Ethylenically unsaturated amine salts of sulfonic, phosphoric, and carboxylic acids

Abstract

Disclosed are ethylenically unsaturated amine salts of sulfonic, phosphoric and carboxylic acids. The salts are surface active agents which are useful in a variety of applications as primary and/or secondary surfactants. The salts are especially useful as surfactants in emulsion polymerization reactions.

What is claimed:  
     
         1 . A polymerizable, surface active agent comprising 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;    wherein the polymerizable, surface active agent is a salt or quaternary nitrogen compound.    
     
     
         2 . A polymerizable, surface active agent according to  claim 1 , wherein the acid is a sulfonic acid, 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.  
     
     
         3 . A polymerizable, surface active agent 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.  
     
     
         4 . A polymerizable, surface active agent according to  claim 3 , 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.  
     
     
         5 . A polymerizable, surface active agent according to  claim 1 , which 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.  
     
     
         6 . A polymerizable, surface active agent according to  claim 5 , 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, 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.  
     
     
         7 . A polymerizable, surface active agent according to  claim 6 , which 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.  
     
     
         8 . A polymerizable, surface active agent according to  claim 1 , which 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.  
     
     
         9 . A polymerizable, surface active agent according to  claim 8 , 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, 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.  
     
     
         10 . A polymerizable, surface active agent according to  claim 8 , 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, 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.  
     
     
         11 . A polymerizable, surface active agent according to  claim 10 , which is of the formula:  
       
         
           
           
               
               
           
         
       
       wherein n and n′ are independently 4-18; and wherein R′ and R″ are independently hydrogen, methyl, ethyl or propyl.  
     
     
         12 . A polymerizable, surface active agent according to  claim 1 , which 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.  
     
     
         13 . A polymerizable, surface active agent according to  claim 12 , 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, 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.  
     
     
         14 . A polymerizable, surface active agent according to  claim 13 , which is of the formula:  
       
         
           
           
               
               
           
         
       
       wherein n=3-18.  
     
     
         15 . A polymerizable, surface active agent according to  claim 1 , which 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.  
     
     
         16 . A polymerizable, surface active agent according to  claim 15 , 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, 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 polymerizable, surface active agent according to  claim 16 , which is of the formula:  
       
         
           
           
               
               
           
         
       
       wherein n=3-18.  
     
     
         18 . A polymerizable, surface active agent according to  claim 1 , which 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.  
     
     
         19 . A polymerizable, surface active agent according to  claim 18 , 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 a conjugate acid of the nitrogenous base, 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.  
     
     
         20 . A polymerizable, surface active agent according to  claim 21 , which is of the formula:  
       
         
           
           
               
               
           
         
       
       wherein n1=2-18; and wherein n2=1-20.  
     
     
         21 . A polymerizable, surface active agent according to  claim 1 , which 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.  
     
     
         22 . A polymerizable, surface active agent according to  claim 21 , 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, 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.  
     
     
         23 . A polymerizable, surface active agent according to  claim 22 , which is of the formula:  
       
         
           
           
               
               
           
         
       
       wherein n=5-17.  
     
     
         24 . A polymerizable, surface active agent according to  claim 1 , which 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 polymerizable, surface active agent 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, 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 polymerizable, surface active agent according to  claim 25 , which is of the formula:  
       
         
           
           
               
               
           
         
       
       wherein n1=0-17  
     
     
         27 . A polymerizable, surface active agent according to  claim 1 , which 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.  
     
     
         28 . A polymerizable, surface active agent according to  claim 27 , 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, 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.  
     
     
         29 . A polymerizable, surface active agent according to  claim 28 , which is of the formula:  
       
         
           
           
               
               
           
         
       
       wherein n1=2-18.  
     
     
         30 . A polymerizable, surface active agent according to  claim 1 , which 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.  
     
     
         31 . A polymerizable, surface active agent according to  claim 30 , 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, 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.  
     
     
         32 . A polymerizable, surface active agent according to  claim 31 , which is of the formula:  
       
         
           
           
               
               
           
         
       
       wherein n1=5-18; and wherein n2=0-20.  
     
     
         33 . A polymerizable, surface active agent according to  claim 1 , which 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.  
     
     
         34 . A polymerizable, surface active agent according to  claim 33 , 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, 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.  
     
     
         35 . A polymerizable, surface active agent according to  claim 34 , which is of the formula:  
       
         
           
           
               
               
           
         
       
       wherein n1=5-18.  
     
     
         36 . A polymerizable, surface active agent according to  claim 34 , which is of the formula:  
       
         
           
           
               
               
           
         
       
       wherein n1=5-18; and wherein n=1-20.  
     
     
         37 . A polymerizable, surface active agent according to  claim 1 , which 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.  
     
     
         38 . A polymerizable, surface active agent according to  claim 37 , 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, 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.  
     
     
         39 . A polymerizable, surface active agent according to  claim 38 , which is of the formula:  
       
         
           
           
               
               
           
         
       
       wherein n=5-18.  
     
     
         40 . A polymerizable, surface active agent according to  claim 1 , which 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 n=1-10.  
     
     
         41 . A polymerizable, surface active agent according to  claim 42 , wherein M +  is a conjugate acid of the nitrogenous base, 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.  
     
     
         42 . A polymerizable, surface active agent according to  claim 41 , which is of the formula:  
       
         
           
           
               
               
           
         
       
       wherein n1=2-18.  
     
     
         43 . A polymerizable, surface active agent according to  claim 1 , which 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.  
     
     
         44 . A polymerizable, surface active agent according to  claim 41 , wherein M +  is a conjugate acid of the nitrogenous base, 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.  
     
     
         45 . A polymerizable, surface active agent according to  claim 44 , which is of the formula:  
       
         
           
           
               
               
           
         
       
       wherein n1=2-18.  
     
     
         46 . A polymerizable, surface active agent according to  claim 1 , which 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.  
     
     
         47 . A polymerizable, surface active agent according to  claim 46 , 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, 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.  
     
     
         48 . A polymerizable, surface active agent according to  claim 47 , which is of the formula:  
       
         
           
           
               
               
           
         
       
       wherein n1=5-17; and wherein n=0-20.  
     
     
         49 . A polymerizable, surface active agent according to  claim 1 , which 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.  
     
     
         50 . A polymerizable, surface active agent according to  claim 1 , which 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, 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=-100; wherein n=1 or 2; wherein p=2 or 3; wherein x=1 or 2; and wherein y=1 or 2.  
     
     
         51 . A polymerizable, surface active agent according to  claim 1 , which 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, 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 whereiny=1 or 2.  
     
     
         52 . An aqueous, surface active solution, comprising: 
 a) a polymerizable, surface active agent, comprising: 
 1. at least one acid, wherein the acid is a sulfonic acid, a carboxylic acid, or a phosphoric acid, 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 moiety;  
    wherein the polymerizable, surface active agent is a salt or quaternary nitrogen compound; and    b) water.    
     
     
         53 . An aqueous, surface active solution, according to  claim 52 , comprising: 
 a) a polymerizable, surface active agent 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; and    b) water.    
     
     
         54 . An aqueous, surface active solution, according to  claim 52 , comprising: 
 a) a polymerizable, surface active agent 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; and    b) water.    
     
     
         55 . An aqueous, surface active solution, according to  claim 52 , comprising: 
 a) a polymerizable, surface active agent 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; and    b) water.    
     
     
         56 . An aqueous, surface active solution, according to  claim 52 , comprising: 
 a) a polymerizable, surface active agent 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; and    b) water.    
     
     
         57 . An aqueous, surface active solution, according to  claim 52 , comprising: 
 a) a polymerizable, surface active agent 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; and    b) water.    
     
     
         58 . An aqueous, surface active solution, according to  claim 52 , comprising: 
 a) a polymerizable, surface active agent 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; and    b) water.    
     
     
         59 . An aqueous, surface active solution, according to  claim 52 , comprising: 
 a) a polymerizable, surface active agent 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; and    b) water.    
     
     
         60 . An aqueous, surface active solution, according to  claim 52 , comprising: 
 a) a polymerizable, surface active agent 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; and    b) water.    
     
     
         61 . An aqueous, surface active solution, according to  claim 52 , comprising: 
 a) a polymerizable, surface active agent 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; and    b) water.    
     
     
         62 . An aqueous, surface active solution, according to  claim 52 , comprising: 
 a) a polymerizable, surface active agent 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; and    b) water.    
     
     
         63 . An aqueous, surface active solution, according to  claim 52 , comprising: 
 a) a polymerizable, surface active agent 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; and    b) water.    
     
     
         64 . An aqueous, surface active solution, according to  claim 52 , comprising: 
 a) a polymerizable, surface active agent 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 n=1-10; and    b) water.    
     
     
         65 . An aqueous, surface active solution, according to  claim 52 , comprising: 
 a) a polymerizable, surface active agent 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; and    b) water.    
     
     
         66 . An aqueous, surface active solution, according to  claim 52 , comprising: 
 a) a polymerizable, surface active agent 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; and    b) water.    
     
     
         67 . An aqueous, surface active solution, according to  claim 52 , comprising: 
 a) a polymerizable, surface active agent 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 alky/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; and    b) water.    
     
     
         68 . An aqueous, surface active solution, according to  claim 52 , comprising: 
 a) a polymerizable, surface active agent 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; wherein m=0-100; wherein n=1 or 2; wherein p=2 or 3; wherein x=1 or 2; and wherein y=1 or 2; and    b) water.    
     
     
         69 . An aqueous, surface active solution, according to  claim 52 , comprising: 
 a) a polymerizable, surface active agent 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; and wherein the number of carbon atoms represented by (R 1 ) n  is at least about 5 when m=0 and q=1; and    b) water.