Ionomers and methods of making same and uses thereof

Patent metadata

Field	Value
Publication number	US-9577279-B2
Application number	US-201113991571-A
Country	US
Kind code	B2
Filing date	Dec 5, 2011
Priority date	Dec 5, 2010
Publication date	Feb 21, 2017
Grant date	Feb 21, 2017

Abstract

Phosphazenium-based ionomers and methods of making them are disclosed. The ionomers are useful in making membranes for fuel cells and other devices that benefit from extremely base-stable membranes. The polymers (ionomers) contain repeating units of formula:

in which all of R 1 , R 2 , W, Y and Z are hydrocarbon.

First claim

The invention claimed is:

1. A polymer comprising a plurality of phosphazenium-containing repeating units (PRU) of formula

wherein R 1a , R 1b , R 1c , R 1d (collectively R 1 ) and R 2b , R 2c and R 2d (collectively R 2 ) are independently chosen from H, (C 1 -C 15 )alkyl, (C 5 -C 10 )cycloalkyl and a point of attachment to a bivalent (C 1 -C 20 )hydrocarbon residue; or
taken together, any pair of R 1 , R 2 form a 5 or 6-membered ring;
W is a direct bond or (C 1 -C 10 )hydrocarbon;
Y is a direct bond or (C 1 -C 10 )hydrocarbon;
Z 1 is a direct bond;
wavy lines indicate the points of attachment to adjacent repeating units of the polymer, and
X is any counterion.

2. A polymer according to claim 1 wherein W is a direct bond or (C 1 -C 10 )alkylene;
Y is a direct bond or (C 1 -C 10 )alkylene.

3. A polymer according to claim 1 wherein all R 1 are methyl and all R 2 are chosen from (C 1 -C 10 )alkyl, (C 5 -C 10 )cycloalkyl and a point of attachment to a bivalent hydrocarbon residue.

4. A polymer according to claim 3 wherein from one to three R 2 are points of attachment to a bivalent hydrocarbon residue and the remainder of R 2 are chosen from cyclopentyl, cyclohexyl and t-butyl.

5. A polymer according to claim 4 wherein one or two of R 2 are points of attachment to a bivalent hydrocarbon residue and the remainder are cyclohexyl.

6. A polymer according to claim 1 wherein said bivalent hydrocarbon residue is of formula:

wherein
W is a direct bond or (C 1 -C 10 )hydrocarbon;
Y is a direct bond or (C 1 -C 10 )hydrocarbon;
Z 1 is a direct bond;
@ is the point of attachment to a nitrogen of phosphazenium; and
wavy lines indicate the points of attachment to adjacent repeating units of the ionomer.

7. A polymer according to claim 2 wherein W is (CH 2 ) 1-5 and Y is (CH 2 ) 1-5 .

8. A polymer according to claim 1 additionally comprising a plurality of HRU of formula:

wherein
W is independently chosen from a direct bond and (C 1 -C 10 )hydrocarbon;
Y is independently chosen from a direct bond and (C 1 -C 10 )hydrocarbon;
Z 2 is hydrogen or (C 1 -C 10 )hydrocarbon; and
wavy lines indicate the points of attachment to adjacent repeating units of the ionomer.

9. A polymer according to claim 8 additionally comprising a plurality of crosslinking repeating units.

10. A polymer according to claim 9 wherein said crosslinking repeating units are of formula:

wherein Z 3 is a (C 1 -C 20 )hydrocarbon.

11. A polymer according to claim 10 wherein Z 3 is phenylene or (CH 2 ) 1-20 .

12. A membrane comprising a polymer according to claim 1 .

Assignees

• Coates Geoffrey W
• Noonan Kevin
• Univ Cornell

Inventors

• Coates Geoffrey W
• Noonan Kevin

Classifications

• Y02E60/523

  Cross-Sectional Technologies · mapped topic

• H01M8/103 Primary

  having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh] · CPC title

• C08F230/02

  containing phosphorus · CPC title

• H01M8/1034

  having phosphorus, e.g. sulfonated polyphosphazenes [S-PPh] · CPC title

• C08F8/40 Primary

  Introducing phosphorus atoms or phosphorus-containing groups · CPC title