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US 7,094,490 B2Granted
Ion conductive block copolymers
AssigneePolyfuel, Inc.
InventorsShuguang Cao, Helen Xu, Thomas Jeanes, Kie Hyun Nam, Jian Ping Chen
Life of this patent
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Abstract
This invention relates to ion conductive copolymers which are useful in forming polymer electrolyte membranes used in fuel cells.
Claims15
A polymer electrolyte membrane comprising an ion conducting block copolymer comprising non-ionic and ionic regions having the formula
- {-L1-[-(AaBb)n]1-z-L2—[(SxCc—SyDd)o]zL3}j wherein
- [(AaBb)n] comprises a non-ionic block, and
- [(SxCc—SyDd)o] comprises an ionic block,
- A and C are phenyl, napthyl, terphenyl, aryl nitrile, substituted aryl nitrile. organopolysiloxane or Ar1—R1—Ar2, wherein R1 is, —C(O)—,—S(O)2—, —P(O)(C6H5)—, —C(O)—Ar3—C(O)—, or —C(O)—Ar4—S(O)2—, and Ar1, Ar2, Ar3, and Ar4 are aromatic groups or substituted aromatic groups and wherein each A and C can be the same or different;
- B and D are —O—Ar5—R2—Ar6—O—, where R2 is a single bond, a cycloaliphatic of the formula CnH2n-2,
- and Ar5 and Ar6 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 —SO3H, —COOH, —PO3H, and SO2NH2SO2Rf, where Rf is a perlyfluoridated hydrocarbon having 1–20 carbon atoms;
- wherein S may be the same or different when more than one S is present and wherein Sx is covalently attached to Cc and Sy is covalently attached to Dd;
- 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 (AaBb)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 (SxCc—SyDd)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 ;
- L1 is a bond or an additional B, L2 is a bond or an additional A and/or D, and L3 is a bond or an additional C,
- and wherein when C is Ar1—R1—Ar2 and R1 is —C(O)—, y=0.
14 more elements
A polymer electrolyte membrane comprising an ion conductive block copolymer comprising non-ionic and ionic regions having the formula
- {-L1-[(AaBb)n-L1-(AeBf)m]1-z-L3-[-(Sx2Cg-Sy2Dh)p-L3-(Sx2Cg-Sy2Dh)p-L3-]z}j wherein
- [(AeBf)m] comprises a non-ionic block, and
- [(Sx1Cc—Sy1Dd)o-(Sx2Cg—Sy2Dh)-] comprises an ionic block, and wherein
- at least one of (AaBb)n or (Sx1Cc—Sy1Dd)o comprise a block within said ion conducting polymer and (AeBf)m and (Sx2Cg—Sy2Dh) are polymers that are random in length, composition or both;
- A and C are phenyl, napthyl, terphenyl, aryl nitrile , substituted aryl nitrile, organopolysiloxane, —Ar1—R1—Ar2—, wherein R1 is, —C(O)—,—S(O)2—, —P(O)(C6H5)—, —C(O)—Ar3—C(O)—, or—C(O)—Ar4—S(O)2—, and Ar1, Ar2, Ar3, and Ar4 are aromatic groups or substituted aromatic groups, wherein each A and C can be the same or different and wherein
- B and D are —O—Ar5—R2—Ar6—O—, where R2 is a single bond, a cycloaliphatic of the formula CnH2n-2,
- and Ar5 and Ar6 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 —SO3H, —COOH, —PO3H, and SO2NH2SO2Rf, where Rf is a perlyfluoridated aliphatic having 1–20 carbon atoms;
- wherein S may be the same or different when more than one S is present and wherein Sx1 and Sy1 are covalently attached to Cc and Dd respectively and Sx2 and Sy2 are covalently attached to Cg and Dh respectively;
- 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 (AaBb)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 (SxCc—SyDd)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 (AeBf)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 (SxCg—SyDh)p;
- x1 and y1 are respectively the percentage of Cc and Dd which contain S, y2 and y2 are preferably the percentage of Cg and Dh which contains S wherein at least one of x1, x2,y1 or y2 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 L1 is independently a bond or an additional A and/or B;
- each L2 is independently a bond or an additional A and/or D;
- each L3 is independently a bond or an additional C and/or D;
- m is between 0 and 100 and p is between 0- and 100;
- and wherein when p=0 and m=0, and C is —Ar1—R1—Ar2—and R1 is —C(O)—, y1=0.
20 more elements
Dependencies are inferred from the claim text.