Gas separation composite membrane and gas separating module, gas separation apparatus and gas separation method using the same

1. A gas separation composite membrane, comprising:

a gas-permeable supporting layer; and

a gas separating layer containing a crosslinked polyimide resin over the gas-permeable supporting layer,

wherein the crosslinked polyimide resin has structure in which a polyimide compound is crosslinked through a specific crosslinking chain;

wherein the specific crosslinking chain has at least one kind of linking group selected from the group consisting of —NR a C(═O)—, —NR b C(═O)O—, —CH 2 OCH 2 —, —CH 2 SCH 2 —, —OC(═O)O—, —C(═O)O − N + (R c ) 3 —, —SO 3 − N + (R d ) 3 — and —PO 3 − N + (R e ) 3 —;

wherein R a , R b , R c , R d and R e each independently represent a hydrogen atom or a substituent; and a plurality of R a , R b , R c , R d and R e may be identical or different, or may be bonded or subjected to ring condensation with each other to form a ring; and

wherein the polyimide compound contains a repeating unit represented by Formula (I), at least one kind of repeating unit represented by Formula (II-a) or (II-b), and at least one kind of repeating unit represented by Formula (III-a) or (III-b):

wherein R in Formula (I) is a group of atoms selected from the group consisting of the groups represented by any one of Formulas (I-a) to (I-g);

wherein, in Formulas (I-a) to (I-g), X 1 represents a single bond or a bivalent linking group; Y 1 represents a methylene group or a vinylene group; R 1 and R 2 each independently represent a hydrogen atom or a substituent, or may bond with each other to form a ring; and the symbol “*” represents a binding site with the carbonyl group of the imide in Formula (I);

wherein R 3 in Formula (II-a) represents an alkyl group, a hydroxyl group, a carboxyl group, a sulfonic acid group, an amino group or a halogen atom; 11 in Formula (II-a) represents an integer of from 0 to 4; R 4 and R 5 in Formula (II-b) each independently represent an alkyl group, a hydroxyl group, a carboxyl group, a sulfonic acid group, an amino group or a halogen atom; R 4 and R 5 in Formula (II-b) may bond with each other to form a ring; m1 and n1 in Formula (II-b) each independently represent an integer of from 0 to 4; and X 2 in Formula (II-b) represents a single bond or a bivalent linking group; and

wherein, in Formulas (III-a) and (III-b), R 6 , R 7 and R 8 each independently represent a substituent; R 7 and R 8 may bond with each other to form a ring; J 1 and J 2 each independently represent at least one kind of linking group selected from the group consisting of —CH 2 SCH 2 —, —OC(═O)O —, —C(═O)O − N + (R c ) 3 —, —SO 3 − N + (R d ) 3 —, and —PO 3 − N + (R e ) 3 —; R c , R d and R e each independently represent a hydrogen atom or a substituent; W 1 represents a single bond or a bivalent linking group; 12, m2 and n2 each independently represent an integer of from 0 to 3; L 1 represents a bivalent linking group; L 2 represents a functional group; p represents an integer of 0 or more; when p is 2 or more, L 1 's and J 2 's may be the same or different from each other; and X 3 represents a single bond or a bivalent linking group.

2. The gas separation composite membrane according to claim 1 , wherein R a , R b , R c , R d and R e each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

3. The gas separation composite membrane according to claim 1 , wherein the specific crosslinking chain contains at least one kind of linking group selected from the group consisting of —C(═O)O − N + (R c ) 3 — and —SO 3 − N + (R d ) 3 —, and —NHC(═O)—.

4. The gas separation composite membrane according to claim 1 , wherein X 1 represents a single bond, —C(Ra) 2 —, —O—, —SO 2 —, —C(═O)—, or —S—; and Ra represents a hydrogen atom or an alkyl group.

5. The gas separation composite membrane according to claim 1 , wherein R 1 and R 2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an acylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonylamino group, a sulfamoyl group, a carbamoyl group, an alkylthio group, an arylthio group, a heterocyclic thio group, a sulfonyl group, a sulfinyl group, a ureido group, a phosphoric acid amide group, a hydroxyl group, a mercapto group, a halogen atom, a cyano group, a sulfo group, a carboxyl group, an oxo group, a nitro group, a hydroxamic acid group, a sulfino group, a hydrazino group, an imino group, a heterocyclic group, a silyl group, or a silyloxy group.

6. The gas separation composite membrane according to claim 1 , wherein X 2 represents a single bond, —C(Ra) 2 —, —O—, —SO 2 —, —C(═O)—, or —S—; and Ra represents a hydrogen atom or an alkyl group.

7. The gas separation composite membrane according to claim 1 , wherein R 6 , R 7 and R 8 in Formulas (III-a) and (III-b) each independently represent an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an acylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonylamino group, a sulfamoyl group, a carbamoyl group, an alkylthio group, an arylthio group, a heterocyclic thio group, a sulfonyl group, a sulfinyl group, a ureido group, a phosphoric acid amide group, a hydroxyl group, a mercapto group, a halogen atom, a cyano group, a sulfo group, a carboxyl group, an oxo group, a nitro group, a hydroxamic acid group, a sulfino group, a hydrazino group, an imino group, a heterocyclic group, a silyl group, or a silyloxy group.

8. The gas separation composite membrane according to claim 1 , wherein W 1 in Formulas (III-a) and (III-b) represents a single bond, an alkylene group, an alkyleneoxy group, an aralkylene group, or an arylene group.

9. The gas separation composite membrane according to claim 1 , wherein L 1 in Formulas (III-a) and (III-b) represents any one of Formulas (L-1) to (L-35) described below, an alkylene group, an alkyleneoxy group or an arylene group

10. The gas separation composite membrane according to claim 1 , wherein the functional group is at least one kind of functional group selected from the group consisting of —NHC(═O)CR f ═CH 2 , —OH, —SH, and —CH═CH 2 ; and R f represent a hydrogen atom or an alkyl group.

11. The gas separation composite membrane according to claim 1 , wherein X 3 represents a single bond, —C(Ra) 2 —, —O—, —SO 2 —, —C(═O)—, or —S—; and Ra represents a hydrogen atom or an alkyl group.

12. The gas separation composite membrane according to claim 1 , wherein R in formula (I) is represented by formula (I-a′)

13. The gas separation composite membrane according to claim 1 , wherein J 1 in formulas (III-a) and (III-b) is at least one kind of linking group selected from the group consisting of —C(═O)O − N + R c 3 —, —SO 3 − N + R d 3 —, and —PO 3 − N + R e 3 —.

14. The gas separation composite membrane according to claim 1 , wherein p in formulas (III-a) and (III-b) is 0.

15. The gas separation composite membrane according to claim 1 , wherein L 2 in formulas (III-a) and (III-b) is —NHC(═O)CR f ═CH 2 , and R f represent a hydrogen atom or an alkyl group.

16. The gas separation composite membrane according to claim 1 , wherein the supporting layer contains a porous layer on a side of the gas separating layer and a nonwoven fabric layer on a side reverse thereto.

17. The gas separation composite membrane according to claim 16 , wherein the porous layer has a molecular weight cut-off of 100,000 or less.

18. The gas separation composite membrane according to claim 1 , wherein a gas to be supplied is a mixed gas of at least carbon dioxide and methane, wherein a transmission rate of the carbon dioxide at 40° C. and 8 atmospheric pressure is more than 20 GPU, and

wherein a ratio of the transmission rate of the carbon dioxide to a transmission rate of the methane (TR CO2 /TR CH4 ) is 20 or more.

19. A gas separation module, comprising the gas separation composite according to claim 1 .

20. A gas separation apparatus, comprising the gas separation module according to claim 19 .

21. A gas separation method, which comprises a step of selectively permeating carbon dioxide from a gas containing carbon dioxide and methane by using the gas separation composite membrane according to claim 1 .

22. The gas separation composite membrane according to claim 1 , wherein the linking group is —C(═O)O − N + (R c ) 3 —.