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

1. A gas separation composite membrane, containing:

a gas-permeable supporting layer; and

a gas separating layer containing a crosslinked organic-inorganic hybrid resin, over the gas-permeable supporting layer,

wherein the crosslinked organic-inorganic hybrid resin has a structure in which a polymer incorporating therein an oxanthrene unit, or a polyimide compound has been crosslinked via a specific crosslinking chain, and the specific crosslinking chain contains a site represented by the following formula (A):

wherein R a represents an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, or *—O—**; the symbol “*” means a bonding hand with M 1 in formula (A); the symbol “**” means a connection site with an adjacent M 1 ; M 1 represents a metal atom selected from the group consisting of Si, Ge, Mg, Al, Ti, Zr and Sb; P a represents a polyimide compound or a polymer incorporating therein an oxanthrene unit; and L a represents a connection site with an adjacent M 1 ,

wherein a structural part derived from the polyimide compound contains a repeating unit represented by formula (I), and a repeating unit represented by formula (III-a) or (III-b):

wherein, in formula (I), R is a group of atoms selected from groups represented by formulas (I-a) to (I-g);

wherein, in formulas (I-a) to (I-g), X 1 represents a single bond or a divalent linking group; Y 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 6 , R 7 and R 8 represent a substituent; J 1 , J 2 and W 1 represent a single bond or a divalent linking group; l2, m2 and n2 represent an integer of from 0 to 3; L 1 represents a divalent linking group; p represents an integer of 0 or more; q represents an integer of 1 or more; X 3 represents a single bond or a divalent linking group; and Lb means a connection site with M 1 in formula (A), and

wherein the polymer incorporating therein an oxanthrene unit contains a repeating unit represented by formula (IV-a), and a repeating unit represented by formula (IV-b):

wherein R 10 to R 20 represent a hydrogen atom or a substituent; J 3 , J 4 and W 2 represent a single bond or a divalent linking group; L 2 represents a divalent linking group; r represents an integer of 0 or more; Y 1 and Y 2 represent a group of atoms for forming a ring with the carbon atom and the benzene ring; Lc means a connection site with M 1 in formula (A).

2. The gas separation composite membrane according to claim 1 , wherein the structural part derived from the polyimide compound further contains a repeating unit represented by formula (II-a) or (II-b):

wherein R 3 , R 4 and R 5 represent an alkyl group, a hydroxyl group, a carboxyl group, a sulfonic acid group, an amino group, a mercapto group, an amide group, an alkoxy group, a sulfone group, or a halogen atom; l1, m1 and n1 represent an integer of from 0 to 4; and X 2 represents a single bond or a divalent linking group.

3. The gas separation composite membrane according to claim 1 , wherein the polymer incorporating therein an oxanthrene unit is a resin with inherent microporosity (PIM).

4. The gas separation composite membrane according to claim 1 ,

wherein a gas to be supplied is a mixed gas of carbon dioxide and methane,

wherein a transmission rate of the carbon dioxide at 40° C. and 40 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 (R CO2 /R CH4 ) is 15 or more.

5. 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.

6. The gas separation composite membrane according to claim 5 , wherein the porous layer has a molecular weight cut-off of 100,000 or less.

7. The gas separation composite membrane according to claim 1 , wherein a crosslinked site ratio [η] of the crosslinked organic-inorganic hybrid resin is 0.13 or more.

8. The gas separation composite membrane according to claim 1 , wherein a crosslinking functional group density [γ] of a raw resin that constitutes the crosslinked organic-inorganic hybrid resin is from 0.7 to 0.95.

9. The gas separation composite membrane according to claim 1 , wherein the crosslinked organic-inorganic hybrid resin is formed by using a compound represented by the following formula (O-1), (O-2), or (O-3) as a crosslinking agent that constitutes the crosslinking chain thereof:

H 2 N-L O -Si(R O ) 3   O-1

HS-L O -Si(R O ) 3   O-2

CH 2 ═CH-L O -Si(R O ) 3   O-3

wherein L O represents a single bond or a linking group; and R O represents an alkoxy group.

10. A method of producing a gas separation composite membrane having a gas separating layer containing a crosslinked organic-inorganic hybrid resin over a gas-permeable supporting layer thereof, comprising:

coating a coating liquid containing a polyimide compound or a polymer incorporating therein an oxanthrene unit, and a crosslinking agent having a metal atom M 1 wherein M 1 represents a metal atom selected from the group consisting of Si, Ge, Mg, Al, Ti, Zr, and Sb, over the supporting layer; and

irradiating an active radiation or applying heat to the coating liquid thereby inducing a crosslinking reaction,

wherein the polyimide compound contains a repeating unit represented by formula (I), and a repeating unit represented by formula (VI-a) or (VI-b):

wherein, in formula (I), R is a group of atoms selected from groups represented by formulas (I-a) to (I-g);

wherein, in formulas (I-a) to (I-g), X 1 represents a single bond or a divalent linking group; Y 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 6 , R 7 and R 8 represent a substituent; J 1 represents a single bond or a divalent linking group; l2, m2 and n2 represent an integer of from 0 to 3; q represents an integer of 1 or more and 4 or less; X 3 represents a single bond or a divalent linking group; and A 1 represents a reactive group, and

wherein the polymer incorporating therein an oxanthrene unit is a polymer containing a repeating unit represented by formula (V):

wherein R 16 to R 20 represent a hydrogen atom or a substituent; J 3 represents a single bond or a divalent linking group; Y 1 and Y 2 represent a group of atoms for forming a ring with the carbon atom and the benzene ring; and A 1 represents a hydroxy group, a carboxyl group, a sulfonic acid group, an alkenyl group, an alkynyl group, or a mercapto group, and

wherein the polyimide compound further contains a repeating unit represented by formula (II-a):

wherein R 3 represents a substituent; and l1 represents an integer of from 0 to 4.

11. The method of producing the organic-inorganic hybrid gas separation composite membrane according to claim 10 , wherein the crosslinking agent is a compound represented by formula (B): (B):

wherein A 2 represents a reactive group; L 3 represents a single bond or a divalent linking group; R 21 , R 22 and R 23 represent an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, or an aryloxy group; and M 1 has the same meaning as that described above.

12. The method of producing a gas separation composite membrane according to claim 11 , wherein the crosslinking agent is a compound represented by formula (O-1), (O-2) or (O-3):

H 2 N-L O -Si(R O ) 3   O-1

HS-L O -Si(R O ) 3   O-2

CH 2 ═CH-L O -Si(R O ) 3   O-3

wherein L O represents a single bond or a divalent linking group; and R O represents an alkyl group, an aryl group, an alkoxy group, or an aryloxy group.

13. A gas separation module, containing the gas separation composite membrane according to claim 1 .

14. A gas separation apparatus, containing the gas separation module according to claim 13 .

15. A gas separation method, which contains 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 .