Polymers of intrinsic microporosity

Patent metadata

Field	Value
Publication number	US-9920168-B2
Application number	US-201615543348-A
Country	US
Kind code	B2
Filing date	Feb 26, 2016
Priority date	Mar 17, 2015
Publication date	Mar 20, 2018
Grant date	Mar 20, 2018

Abstract

A polymer of intrinsic microporosity having a repeating subunit including a spirobisindane imide moiety as illustrated below.

First claim

The invention claimed is:

1. A polymer of intrinsic microporosity comprising a repeating unit as represented by Formula Ia:

wherein:
n, n′ and n″ are each 1;
L is a linking group selected from a covalent bond, ketone, sulfone group or hydrocarbon comprising from 1 to 6 carbon atoms;
R 1 , R 2 , R 3 , and R 4 are independently selected from alkyl groups comprising from 1 to 6 carbon atoms, with the proviso that:
i) R 1 and R 2 may alternatively collectively form a ketone group or a 9,9′-fluorene group, and
ii) R 3 and R 4 may collectively form a ketone group or a 9,9′-fluorene group;

R 5 and R 6 are independently selected from: a bond and an alkylene group comprising from 1 to 6 carbon atoms;
X and X′ are independently selected from: a carboxylic acid and sulfonic acid and their corresponding salt or ester, imino, amide, nitrile, hydrogen, hydroxyl and alkenyl comprising from 1 to 6 carbon atoms, with the proviso that no more than one of X and X′ is selected from hydrogen or hydroxyl; and
Y and Y′ is independently selected from hydrogen, hydroxyl or sulfonate group including its corresponding salt or ester, which may be located at any open position on the ring; and
Z and Z′ are independently selected from: carboxylic acid or sulfonate including their corresponding salts or esters; hydrogen, hydroxyl, nitrile, and alkoxy comprising from 1 to 6 carbon atoms, which may be located at any open position on the ring.

2. The polymer of claim 1 wherein Z, Z′, Y and Y′ are hydrogen or hydroxyl.

3. The polymer of claim 1 wherein R 1 , R 2 , R 3 , and R 4 are independently selected from: methyl, R 1 and R 2 collectively form a ketone, and R 3 and R 4 collectively form a ketone group.

4. The polymer of claim 1 wherein R 5 and R 6 are independently selected from a covalent bond and a methylene group.

5. The polymer of claim 1 wherein at least one X and X′ is a nitrile group.

6. The polymer of claim 1 wherein at least one of X and X′ is selected from a carboxylic acid and its corresponding salt or ester, iminocarbamate or iminocarbonate.

7. A membrane comprising the polymer of claim 1 .

8. A polymer of intrinsic microporosity comprising a repeating unit as represented by Formula Ib:

wherein:
R 1 , R 2 , R 3 , and R 4 are independently selected from alkyl groups comprising from 1 to 6 carbon atoms, with the proviso that:
i) R 1 and R 2 may alternatively collectively form a ketone group or a 9,9′-fluorene group, and
ii) R 3 and R 4 may collectively form a ketone group or a 9,9′-fluorene group;

R 5 and R 6 are independently selected from: a bond and an alkylene group comprising from 1 to 6 carbon atoms;
X and X′ are independently selected from: a carboxylic acid and sulfonic acid and their corresponding salt or ester, imino, amide, nitrile, hydrogen, hydroxyl and alkenyl comprising from 1 to 6 carbon atoms, with the proviso that no more than one of X and X′ is selected from hydrogen or hydroxyl; and
Y and Y′ is independently selected from hydrogen, hydroxyl or sulfonate group including its corresponding salt or ester, which may be located at any open position on the ring; and
Z and Z′ are independently selected from: carboxylic acid or sulfonate including their corresponding salts or esters; hydrogen, hydroxyl, nitrile, and alkoxy comprising from 1 to 6 carbon atoms, which may be located at any open position on the ring.

9. The polymer of claim 8 wherein Z, Z′, Y and Y′ are hydrogen or hydroxyl.

10. The polymer of claim 8 wherein R 1 , R 2 , R 3 , and R 4 are independently selected from: methyl, R 1 and R 2 collectively form a ketone, and R 3 and R 4 collectively form a ketone group; and wherein R 5 and R 6 are independently selected from a covalent bond and a methylene group.

11. The polymer of claim 8 wherein at least one of X and X′ is selected from: a nitrile group, carboxylic acid and its corresponding salt or ester, iminocarbamate and iminocarbonate.

Assignees

• Dow Global Technologies Llc

Inventors

• Hefner Jr Robert E
• Cramm Brian L
• Tomlinson Ian A
• Huffman Lauren M
• Roy Abhishek

Classifications

• C08G73/1007 Primary

  from tetracarboxylic acids or derivatives and diamines · CPC title

• B01D67/0006 Primary

  by chemical reactions (in-situ polymerisation, polycondensation, cross-linking or reaction for manufacturing composite membranes B01D69/125) · CPC title

• C08J5/18

  Manufacture of films or sheets · CPC title

• C08G2340/00

  Filter material · CPC title

• C08G73/1082 Primary

  wholly aromatic in the tetracarboxylic moiety · CPC title