous base.  
     
     
         27 . A method according to  claim 26 , wherein R 1  is a saturated or unsaturated hydrocarbon group having from about 6-24 carbon atoms; wherein n=1-5; and wherein M +  is a conjugate acid of the nitrogenous base, selected from the group consisting essentially of allyl amine, diallyl amine, triallyl amine, methallyl amine, N-methyl N-allyl amine, or 2-(dimethylamino)ethyl acrylate, or a mixture thereof.  
     
     
         28 . A method according to  claim 1 , wherein the polymerizable, surface active agent is of the formula: 
       (R 1 ) n —Ar—O(CH 2 CH(R′)O) m (SO 3   − M + ) 
       wherein R 1  is a saturated or unsaturated hydrocarbon group having from about 1-24 carbon atoms; wherein Ar is a phenyl, polyphenyl, napthyl, polynapthyl, styryl, or polystyryl group, and mixtures thereof; wherein R′ is methyl or hydrogen; wherein M +  is a conjugate acid of the nitrogenous base; wherein n 1-4; wherein the total number of carbon atoms represented by (R 1 ) n  is at least 5; and wherein m=0-100.  
     
     
         29 . A method according to  claim 28 , wherein, R 1  is a saturated or unsaturated hydrocarbon group having from about 6-24 carbon atoms; wherein Ar is phenyl; wherein M +  is a conjugate acid of the nitrogenous base, selected from the group consisting of allyl amine, diallyl amine, triallyl amine, methallyl amine, N-methyl N-allyl amine, or 2-(dimethylamino)ethyl acrylate, and mixtures thereof; wherein n=1; and wherein m=0-100.  
     
     
         30 . A method according to  claim 1 , wherein the polymerizable, surface active agent is of the formula: 
       R 1 O(CH 2 CH(R′)O) n (SO 3   − M + ) 
       wherein R 1  is a saturated or unsaturated hydrocarbon group having from about 1-24 carbon atoms; wherein R′ is methyl or hydrogen; wherein n=0-100; and wherein M +  is a conjugate acid of the nitrogenous base.  
     
     
         31 . A method according to  claim 30 , wherein R 1  is a saturated or unsaturated hydrocarbon group having from about 6-24 carbon atoms; wherein R′ is methyl or hydrogen; wherein n=0-100; and wherein M +  is a conjugate acid of the nitrogenous base, selected from the group consisting of allyl amine, diallyl amine, triallyl amine, methallyl amine, N-methyl N-allyl amine, or 2-(dimethylamino)ethyl acrylate, and mixtures thereof.  
     
     
         32 . A method according to  claim 31 , wherein the polymerizable, surface active agent is of the formula:  
       
         
           
           
               
               
           
         
       
       wherein n1=5-18.  
     
     
         33 . A method according to  claim 31 , wherein the polymerizable, surface active agent is of the formula:  
       
         
           
           
               
               
           
         
       
       wherein n1=5-18; and wherein n=1-20.  
     
     
         34 . A method according to  claim 1 , wherein the polymerizable, surface active agent is of the formula: 
       R 1 CO 2   − M +   
       wherein R 1  is a saturated or unsaturated hydrocarbon group having from about 4-24 carbon atoms; and wherein M +  is a conjugate acid of the nitrogenous base.  
     
     
         35 . A method according to  claim 34 , wherein R 1  is a saturated or unsaturated hydrocarbon group having from about 6-24 carbon atoms; and wherein M +  is a conjugate acid of the nitrogenous base, selected from the group consisting of allyl amine, diallyl amine, triallyl amine, methallyl amine, N-methyl N-allyl amine, or 2-(dimethylamino)ethyl acrylate, and mixtures thereof.  
     
     
         36 . A method according to  claim 35 , wherein the polymerizable, surface active agent is of the formula:  
       
         
           
           
               
               
           
         
       
       wherein n=5-18.  
     
     
         37 . A method according to  claim 1 , wherein the polymerizable, surface active agent is of the formula: 
       R 1 CON(R′)(CH 2 ) n CO 2 M +   
       wherein R 1  is a saturated or unsaturated hydrocarbon group having from about 1-24 carbon atoms; wherein R′ is methyl, ethyl, propyl or hydrogen; wherein M +  is a conjugate acid of the nitrogenous base; and wherein n1-10.  
     
     
         38 . A method according to  claim 37 , wherein M +  is a conjugate acid of the nitrogenous base, selected from the group consisting of allyl amine, diallyl amine, triallyl amine, methallyl amine, N-methyl N-allyl amine, or 2-(dimethylamino)ethyl acrylate, and mixtures thereof; wherein R′ is methyl, ethyl, propyl or hydrogen; and wherein n=2-5.  
     
     
         39 . A method according to  claim 1 , wherein the polymerizable, surface active agent is of the formula: 
       R 1 CON(R′)(CH 2 ) n SO 3 M +   
       wherein R 1  is a saturated or unsaturated hydrocarbon group having from about 1-24 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.  
     
     
         40 . A method according to  claim 39 , wherein M +  is a conjugate acid of the nitrogenous base, selected from the group consisting of allyl amine, diallyl amine, triallyl amine, methallyl amine, N-methyl N-allyl amine, or 2-(dimethylamino)ethyl acrylate, and mixtures thereof; wherein R′ is methyl, ethyl, propyl or hydrogen; and wherein n=2-5.  
     
     
         41 . A method according to  claim 1 , wherein the polymerizable, surface active agent is of the formula: 
       R 1 O(CH 2 CH(R′)O) n COCH 2 SO 3   − M +   
       wherein R 1  is a saturated or unsaturated hydrocarbon group having from about 1-24 carbon atoms; wherein R′ is methyl or hydrogen; wherein n=0-100; wherein M +  is a conjugate acid of the nitrogenous base.  
     
     
         42 . A method according to  claim 41 , wherein R 1  is a saturated or unsaturated hydrocarbon group having from about 6-24 carbon atoms; wherein R′ is methyl or hydrogen; wherein M + is a conjugate acid of the nitrogenous base, selected from the group consisting of allyl amine, diallyl amine, triallyl amine, methallyl amine, N-methyl N-allyl amine, or 2-(dimethylamino)ethyl acrylate, and mixtures thereof; and wherein n=0-100.  
     
     
         43 . A method according to  claim 1 , wherein the polymerizable, surface active agent is of the formula: 
       R 1 O(PO 3 ) x− M +   y   
       wherein R 1  is a saturated or unsaturated hydrocarbon group having from about 1-24 carbon atoms, phenyl, polyphenyl, napthyl, polynapthyl, styryl, or polystyryl group, an alkyl/alkoxylate substituted phenyl, an alkyl/alkoxylate substituted or poly-substituted polyphenyl, an alkyl/alkoxylate substituted or poly-substituted napthyl, an alkyl/alkoxylate substituted or poly-substituted polynapthyl, an alkyl/alkoxylate substituted or poly-substituted styryl, or an alkyl/alkoxylate substituted or poly-substituted polystyryl group, and mixtures thereof; wherein M +  is a conjugate acid of the nitrogenous base; wherein x=1 or 2; and wherein y=1 or 2.  
     
     
         44 . A method according to  claim 1 , wherein the polymerizable, surface active agent is of the formula: 
       [R 1 O(CH 2 CH(R′)O) m ] n P(O) p   x− M +   y   
       wherein R 1  is a saturated or unsaturated hydrocarbon group having from about 1-24 carbon atoms; wherein R′ is methyl or hydrogen; wherein M +  is a conjugate acid of the nitrogenous base, selected from the group consisting of allyl amine, diallyl amine, triallyl amine, methallyl amine, N-methyl N-allyl amine, or 2-(dimethylamino)ethyl acrylate, and mixtures thereof; m=0-100; wherein n=1 or 2; wherein p=2 or 3; wherein x=1 or 2; and wherein y=1 or 2.  
     
     
         45 . A method according to  claim 1 , wherein the polymerizable, surface active agent is of the formula: 
       [(R 1 ) n ArO(CH 2 CH(R′)O) m ] q P(O) p   x− M +   y   
       wherein R 1  is a saturated or unsaturated hydrocarbon group having from about 1-24 carbon atoms; wherein Ar is phenyl; wherein R′ is methyl or hydrogen; wherein M +  is a conjugate acid of the nitrogenous base, selected from the group consisting of allyl amine, diallyl amine, triallyl amine, methallyl amine, N-methyl N-allyl amine, or 2-(dimethylamino)ethyl acrylate, and mixtures thereof; wherein n=1-4; wherein m=0-100; wherein q=1 or 2; wherein p=2 or 3; wherein x=1 or 2; and wherein y=1 or 2.  
     
     
         46 . A method according to  claim 1 , wherein at least one of the ethylenically unsaturated monomers is styrene and is reacted with at least one acrylic monomer.  
     
     
         47 . A method according to  claim 1 , wherein at least one of the ethylenically unsaturated monomers is at least one non-aromatic vinyl compound.  
     
     
         48 . A method according to  claim 1 , wherein at least one of the ethylenically unsaturated monomers is vinyl acetate and is reacted with at least one acrylic monomer.  
     
     
         48 . A method according to  claim 1 , wherein at least one of the ethylenically unsaturated monomers is at least one acrylic monomer.  
     
     
         49 . A method according to  claim 1 , wherein the polymerizable, surface active agent and the monomer are combined in a ratio of about 0.01:1 to about 3:1 on a weight basis.  
     
     
         50 . A method according to  claim 49 , wherein the polymerizable, surface active agent is present in the mixture in a concentration of about 1-10 weight percent, based on the total weight of the ethylenically unsaturated monomer present in the mixture.  
     
     
         51 . A method according to  claim 50 , wherein the polymerizable, surface active agent is present in the mixture in a concentration of about 1-3 weight percent, based on the total weight of the ethylenically unsaturated monomer present in the mixture.  
     
     
         52 . A method according to  claim 1 , wherein the polymerizable surface active agent is formed by contacting the acid with the nitrogenous base.  
     
     
         53 . A method according to  claim 1 , wherein the polymerizable surface active agent is formed by contacting the nitrogenous base with the acid.  
     
     
         54 . A method according to  claim 1 , wherein steps (a) and (b) occur simultaneously.  
     
     
         55 . A method according to  claim 1 , wherein steps (a) and (b) occur simultaneously and wherein the method is self-initiating.  
     
     
         56 . A method according to  claim 1 , wherein the mixture is substantially free of non-polymerizable, surface active agents.  
     
     
         57 . A method according to  claim 1 , wherein the mixture further comprises a supplemental surface active agent (iii); wherein the supplemental surface active agent is a sodium, potassium, calcium, magnesium, or ammonium salt of a substantially saturated anionic surfactant, or a nonionic, cationic, or amphoteric surfactant, or a mixture thereof; and wherein the supplemental surface active agent is provided in a concentration of about 0.01 to about 20.0 percent by weight, based on the total weight of polymerizable surface active agent and supplemental surface active agent.  
     
     
         58 . A method according to  claim 5 , wherein R 1  is a hydrocarbon group containing from about 2-20 carbon atoms and at least one double bond, and wherein R 2  and R 3  are hydrogen.  
     
     
         59 . A method according to  claim 1  or  claim 57 , wherein the mixture further comprises an initiator.  
     
     
         60 . A method according to  claim 1  or  claim 57 , wherein the mixture is an emulsion, suspension or dispersion.  
     
     
         61 . An emulsion, suspension or dispersion of polymers, suitable for use in coating, adhesive, sealant and/or elastomer applications, prepared by the method of  claim 1  or  claim 57 .  
     
     
         62 . A method according to  claim 1 , wherein the polymerizable surface active agent is provided as a solution.  
     
     
         63 . Polymers suitable for use in coating, adhesive, sealant and/or elastomer applications, prepared by the method of  claim 1  or  claim 57 .  
     
     
         64 . A pre-polymerization mixture comprising: 
 a) at least one ethylenically unsaturated monomer; and    b) at least one polymerizable surface active agent;    wherein the polymerizable, surface active agent is a salt or quaternary nitrogen compound comprising: 
 a) at least one acid, wherein the acid is a sulfonic 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 moiety; and  
   
     
     
         65 . A polymer comprising: 
 a) at least one monomer unit; and    b) at least one surface active agent unit;    wherein the monomer unit is derived from an ethylenically unsaturated monomer; wherein the surface active agent is derived from a polymerizable surface active agent;    and wherein the ethylenically unsaturated monomer and the polymerizable surface active agent have co-polymerized to form the polymer.    
     
     
         66 . A method for forming polymers comprising: 
 a) preparing a mixture comprising: 
 i) at least one ethylenically unsaturated monomer;  
 ii) at least one acid, wherein the acid is a sulfonic acid, a carboxylic acid, or a phosphoric acid, or a mixture thereof; and  
 iii) at least one nitrogenous base, wherein the nitrogenous base contains at least one nitrogen atom and at least one ethylenically unsaturated moiety;  
   b) polymerizing the mixture.    
     
     
         67 . A method according to  claim 66 , wherein the acid and the nitrogenous base form a polymerizable, surface active agent; wherein the polymerizable, surface active agent is a salt or quaternary nitrogen compound; wherein the polymerizable surface active agent is capable of polymerization with itself, copolymerization with the ethylenically unsaturated monomer and/or co-polymerizing with a partially polymerized polymer particle; and wherein the polymerizable, surface active agent is substantially completely consumed by polymerization with itself, co-polymerization with the monomer and/or co-polymerization with a partially polymerized polymer particle.  
     
     
         68 . A method according to  claim 67 , wherein a portion of the nitrogenous base polymerizes with itself, co-polymerizes with the monomer or co-polymerizes with a partially polymerized polymer.  
     
     
         69 . A method for forming polymers comprising: 
 a) preparing a mixture comprising: 
 i) at least one ethylenically unsaturated monomer;  
 ii) at least one homopolymeric surface active agent, the homopolymeric surface active agent being a polymer formed by polymerizing and/or co-polymerizing at least one polymerizable, surface active agent;  
 wherein the polymerizable, surface active agent is a salt or quaternary nitrogen compound comprising: 
 a) at least one acid, wherein the acid is a sulfonic 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 moiety;  
 
   b) polymerizing the mixture.    
     
     
         70 . A method according to  claim 69 , wherein the homopolymeric surface active agent is capable of polymerization with itself, co-polymerization with the monomer or co-polymerization with a partially polymerized polymer particle.  
     
     
         71 . A homopolymeric surface active agent formed by polymerizing at least one polymerizable, surface active agent, wherein the polymerizable, surface active agent is a salt comprising: 
 a) at least one acid, wherein the acid is a sulfonic 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 moiety.