High performance, durable polymers including poly(phenylene)

Patent metadata

Field	Value
Publication number	US-9580541-B1
Application number	US-201514933981-A
Country	US
Kind code	B1
Filing date	Nov 5, 2015
Priority date	Nov 5, 2014
Publication date	Feb 28, 2017
Grant date	Feb 28, 2017

Abstract

The present invention relates to functionalized polymers including a poly(phenylene) structure. In some embodiments, the polymers and copolymers of the invention include a highly localized concentration of acidic moieties, which facilitate proton transport and conduction through networks formed from these polymers. In addition, the polymers can include functional moieties, such as electron-withdrawing moieties, to protect the polymeric backbone, thereby extending its durability. Such enhanced proton transport and durability can be beneficial for any high performance platform that employs proton exchange polymeric membranes, such as in fuel cells or flow batteries.

First claim

The invention claimed is:

1. A composition comprising a structure having the formula (I):

or a salt thereof, wherein:
each R 3 is, independently, H, optionally substituted C 1-12 alkyl, optionally substituted C 1-12 haloalkyl, optionally substituted C 1-12 perfluoroalkyl, R S , R P , or R F , wherein R S is an acidic moiety comprising a sulfonyl group, R P is an acidic moiety comprising a phosphoryl group, and R F is an electron-withdrawing moiety selected from the group consisting of optionally substituted aryloyl, carboxyaldehyde, optionally substituted alkanoyl, and optionally substituted alkyl;
each Ar L is, independently, a bivalent linker comprising optionally substituted arylene;
each R 1 is, independently, H, R S , R P , or R F ;
each Ar M is, independently, a bivalent linker comprising optionally substituted arylene;
each q is, independently, an integer of from 1 to 5;
m is an integer of from about 1 to 500; and
wherein at least one R 1 or Ar L in formula (I) comprises R S , R P , or R F .

2. The composition of claim 1 , wherein each and every R 3 is, independently, R S , R P , or R F .

3. The composition of claim 1 , wherein R S is —SO 2 —R S1 or —SO 2 —NR N1 —R S2 or —SO 2 —NR N1 —SO 2 —R S3 , wherein each R S1 is independently, H, optionally substituted alkyl, optionally substituted haloalkyl, optionally substituted perfluoroalkyl, optionally substituted aryl, optionally substituted alkaryl, or hydroxyl; each R N1 is, independently, H or optionally substituted C 1-12 alkyl, optionally substituted aryl, or optionally substituted alkaryl; each R S2 is, independently, H, hydroxyl, optionally substituted alkyl, optionally substituted alkylsulfonyl, optionally substituted aryl, or optionally substituted alkaryl; and each R S3 is, independently, H, hydroxyl, optionally substituted alkyl, optionally substituted C 1-12 haloalkyl, optionally substituted perfluoroalkyl, optionally substituted aryl, or optionally substituted alkaryl.

4. The composition of claim 1 , wherein R P is —P(O)(OH) 2 or —O—PO(OH) 2 or —P(O)<R P1 R P2 or —P(O)<R Ar R P2 or —P(O)<R Ar R Ar , and wherein each of R P1 and R P2 is, independently, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted aryl, optionally substituted alkaryl, optionally substituted aryloxy, hydroxyl, or H; and each of R Ar is, independently, optionally substituted aryl, optionally substituted alkaryl, or optionally substituted aryloxy.

5. The composition of claim 1 , wherein each and every R 1 and Ar L in formula (I) comprises R S , R P , or R F .

6. The composition of claim 1 , wherein R F is substituted with perfluoroalkyl.

7. The composition of claim 1 , wherein Ar L is optionally substituted phenylene, optionally substituted naphthylene, or optionally substituted phenanthrylene.

8. The composition of claim 7 , wherein the optional substitution for Ar L is R S , R P , or R F .

9. The composition of claim 1 , wherein Ar M is optionally substituted phenylene, optionally substituted naphthylene, or optionally substituted phenanthrylene.

10. The composition of claim 9 , wherein the optional substitution for Ar M is R S , R P , R F , or a label.

11. The composition of claim 1 , further comprising the structure having the formula (I) covalently bonded to a structure having the formula (III′):

or a salt thereof, by way of a linking segment L,
wherein:
each R S is, independently, an acidic moiety comprising a sulfonyl group;
each R 1 is, independently, H, R S , R P , or R F , wherein R P is an acidic moiety comprising a phosphoryl group and R F is an electron-withdrawing moiety; and
each R 2 is, independently, H, R S , R P , R F , halo, optionally substituted C 1-12 alkyl, optionally substituted C 1-12 haloalkyl, optionally substituted C 1-12 perfluoroalkyl, or a label.

12. A composition comprising a structure having the formula (II):

or a salt thereof, wherein:
each R 3 is, independently, H, optionally substituted C 1-12 alkyl, optionally substituted C 1-12 haloalkyl, optionally substituted C 1-12 perfluoroalkyl, R S , R P , or R F , wherein R S is an acidic moiety comprising a sulfonyl group, R P is an acidic moiety comprising a phosphoryl group, and R F is an electron-withdrawing moiety selected from the group consisting of optionally substituted aryloyl, carboxyaldehyde, optionally substituted alkanoyl, and optionally substituted alkyl;
each Ar L is, independently, a bivalent linker comprising optionally substituted arylene;
each R 1 is, independently, H, R S , R P , or R F ;
each Ar M is, independently, a bivalent linker comprising optionally substituted arylene;
each q is, independently, an integer of from 1 to 5;
each of m and n is, independently, an integer of from about 1 to 500;
L is a linking segment; and
Ar H is a hydrophobic segment, and
wherein at least one R 1 or Ar L in formula (II) comprises R S , R P , or R F .

13. The composition of claim 12 , wherein L comprises a covalent bond, carbonyl, oxy, phosphonoyl, phosphoryl, sulfonyl, sulfinyl, sultam, imino, nitrilo, optionally substituted C 1-12 alkylene, optionally substituted C 1-12 alkyleneoxy, optionally substituted C 1-12 heteroalkylene, optionally substituted C 1-12 heteroalkyleneoxy, optionally substituted C 4-18 arylene, optionally substituted C 4-18 aryleneoxy, optionally substituted polyphenylene, or a structure of formula (I).

14. The composition of claim 12 , wherein Ar H comprises a structure of formula (I), a sulfone subunit, an arylene sulfone subunit, an ether sulfone subunit, an arylene ether subunit, a perfluoroalkyl subunit, or a perfluoroalkoxy subunit.

15. The composition of claim 12 , wherein m is less than n.

16. A composition having the formula (IV):

or a salt thereof, wherein:
each R 3 is, independently, H, R S , R P , or R F , wherein R S is an acidic moiety comprising a sulfonyl group, R P is an acidic moiety comprising a phosphoryl group, and R F is an electron-withdrawing moiety selected from the group consisting of optionally substituted aryloyl, carboxyaldehyde, optionally substituted alkanoyl, and optionally substituted alkyl;
each Ar L is, independently, a bivalent linker comprising optionally substituted arylene;
each R 1 is, independently, H, R S , R P , or R F ;
each Ar M is, independently, a bivalent linker comprising optionally substituted arylene;
each q is, independently, an integer of from 1 to 5;
m is an integer of from about 1 to 500;
L′ is a sublink;
wherein at least one R 1 or Ar L in formula (IV) comprises R S , R P , or R F ; and
each R L is, independently, a electrophilic reactive end group.

17. The composition of claim 16 , wherein L′ comprises a covalent bond, carbonyl, oxy, phosphonoyl, phosphoryl, sulfonyl, sulfinyl, sultam, imino, nitrilo, optionally substituted C 1-12 alkylene, optionally substituted C 1-12 alkyleneoxy, optionally substituted C 1-12 heteroalkylene, optionally substituted C 1-12 heteroalkyleneoxy, optionally substituted C 4-18 arylene, optionally substituted C 4-18 aryleneoxy, optionally substituted polyphenylene, or a st

Assignees

• Sandia Corp

Inventors

• Fujimoto Cy
• Pratt Harry
• Anderson Travis Mark

Classifications

• C08G61/10 Primary

  only aromatic carbon atoms, e.g. polyphenylenes · CPC title

• C08G2261/312

  Non-condensed aromatic systems, e.g. benzene · CPC title

• C08G2261/148

  Side-chains having aromatic units · CPC title

• C08G2261/46

  Diels-Alder reactions · CPC title

• C08G2261/80

  Functional group cleavage, e.g. removal of side-chains or protective groups · CPC title