Fluorinated polymer blocks for PEM applications
A fluorine-containing polymer segment includes at least one substituent for proton transfer that has one or more fluorine atoms. The fluorine-containing polymer segment is useful for forming hydrophilic polymer blocks that are used in block copolymers. Block copolymers useful for fuel cell applications incorporate the hydrophilic polymer blocks formed from the fluorine containing polymer segments.
1. A block copolymer comprising a hydrophilic polymer block D w , comprising a polymer segment D having formula 3:
wherein:
U 1 comprises a cycloalkyl substituted with at least one fluorine atom;
Y 1 is —O—, —S—, —CO—, —SO 2 —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —P(O)(T 1 )—, —C(CH 3 )(T 1 )—, —P(O)(R 4 )—, diphenyl methylene, diphenyl silicon, fluorenyl, an alkylene, a bond directly to the next moiety, or
R 1 , R 2 , and R 3 are each independently H, C 1-10 alkyl, C 6-18 aryl, C 6-18 aralkyl, SO 3 H, —SO 3 − M + , —COOH, —COO − M + , —PO 3 H 2 , —PO 3 H − M + , or —PO 3 2− M 2 + , —PO 3 2− M 2+ ;
R 4 is H, C 1-10 alkyl, C 6-18 aryl, or C 6-18 aralkyl;
T 1 comprises a component selected from the group consisting of substituents having fluorine atoms, —SO 3 H, —SO 3 − M + , —COOH, —COO − M + , —PO 3 H 2 , —PO 3 H − M + , —PO 3 2− M 2 + , and —PO 3 2− M 2+ and M is an alkali or alkaline-earth metal, ammonium, or alkylammonium;
w is an integer greater than 1;
i is an integer from 1 to 6; and
q is an integer from 1 to 6.
2. The block copolymer of claim 1 wherein T 1 is given by formula 4:
wherein:
Y 2 and Y 4 are each independently absent, —O—, —S—, —CO—, —SO 2 —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —P(O)(R 4 )—, diphenyl methylene, diphenyl silicon, fluorenyl, or an alkylene;
U 2 is a moiety having at least one fluorine atom;
R 4 is H, C 1-10 alkyl, C 6-18 aryl, or C 6-18 aralkyl;
R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , and R 13 are each independently H, CF 3 , C 1-10 alkyl, C 1-10 alkyl substituted with at least one fluorine atom, perfluorinated C 1-10 alkyl, C 3 cycloalkyl, C 1-10 cycloalkyl substituted with at least one fluorine atom, perfluorinated C 1-10 cycloalkyl, C 6-18 aryl, C 6-18 aryl substituted with at least one fluorine atom, perfluorinated C 6-18 aryl, C 6-18 aralkyl, C 6-18 aralkyl substituted with at least one fluorine atom, perfluorinated C 6-18 aralkyl, arylSO 3 H, —SO 3 H, —SO 3 − M + , —COOH, —COO − M + , —PO 3 H 2 , —PO 3 H − M + , —PO 3 2− M 2 + or —PO 3 2− M 2+ ;
M is a metal, ammonium, or alkylamonium;
r is an integer from 0 to 30;
l is an integer from 0 to 30;and
j is an integer from 0 to 30;
with the proviso that when j>1, the Y 2 between sequential aromatic rings are the same or different and the R 5 , R 6 , R 7 , R 8 , and R 9 on sequential aromatic rings are the same or different and when q>1, the Y 4 between sequential aromatic rings are the same or different and the R 5 , R 6 , R 7 , R 8 , and R 9 on sequential aromatic rings are the same or different.
3. The block copolymer of claim 2 wherein U 1 and U 2 each independently comprise a branched or unbranched alkyl substituted with at least one fluorine atom or a cycloalkyl substituted with at least one fluorine atom.
4. The block copolymer of claim 3 wherein U 1 and U 2 each independently comprise a branched or unbranched C 1-10 alkyl substituted with at least one fluorine atom or a C 3-15 cycloalkyl substituted with at least one fluorine atom.
5. The block copolymer of claim 3 wherein U 1 and U 2 each independently comprise a perfluorinated alkyl or perfluorinated cycloalkyl groups.
6. An ion conductive membrane made from the block copolymer of claim 1 .
7. A block copolymer comprising a hydrophilic polymer block D w , comprising a polymer segment D having formula 3:
wherein:
T 1 is given by formula 4:
Y 1 is —O—, —S—, —CO—, —SO 2 —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —P(O)(T 1 )—, —C(CH 3 )(T 1 )—, —P(O)(R 4 )—, diphenyl methylene, diphenyl silicon, fluorenyl, an alkylene, a bond directly to the next moiety, or
Y 2 and Y 4 are each independently absent, —O—, —S—, —CO—, —SO 2 —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —P(O)(R 4 )—, diphenyl methylene, diphenyl silicon, fluorenyl, or an alkylene;
R 1 , R 2 , and R 3 are each independently H, C 1-10 alkyl, C 6-18 aryl, C 6-18 aralkyl, SO 3 H, —SO 3 − M + , —COOH, —COO − M + , —PO 3 H 2 , —PO 3 H − M + , or —PO 3 2− M 2 + , —PO 3 2− M 2+ ;
R 4 is H, C 1-10 alkyl, C 6-18 aryl, or C 6-18 aralkyl;
R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , and R 13 are each independently H, CF 3 , C 1-10 alkyl, C 1-10 alkyl substituted with at least one fluorine atom, perfluorinated C 1-10 alkyl, C 3 cycloalkyl, C 1-10 cycloalkyl substituted with at least one fluorine atom, perfluorinated C 1-10 cycloalkyl, C 6-18 aryl, C 6-18 aryl substituted with at least one fluorine atom, perfluorinated C 6-18 aryl, C 6-18 aralkyl, C 6-18 aralkyl substituted with at least one fluorine atom, perfluorinated C 6-18 aralkyl, arylSO 3 H, —SO 3 H, —SO 3 − M + , —COOH, —COO − M + , —PO 3 H 2 , —PO 3 H − M + , —PO 3 2− M 2 + , or —PO 3 2− M 2+ ;
w is an integer;
i is an integer from 1 to 6;
q is an integer from 1 to 6; and
M is a metal, ammonium, or alkylamonium;
r is an integer from 0 to 30;
l is an integer from 0 to 30;
j is an integer from 0 to 30;
with the proviso that when j>1, the Y 2 between sequential aromatic rings are the same or different and the R 5 , R 6 , R 7 , R 8 , and R 9 on sequential aromatic rings are the same or different and when q>1, the Y 4 between sequential aromatic rings are the same or different and the R 5 , R 6 , R 7 , R 8 , and R 9 on sequential aromatic rings are the same or different; and
U 1 and U 2 each independently comprise a moiety having formulae 5-8:
8. The block copolymer of claim 7 , wherein block D w has formula 9:
and n is an integer.
9. The block copolymer of claim 7 wherein T 1 comprises a moiety having formula 10:
10. The block copolymer of claim 9 wherein the moiety having formula 10 is made by reaction scheme 1:
11. A block copolymer comprising a hydrophilic polymer block D w , comprising a polymer segment D having formula 3:
wherein:
U 1 is a moiety having at least one fluorine atom;
Y 1 is —O—, —S—, —CO—, —SO 2 —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —P(O)(T 1 )—, —C(CH 3 )(T 1 )—, —P(O)(R 4 )—, diphenyl methylene, diphenyl silicon, fluorenyl, an alkylene, a bond directly to the next moiety, or
R 1 , R 2 , and R 3 are each independently H, C 1-10 alkyl, C 6-18 aryl, C 6-18 aralkyl, SO 3 H, —SO 3 − M + , —COOH, —COO − M + , —PO 3 H 2 , —PO 3 H − M + , or —PO 3 2− M 2 + , —PO 3 2− M 2+ ;
R 4 is H, C 1-10 alkyl, C 6-18 aryl, or C 6-18 aralkyl;
T 1 comprises a component selected from the group consisting of substituents having fluorine atoms, —SO 3 H, —SO 3 − M + , —COOH, —COO − M + , —PO 3 H 2 , —PO 3 H − M + ,—PO 3 2− M 2 + , and —PO 3 2− M 2+ and M is an alkali or alkaline-earth metal, ammonium, or alkylammonium;
w is an integer greater than 1;
i is an integer from 3 to 6; and
q is an integer from 1 to 6.
12. A block copolymer comprising a hydrophilic polymer block D w , comprising a polymer segment D having formula 3:
wherein:
T 1 is given by formula 4:
Y 1 is —O—, —S—, —CO—, —SO 2 —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —P(O)(T 1 )—, —C(CH 3 )(T 1 )—, —P(O)(R 4 )—, diphenyl methylene, diphenyl silicon, fluorenyl, an alkylene, a bond directly to the next moiety, or
Y 2 and Y 4 are each independently absent, —O—, —S—, —CO—, —SO 2 —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —P(O)(R 4 )—, diphenyl methylene, diphenyl silicon, fluorenyl, or an alkylene;
R 1 , R 2 , and R 3 are each independently H, C 1-10 alkyl, C 6-18 aryl, C 6-18 aralkyl, SO 3 H, —SO 3 − M 30 , —COOH, —COO − M − , —PO 3 H 2 , —PO 3 H − M + , or —PO 3 2− M 2 + , —PO 3 2− M + ;
R 4 is H, C 1-10 alkyl, C 6-18 aryl, or C 6-18 aralkyl;
R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , and R 13 are each independently H, CF 3 , C 1-10 alkyl, C 1-10 alkyl substituted with at least one fluorine atom, perfluorinated C 1-10 alkyl, C 3 cycloalkyl, C 1-10 cycloalkyl substituted with at least one fluorine atom, perfluorinated C 1-10 cycloalkyl, C 6-18 aryl, C 6-18 aryl substituted with at least one fluorine atom, perfluorinated C 6-18 aryl, C 6-18 aralkyl, C 6-18 aralkyl substituted with at least one fluorine atom, perfluorinated C 6-18 aralkyl, arylSO 3 H, —SO 3 H, —SO 3 − M + , —COOH, —COO − M + , —PO 3 H 2 , —PO 3 H − M + , —PO 3 2− M 2 + , or —PO 2− M 2+ ;
w is an integer;
i is an integer from 0 to 6;
q is an integer from 0 to 6, with the proviso that i and q are not both simultaneously 0 and that when q is 0, T 1 includes a moiety having at least one fluorine atom; and
M is a metal, ammonium, or alkylamonium;
r is an integer from 0 to 30;
l is an integer from 0 to 30;
j is an integer from 0 to 30;
with the proviso that when j>1, the Y 2 between sequential aromatic rings are the same or different and the R 5 , R 6 , R 7 , R 8 , and R 9 on sequential aromatic rings are the same or different and when q>1, the Y 4 between sequential aromatic rings are the same or different and the R 5 , R 6 , R 7 , R 8 , and R 9 on sequential aromatic rings are the same or different; and
U 1 and U 2 each independently comprise a moiety having formulae 5-8:
wherein block D w has formula 9:
and n is an integer.
13. A block copolymer comprising a hydrophilic polymer block D w , comprising a polymer segment D having formula 3:
wherein:
T 1 is given by formula 4:
Y 1 is —O—, —S—, —CO—, —SO 2 —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —P(O)(T 1 )—, —C(CH 3 )(T 1 )—, —P(O)(R 4 )—, diphenyl methylene, diphenyl silicon, fluorenyl, an alkylene, a bond directly to the next moiety, or
Y 2 and Y 4 are each independently absent, —O—, —S—, —CO—, —SO 2 —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —P(O)(R 4 )—, diphenyl methylene, diphenyl silicon, fluorenyl, or an alkylene;
R 1 , R 2 , and R 3 are each independently H, C 1-10 alkyl, C 6-18 aryl, C 6-18 aralkyl, SO 3 H, —SO 3 − M + , —COOH, —COO − M + , —PO 3 H 2 , —PO 3 H − M + , or —PO 3 2− M 2 + , —PO 3 2− M 2+ ;
R 4 is H, C 1-10 alkyl, C 6-18 aryl, or C 6-18 aralkyl;
R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , and R 13 are each independently H, CF 3 , C 1-10 alkyl, C 1-10 alkyl substituted with at least one fluorine atom, perfluorinated C 1-10 alkyl, C 3 cycloalkyl, C 1-10 cycloalkyl substituted with at least one fluorine atom, perfluorinated C 1-10 cycloalkyl, C 6-18 aryl, C 6-18 aryl substituted with at least one fluorine atom, perfluorinated C 6-18 aryl, C 6-18 aralkyl, C 6-18 aralkyl substituted with at least one fluorine atom, perfluorinated C 6-18 aralkyl, arylSO 3 H, —SO 3 H, —SO 3 − M + , —COOH, —COO − M + , —PO 3 H 2 , —PO 3 H − M + , —PO 3 2− M 2 + , or —PO 3 2− M 2+ ;
w is an integer;
i is an integer from 1 to 6;
q is an integer from 1 to 6; and
M is a metal, ammonium, or alkylamonium;
r is an integer from 0 to 30;
l is an integer from 0 to 30;
j is an integer from 0 to 30;
with the proviso that when j>1, the Y 2 between sequential aromatic rings are the same or different and the R 5 , R 6 , R 7 , R 8 , and R 9 on sequential aromatic rings are the same or different and when q>1, the Y 4 between sequential aromatic rings are the same or different and the R 5 , R 6 , R 7 , R 8 , and R 9 on sequential aromatic rings are the same or different; and
U 1 and U 2 each independently comprise a moiety having formulae 5-8:
wherein T 1 comprises a moiety having formula 10:
14. The block copolymer of claim 13 wherein the moiety having formula 10 is made by reaction scheme 1:
15. A block copolymer comprising a hydrophilic polymer block D w , comprising a polymer segment D having formula 3:
wherein:
U 1 is a moiety having at least one fluorine atom;
Y 1 is —O—, —S—, —CO—, —SO 2 —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —P(O)(T 1 )—, —C(CH 3 )(T 1 )—, —P(O)(R 4 )—, diphenyl methylene, diphenyl silicon, fluorenyl, an alkylene, a bond directly to the next moiety, or
R 1 , R 2 , and R 3 are each independently H, C 1-10 alkyl, C 6-18 aryl, C 6-18 aralkyl, SO 3 H, —SO 3 − M + , —COOH, —COO − M + , —PO 3 H 2 , —PO 3 H − M + , or —PO 3 2− M 2 + , —PO 3 2− M 2+ ;
R 4 is H, C 1-10 alkyl, C 6-18 aryl, or C 6-18 aralkyl;
T 1 comprises T 1 to include one of: a perflourinated acid, or a moiety that includes a cycloalkyl substituted with at least one fluorine atom:
w is an integer greater than 1;
i is an integer from 1 to 6; and
q is an integer from 1 to 6.
16. A block copolymer comprising a hydrophilic polymer block D w , comprising a polymer segment D having formula 3:
wherein:
T 1 is given by formula 4:
Y 1 is —O—, —S—, —CO—, —SO 2 —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —P(O)(T 1 )—, —C(CH 3 )(T 1 )—, —P(O)(R 4 )—, diphenyl methylene, diphenyl silicon, fluorenyl, an alkylene, a bond directly to the next moiety, or
Y 2 and Y 4 are each independently absent, —O—, —S—, —CO—, —SO 2 —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —P(O)(R 4 )—, diphenyl methylene, diphenyl silicon, fluorenyl, or an alkylene;
R 1 , R 2 , and R 3 are each independently H, C 1-10 alkyl, C 6-18 aryl, C 6-18 aralkyl, SO 3 H, —SO 3 − M + , —COOH, —COO − M + , —PO 3 H 2 , —PO 3 H − M + , or —PO 3 2− M 2 + , —PO 3 2− M 2+ ;
R 4 is H, C 1-10 alkyl, C 6-18 aryl, or C 6-18 aralkyl;
R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , and R 13 are each independently H, CF 3 , C 1-10 alkyl, C 1-10 alkyl substituted with at least one fluorine atom, perfluorinated C 1-10 alkyl, C 3 cycloalkyl, C 1-10 cycloalkyl substituted with at least one fluorine atom, perfluorinated C 1-10 cycloalkyl, C 6-18 aryl, C 6-18 aryl substituted with at least one fluorine atom, perfluorinated C 6-18 aryl, C 6-18 aralkyl, C 6-18 aralkyl substituted with at least one fluorine atom, perfluorinated C 6-18 aralkyl, arylSO 3 H, —SO 3 H, —SO 3 − M + , —COOH, —COO − M + , —PO 3 H 2 , —PO 3 H − M + , —PO 3 2− M 2 + , or —PO 3 2− M 2+ ;
w is an integer;
i is an integer from 0 to 6;
q is an integer from 0 to 6, with the proviso that i and q are not both simultaneously 0 and that when q is 0, T 1 includes a moiety having at least one fluorine atom; and
M is a metal, ammonium, or alkylamonium;
r is an integer from 0 to 30;
l is an integer from 0 to 30;
j is an integer from 0 to 30;
with the proviso that when j>1, the Y 2 between sequential aromatic rings are the same or different and the R 5 , R 6 , R 7 , R 8 , and R 9 on sequential aromatic rings are the same or different and when q>1, the Y 4 between sequential aromatic rings are the same or different and the R 5 , R 6 , R 7 , R 8 , and R 9 on sequential aromatic rings are the same or different; and
U 1 and U 2 each independently comprise a moiety having formulae 5-8:
wherein T 1 comprises a moiety having formula 10:
and wherein the moiety having formula 10 is made by reaction scheme 1: