Perfluoroamidated and hydrolyzed maleic anhydride copolymers

Abstract

A composition which provides stain resistance and soil resistance to substrates comprising a copolymer of Formula 1 wherein D is at least one vinyl monomer selected from the group consisting of aryl olefin, vinyl ether, allyl ether, alpha olefin and diene; each M is independently H, NH 4 , Ca, Mg, Al, or a Group I metal; R is H, a C 1 -C 16 alkyl group, or an arylalkyl group; R f is a fully fluorinated straight or branched C 2 to C 20 aliphatic radical, or mixture thereof, which is optionally interrupted by at least one oxygen atom; x is 1 to about 10, or a mixture thereof; k and h are each independently a positive integer; i and j are each independently zero or a positive integer, provided that i and j are not both simultaneously zero; the molar ratio of k to (h+i+j) is from about 3:1 to about 1:3, and the molar ratio of h to (i+j) is from about 1:99 to about 22:78 is disclosed.

1 . A copolymer comprising the monomers of Formula 1  
     
       
         
         
             
             
         
       
     
     wherein 
 D is at least one vinyl monomer selected from the group consisting of aryl olefin, vinyl ether, allyl ether, alpha olefin and diene;  
 each M is independently H, NH 4 , Ca, Mg, Al, or a Group I metal;  
 R is H, a C 1 -C 16  alkyl group, or an arylalkyl group;  
 R f  is a fully fluorinated straight or branched C 2  to C 20  aliphatic radical, or mixture thereof, which is optionally interrupted by at least one oxygen atom;  
 x is 1 to about 10, or a mixture thereof;  
 k and h are each independently a positive integer;  
 i and j are each independently zero or a positive integer, provided that i and j are not both simultaneously zero;  
 the molar ratio of k to (h+i+j) is from about 3:1 to about 1:3, and the molar ratio of h to (i+j) is from about 1:99 to about 22:78.  
 
   
   
       2 . The composition of  claim 1  wherein R f  is a perfluoroalkyl radical having the formula F(CF 2 CF) n , wherein n is 1 to about 10, or mixtures thereof.  
   
   
       3 . The composition of  claim 1  wherein D is styrene, butylvinyl ether, phenyl allyl ether, 1-octene, or 1,3-butadiene.  
   
   
       4 . The composition of  claim 1  wherein M is H, Na or K, or wherein one M is H and the others are Na or K.  
   
   
       5 . The composition of  claim 1  in the form of a dispersion or solution.  
   
   
       6 . The composition of  claim 1  further comprising a surfactant, stain resist agent, soil resist agent, water repellent, oil repellent, antistatic agent, antimicrobial agent, softener, antioxidant, light fastness agent, color fastness agent, or water.  
   
   
       7 . The composition of  claim 1  prepared by contacting a maleic anhydride copolymer with a N-(perfluoroalkylalkyl) amine.  
   
   
       8 . The composition of  claim 7  wherein the N-(perfluoroalkylalkyl) amine is of formula 2  
       R f —(CH 2 ) x NRH   Formula 2  
     wherein 
 R f  is perfluoroalkyl radical having the formula F(CF 2 CF) n , wherein n is 1 to about 10, or mixtures thereof, and  
 x is 1 to about 10.  
 
   
   
       9 . The composition of  claim 1  having a molar ratio of h to (i+j) of from about 5:95 to about 20:80.  
   
   
       10 . The composition of  claim 1  wherein the molecular weight is at least 800.  
   
   
       11 . A method of providing stain resistance and soil resistance to substrates comprising application in a single step to said substrate of the composition of Formula 1  
     
       
         
         
             
             
         
       
     
     wherein 
 D is at least one vinyl monomer selected from the group consisting of aryl olefin, vinyl ether, allyl ether, alpha olefin and diene;  
 each M is independently H, NH 4 , Ca, Mg, Al, or a Group I metal;  
 R is H, a C 1 -C 16  alkyl group, or an arylalkyl group;  
 R f  is a fully fluorinated straight or branched C 2  to C 20  aliphatic radical, or mixture thereof, which is optionally interrupted by at least one oxygen atom;  
 x is 1 to about 10, or a mixture thereof;  
 k and h are each independently a positive integer;  
 i and j are each independently a positive integer, or i is zero and j is a positive integer;  
 such that the molar ratio of k to (h+i+j) is from about 3:1 to about 1:3, and the molar ratio of h to (i+j) is from about 1:99 to about 22:78.  
 
   
   
       12 . The method of  claim 11  wherein the composition is applied to fibrous substrates at from about 100 ppm to about 1000 ppm by weight of substrate.  
   
   
       13 . The method of  claim 11  wherein the composition is applied as an aqueous dispersion or solution.  
   
   
       14 . The method of  claim 11  wherein the composition is applied by means of exhaustion, spray, foam, flex-nip, nip, pad, kiss-roll, beck, skein, winch, liquid injection, overflow flood, brush, roll, spray or immersion.  
   
   
       15 . The method of  claim 11  wherein the substrate is heated after application of the composition.  
   
   
       16 . The method of  claim 11  wherein the composition is applied in the presence of a surfactant, stain resist agent, soil resist agent, water repellent, oil repellent, antistatic agent, antimicrobial agent, softener, antioxidant, light fastness agent, color fastness agent, or water.  
   
   
       17 . A substrate to which has been applied a composition of Formula 1  
     
       
         
         
             
             
         
       
     
     wherein 
 D is at least one vinyl monomer selected from the group consisting of aryl olefin, vinyl ether, allyl ether, alpha olefin and diene;  
 each M is independently H, NH 4 , Ca, Mg, Al, or a Group I metal;  
 R is H, a C 1 -C 16  alkyl group, or an arylalkyl group;  
 R f  is a fully fluorinated straight or branched C 2  to C 20  aliphatic radical, or mixture thereof, which is optionally interrupted by at least one oxygen atom;  
 x is 1 to about 10, or a mixture thereof;  
 k and h are each independently a positive integer;  
 i and j are each independently a positive integer, or i is zero and j is a positive integer;  
 the molar ratio of k to (h+i+j) is from about 3:1 to about 1:3, and the molar ratio of h to (i+j) is from about 1:99 to about 22:78.  
 
   
   
       18 . The substrate of  claim 17  selected from the group consisting of a fibrous substrate and a hard surface substrate.  
   
   
       19 . The substrate of  claim 18  which is a fiber, fabric, textile, carpet or leather.  
   
   
       20 . The substrate of  claim 19  which is a polyamide, nylon, wool, polyester, polyolefin, polyaramid, acrylic, wool, cotton, jute, sisal, sea grass, coir and blends thereof.  
   
   
       21 . The substrate of  claim 18  which is stone, masonry, concrete, unglazed tile, brick, porous clay, granite, limestone, grout, mortar, marble, wood, gypsum board, terrazzo, and composite materials.