Gas separation membrane, gas separation module, gas separation apparatus, and gas separation method

Patent metadata

Field	Value
Publication number	US-2018021740-A1
Application number	US-201715679160-A
Country	US
Kind code	A1
Filing date	Aug 17, 2017
Priority date	Feb 27, 2015
Publication date	Jan 25, 2018
Grant date	—

Abstract

A gas separation membrane has a gas separation layer containing a poly(benzoxazole-imide) compound in which the poly(benzoxazole-imide) compound having structural units represented by General formulae (I) and (II), or structural units represented by General formulae (I), (II) and (III) satisfies a specific molar quantity condition.

In the formulae, X and Y each represent a single bond or a specific divalent linking group; L represents a specific divalent linking group including a phenylene group; and R represents a specific group. A gas separation module and a gas separation method use the gas separation membrane. A gas separation apparatus includes the gas separation module.

First claim

What is claimed is:

1 . A gas separation membrane comprising:
a gas separation layer containing a poly(benzoxazole-imide) compound, wherein the poly(benzoxazole-imide) compound satisfies a condition (A) or (B): (A) the poly(benzoxazole-imide) compound has a structural unit represented by General formula (I) and a structural unit represented by General formula (II), and in the poly(benzoxazole-imide) compound, a molar quantity m of the structural unit represented by General formula (I) and a molar quantity n of the structural unit represented by General formula (II) satisfy Mathematical expression 1; (B) the poly(benzoxazole-imide) compound has the structural unit represented by General formula (I), the structural unit represented by General formula (II), and a structural unit represented by General formula (III), and in the poly(benzoxazole-imide) compound, the molar quantity m of the structural unit represented by General formula (I), the molar quantity n of the structural unit represented by General formula (II), and a molar quantity q of the structural unit represented by General formula (III) satisfy Mathematical expression 2:
0.25≦ m/n≦ 9.00(0< n )  Mathematical expression 1:

0.25≦ m /( n+q )≦9.00(0< n, 0< q )  Mathematical expression 2:

where X and Y each represent a single bond, a divalent linking group selected from Group (IV) of linking groups, or a divalent linking group formed by combining one or two or more linking groups selected from Group (IV);
L represents a divalent linking group including a phenylene group provided that the phenylene group does not have an —OR group as a substituent; and
R represents a hydrogen atom, COR 1 , or Si(R 2 ) 3 where R 1 and R 2 each represent an alkyl group.

2 . The gas separation membrane according to claim 1 , wherein the poly(benzoxazole-imide) compound satisfies the condition (B), and L is a divalent linking group selected from Group (V).

3 . The gas separation membrane according to claim 2 , wherein L is a divalent linking group represented by the following formula.

4 . The gas separation membrane according to claim 1 , wherein Y is a single bond or a divalent linking group selected from Group (IV-1).

5 . The gas separation membrane according to claim 1 , wherein Y is a divalent linking group selected from Group (IV-2).

6 . The gas separation membrane according to claim 1 , wherein Y is a divalent linking group represented by the following formula.

7 . The gas separation membrane according to claim 1 , wherein X is a single bond or a divalent linking group represented by the following formula.

8 . The gas separation membrane according to claim 1 , wherein the gas separation layer further contains a polymer other than the poly(benzoxazole-imide) compound.

9 . The gas separation membrane according to claim 1 , wherein the gas separation layer is formed by heat-treating a layer containing a polyimide compound having a structural unit represented by General formula (VI) and a structural unit represented by General formula (VII)

where X, Y, and L respectively have the same definition as X, Y, and L in General formulae (II) and (III); and R Z represents a hydrogen atom, COR 1 , or Si(R 2 ) 3 where R 1 and R 2 each represent an alkyl group.

10 . The gas separation membrane according to claim 9 , wherein R Z is COR 1 or Si(R 2 ) 3 where R 1 and R 2 each represent an alkyl group.

11 . The gas separation membrane according to claim 9 , wherein R Z is COR 1 where R 1 represents an alkyl group.

12 . The gas separation membrane according to claim 9 , wherein R Z is COCH 3 .

13 . The gas separation membrane according to claim 9 , wherein R Z is Si(R 2 ) 3 where R 2 represents an alkyl group.

14 . The gas separation membrane according to claim 9 , wherein a temperature of the heat-treating is 300° C. to 600° C.

15 . The gas separation membrane according to claim 1 , wherein the gas separation membrane is an asymmetric membrane.

16 . The gas separation membrane according to claim 1 , further comprising:
a siloxane compound layer disposed on the gas separation layer, wherein a Si ratio of the siloxane compound layer after immersion in chloroform to the siloxane compound layer before immersion in chloroform, the Si ratio being calculated by Mathematical expression (I), is 0.6 to 1.0;
Si ratio=(Si−Kα X-ray intensity after immersion in chloroform)/(Si−Kα X-ray intensity before immersion in chloroform)  Mathematical expression (I)

17 . The gas separation membrane according to claim 16 , wherein the siloxane compound layer contains an organopolysiloxane compound having a structure in which siloxane compounds are linked to each other through a linking group selected from the group consisting of *—O-M-O—*, *—S-M-S—*, *—NR a C(═O)—*, *—NR b C(═O)NR b —*, *—O—CH 2 —O—*, *—S—CH 2 CH 2 —*, *—OC(═O)O—*, *—CH(OH)CH 2 OCO—*, *—CH(OH)CH 2 O—*, *—CH(OH)CH 2 S—*, *—CH(OH)CH 2 NR c —*, *—CH(CH 2 OH)CH 2 OCO—*, *—CH(CH 2 OH)CH 2 O—*, *—CH(CH 2 OH)CH 2 S—*, *—CH(CH 2 OH)CH 2 NR c —*, *—CH 2 CH 2 —*, *—C(═O)O − N + (R d ) 3 —*, *—SO 3 − N + (R e ) 3 —*, and *—PO 3 H − N + (R f ) 3 —*
where M represents a divalent to tetravalent metal atom; R a , R b , R e , R d , R e , and R f each independently represent a hydrogen atom or an alkyl group; and the symbol * represents a linking site.

18 . The gas separation membrane according to claim 17 , wherein the metal atom M is a metal atom selected from the group consisting of Be, Mg, Ca, Sc, Y, Ti, Zr, V, Cr, Mo, Mn, Fe, Co, Ni, Cu, Zn, B, Al, Ga, and In.

19 . The gas separation membrane according to claim 16 , wherein the siloxane compound layer has at least one structure represented by (a) or (b);
(a) a structure having a structure represented by General formula (1) and a structure represented by General formula (2) or General formula (3), and (b) a structure represented by General formula (4),

where R S represents an alkyl group or an aryl group; L A represents a single bond or a divalent linking group; X A represents a linking group selected from the group consisting of *—O-M 1 -O—*, *—S-M 1 -S—*, *—O—CH 2 —O—*, —S—CH 2 CH 2 —*, —OC(═O)O—*, —CH 2 CH 2 —*, and *—C(═O)O − N + (R d ) 3 —*
where M 1 represents Zr, Fe, Zn, B, Al, Ti, In, or Ga; R d represents a hydrogen atom or an alkyl group; a1 and b1 are each an integer of 2 or more; the symbol * represents a linking site; and the symbol ** represents a linking site in a siloxane b

Assignees

• Fujifilm Corp

Inventors

• Hironaka Koji
• Kodama Keisuke
• Sano Satoshi

Classifications

• C01B32/55

  Solidifying · CPC title

• B01D69/02

  characterised by their properties · CPC title

• C10L3/104

  Carbon dioxide · CPC title

• C08G73/22

  Polybenzoxazoles · CPC title

• C10L2290/548

  Membrane- or permeation-treatment for separating fractions, components or impurities during preparation or upgrading of a fuel · CPC title