Liquid compositions of fluorinated anion exchange polymers

Patent metadata

Field	Value
Publication number	US-9580592-B2
Application number	US-201213980601-A
Country	US
Kind code	B2
Filing date	Jan 18, 2012
Priority date	Jan 21, 2011
Publication date	Feb 28, 2017
Grant date	Feb 28, 2017

Abstract

A liquid composition comprising:
a liquid medium comprising at least one aprotic polar organic solvent and less than 25 wt % based on the total weight of the composition of an alcohol; and at least 5 wt % based on the total weight of the composition of at least one fluorinated anion exchange polymer comprising a fluorocarbon backbone and side-chains covalently attached to the backbone having terminal groups of formula (I): —SO 2 NR 1 Q + X − , wherein Q + is a group comprising at least one quaternary nitrogen atom, and R 1 is H or a C 1 -C 20 alkyl group, or forms a ring together with a group in Q + , wherein the ring contains 2 to 10 carbon atoms and, optionally, up to 4 heteroatoms; and X − is an anion selected among the group consisting of organic anions and lipophilic inorganic anions is disclosed. The liquid composition is suitable for the preparation of ion exchange membranes and as binders for electrocatalytic layers for use in electrochemical applications.

First claim

The invention claimed is:

1. A liquid composition comprising:
a liquid medium comprising at least one aprotic polar organic solvent and less than 25 wt % based on the total weight of the liquid composition of an alcohol; and
at least 5 wt % based on the total weight of the liquid composition of at least one fluorinated anion exchange polymer (P) comprising a fluorocarbon backbone and side-chains covalently attached to the backbone having terminal groups of formula (I): —SO 2 NR 1 Q + X − , wherein Q + is a group comprising at least one quaternary nitrogen atom, and R 1 is H or a C 1 -C 20 alkyl group, or forms a ring together with a group in Q + , wherein the ring contains 2 to 10 carbon atoms and, optionally, up to 4 heteroatoms; and X − is an anion selected from the group consisting of organic anions and lipophilic inorganic anions.

2. The liquid composition according to claim 1 wherein X − is an organic anion selected from the group consisting of R A1 SO 3 − , wherein R A1 is a C 1 -C 20 linear or branched, optionally fluorinated, alkyl or substituted or non-substituted aryl group, and of R A2 COO − , wherein R A2 is a C 1 -C 20 linear or branched, optionally fluorinated, alkyl or substituted or non-substituted aryl group.

3. The liquid composition according to claim 1 wherein X − is a lipophilic inorganic anion selected from the group consisting of I − , ClO 4 − , SCN − , and NO 3 − .

4. The liquid composition according to claim 1 wherein the aprotic organic solvent is selected from the group consisting of aliphatic and cycloaliphatic amides and aliphatic sulphoxides.

5. The liquid composition according to claim 1 wherein the fluorinated backbone of said fluorinated anion exchange polymer (P) is a linear random polymer chain comprising repeating units represented by the formula (II):

wherein R F is F, Cl, —CF 3 ; p is an integer of 0 to 16, q is an integer of 1 to 10 and the ratio of p′/q′ is in the range 0.5 to 16 where p′ is an average value of all p in the repeating units and q′ is an average value of all p in the repeating units.

6. The liquid composition according to claim 5 wherein the fluorinated anion exchange polymer (P) comprises repeating units represented by formula (III):

wherein R F is selected from the group consisting of F, Cl, and —CF 3 ; R′ F is selected from the group consisting of F, Cl, and —CF 3 ; m is an integer equal to 0 or 1, n is an integer from 0 to 10; R 1 , Q + and X − are as defined in claim 1 .

7. The liquid composition according to claim 1 wherein the group of formula (I) has the following structure:

wherein Y is a C 6 -C 10 aryl group, a heteroaryl group or CR 7 R 8 wherein R 7 is H, a halogen atom or a C 1 -C 20 alkyl group or forms a ring together with one of R 2 , R 5 , or R 8 , and R 8 is H, a halogen atom or a C 1 -C 20 alkyl group or forms a ring together with one of R 3 , R 6 , or R 7 , each of the rings formed by R 7 or R 8 containing 2 to 10 carbon atoms and optionally 1 to 4 heteroatoms, and the heteroaryl group contains 5 to 10 ring atoms; R 1 is H or a C 1 -C 20 alkyl group, or forms a ring together with one of R 2 or R 5 , wherein the ring contains 2 to 10 carbon atoms and 1 to 4 heteroatoms; R 2 is a C 1 -C 20 alkyl group or forms a ring together with one of R 1 , R 3 , R 5 , R 7 or R 9 , wherein the ring contains 2 to 10 carbon atoms and 1 to 4 heteroatoms; R 3 is a C 1 -C 20 alkyl group or forms a ring together with one of R 2 , R 6 , R 8 or R 10 , wherein the ring contains 2 to 10 carbon atoms and 1 to 4 heteroatoms; R 4 is a C 1 -C 20 alkyl group; R 5 is H, a halogen atom or a C 1 -C 20 alkyl group, or forms a ring together with one of R 1 , R 2 , R 7 or R 9 , wherein the ring contains 2 to 10 carbon atoms and optionally 1 to 4 heteroatoms; R 6 is H, a halogen atom or a C 1 -C 20 alkyl group, or forms a ring together with one of R 3 , R 8 or R 10 , wherein the ring contains 2 to 10 carbon atoms and optionally 1 to 4 heteroatoms; each R 9 is independently H, a halogen atom or a C 1 -C 20 alkyl group, or forms a ring together with one of R 2 or R 5 , wherein the ring contains 2 to 10 carbon atoms and optionally 1 to 4 heteroatoms; each R 10 is independently H, a halogen atom or a C 1 -C 20 alkyl group, or forms a ring together with one of R 3 or R 6 , wherein the ring contains 2 to 10 carbon atoms and optionally 1 to 4 heteroatoms; z is an integer from 0 to 4; and wherein the ring structures in the group of formula (II) can be bridged by C 1 -C 4 alkylene groups.

8. The liquid composition according to claim 7 wherein R 1 =H, R 2 =R 3 =CH 3 , R 5 =R 6 =R 9 =R 10 =H, z=1 and Y=CR 8 R 9 , wherein R 8 =R 9 =CH 3 .

9. The liquid composition according to claim 1 further comprising catalyst particles.

10. A process for preparing the liquid composition of claim 1 , said process comprising the step of dissolving at least one fluorinated anion exchange polymer (P) comprising a fluorocarbon backbone and side-chains covalently attached to the backbone having terminal groups of formula (I): —SO 2 NR 1 Q + X − in a liquid medium comprising at least one aprotic polar organic solvent and less than 25 wt % based on the total weight of the liquid composition of an alcohol, wherein R 1 , Q + and X − are as defined in claim 1 .

Assignees

• Petricci Silvia
• Guarda Pier Antonio
• Oldani Claudio
• Marchionni Giuseppe
• Solvay Specialty Polymers It

Inventors

• Petricci Silvia
• Guarda Pier Antonio
• Oldani Claudio
• Marchionni Giuseppe

Classifications

• C08L29/10 Primary

  Homopolymers or copolymers of unsaturated ethers (C08L35/08 takes precedence) · CPC title

• C08J5/20

  Manufacture of shaped structures of ion-exchange resins · CPC title

• C08F8/44 Primary

  Preparation of metal salts or ammonium salts · CPC title

• B01J31/08

  Ion-exchange resins · CPC title

• C08J2327/12

  containing fluorine atoms · CPC title