Ion conductive block copolymers

Abstract

This invention relates to ion conductive copolymers which are useful in forming polymer electrolyte membranes used in fuel cells.

1 . An ion conductive block copolymer composition comprising non-ionic and ionic regions having the formula  
       {-[-L 1 -(A a B b ) n ] 1-z L 2 -[-(S x C c -S y D d ) o -] z L 3 } j  wherein  -[-(A a B b ) n ] 1-z - comprises a non-ionic polymer, and    -[-(S x C c -S y D d ) o -] z  comprises an ionic polymer, and wherein    at least one of said non-ionic or ionic polymers comprises a block within said ion conducting copolymer;    A and C are phenyl, napthyl, terphenyl, aryl nitrile, substituted aryl nitrile, organopolysiloxane—Ar 1 —R 1 —Ar 2 —, where R 1  is, —C(O)—, —S(O) 2 —, —P(O)(C 6 H 5 )—, —C(O)—Ar 3 —C(O)—, or —C(O)—Ar 4 —S(O) 2 —, and Ar 1 , Ar 2 , Ar 3 , and Ar 4  are aromatic groups or substituted aromatic groups and wherein each A and C can be the same or different;    B and D are —O—Ar 5 —R 2 —Ar 6 —O—, where R 2  is a single bond, a cycloaliphatic of the formula C n H 2n-2 ,                          and Ar 5  and Ar 6  are aromatic groups or substituted aromatic groups and wherein each B and D can be the same or different;    S is an ion conducting group selected from the group —SO 3 H, —COOH, —PO 3 H, and SO 2 NH 2 SO 2 R f , where R f  is a polyfluoridated hydrocarbon having 1-20 carbon atoms;    wherein S may be the same or different when more than one S is present;    n is an integer between 1 and 100;    o is an integer between 1 and 100;    a and b are integers each between 1 and n, where a indicates the number of different A and b the number of different B present in the non-ionic polymer (A a B b ) n ;    c and d are integers between 1 and o, where c indicates the number of different C and d the number of different D present in the ionic polymer (S x C c -S y D d ) o ;    x and y are respectively the percentage of C and D which contain S, wherein at least one of x or y is greater than 0%;    z is o divided by the sum of n and o and has a range from 0.001 to 1.0;    j is an integer between 1 and 200 and L 1  is a bond or an additional B, L 2  is a bond or an additional A and/or D, and L 3  is a bond or an additional D.    
   
   
       2 . The ion conductive polymer of  claim 1  wherein S is randomly distributed within said ionic polymer.  
   
   
       3 . The ion conductive polymer of  claim 1  wherein S is in predetermined positions within said ionic polymer.  
   
   
       4 . The ion conductive polymer of  claim 1  wherein said ionic and non-ionic polymers comprise blocks in said ion conductive polymer.  
   
   
       5 . The ion conductive polymer of  claim 1  wherein o is between 2 and 20, and A and C are Ar 1 —C(O)—Ar 2 , B and D are same or different of cyclohexydyl or fluorenyl, S is SO 3 H, x+y is between 20 and 40%, z is between 0.2 and 0.5 and j is an integer between 60 and 150.  
   
   
       6 . An ion conductive block copolymer composition comprising non-ionic and ionic regions having the formula  
       {-[-L i -(A a B b ) n -L 1 -(A e B f ) m ] 1-z -L 2 -[-(S x1 C c -S y1 D d ) o -L 3 -(S x2 C g -S y2 D h ) p -L 3 -] z } j  wherein  -[-(A a B b ) n -(A e B f ) m ] 1-z - comprises a non-ionic polymer, and    -[-(S x1 C c -S y1 D d ) o -(S x2 C g -S y2 D h )-] z  comprises an ionic polymer, and wherein    at least one of (A a B b ) n  or (S x1 C c -S y1 D d ) o  are polymers comprising a block within said ion conducting polymer and (A e B f ) m ] and -(S x2 C g -S y2 D h ) are polymers which are random in length composition or both;    A and C are phenyl, napthyl, terphenyl, aryl nitrile, substituted aryl nitrile, organopolysiloxane—Ar 1 —R 1 —Ar 2 —, where R 1  is, —C(O)—, —S(O) 2 —, —P(O)(C 6 H 5 )—, —C(O)—Ar 3 —C(O)—, or —C(O)—Ar 4 —S(O) 2 , and Ar 1 , Ar 2 , Ar 3 , and Ar 4  are aromatic groups of substituted aromatic groups wherein each A and C can be the same or different;    B and D are —O—Ar 5 —R 2 —Ar 6 —O—, where R 2  is a single bond, a cycloaliphatic of the formula C n H 2n-2 ,                          and Ar 5  and Ar 6  are aromatic groups or substituted aromatic groups, wherein each B and D can be the same or different;    S is an acidic or basic group covalently attached to C and/or D selected from the group —SO 3 H, —COOH, —PO 3 H, and SO 2 NH 2 SO 2 R f , where R f  is a polyfluoridated aliphatic having 1-20 carbon atoms; wherein S may be the same or different when more than one S is present;    n is an integer between 1 and 200;    m is an integer between 1 and 200;    a and b are integers each between 1 and n, where a indicates the number of different A and b the number of different B present in the non-ionic polymer (A a B b ) n ;    c and d are integers between 1 and 0, where c indicates the number of different C and d the number of different D present in the hydrophilic polymer (S x C c -S y D d ) o ;    e and f are integers each between 0 and m, where e indicates the number of different C and f the number of different D present in the ionic polymer (A e B f ) m ;    g and h are integers between 0 and p, where g indicates the number of different C and h the number of different D present in the ionic polymer (S x C g -S y D h ) p ;    X 1  and Y 1  are respectively the percentage of C c  and D d  which contain S, X 2  and Y 2  are preferably the percentage of C g  and D h  which contains S wherein at least one of X 1 , X 2 , Y 1  or Y 2  is greater than 0%;    z is o plus p divided by the sum of m, n, o and p, where z has a range of from 0.001 to 1.0;    j is an integer between 1 and 200;    each L 1  is independently a bond or an additional A and/or B;    each L 2  is independently a bond or an additional A and/or D; and    each L 3  is independently a bond or an additional C and/or D.    m is between 0 and 100 and p is between O— and 100.    
   
   
       7 . The ion conductive copolymer of  claim 6  wherein (A a B b ) n  and (S x1 C c -S y1 D d ) comprise blocks within said ion conductive block copolymer.  
   
   
       8 . The ion conducting polymer of  claim 6  wherein the ion conducting groups S are randomly distributed in the ionic polymer.  
   
   
       9 . The ion conductive polymer of  claim 6  wherein the ion conducting groups S are located in a predetermined position within said ionic polymer.  
   
   
       10 . The ion conductive polymer of  claim 6  wherein m and p are random numbers.  
   
   
       11 . The ion conductive polymer composition of  claim 5  wherein O is between 2 and 20, N is between 2 and 20, A and C are Ar 1 —C(O)—Ar 2 , B and D are  
     
       
         
         
             
             
         
       
     
     S is SO 3 H, x+y is between 20 and 40%, z is between 0.2 and 0.5 and j is an integer between 60 and 150.