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

Patent metadata

Field	Value
Publication number	US-9452392-B2
Application number	US-201414457577-A
Country	US
Kind code	B2
Filing date	Aug 12, 2014
Priority date	Feb 17, 2012
Publication date	Sep 27, 2016
Grant date	Sep 27, 2016

Abstract

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, in which 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.

First claim

The invention claimed is:

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

Assignees

• Fujifilm Corp

Inventors

• Sano Satoshi
• Nagata Ichiro
• Kodama Keisuke

Classifications

• C08G73/1067

  Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound · CPC title

• B01D69/125

  In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction · CPC title

• C08G73/1039

  comprising halogen-containing substituents · CPC title

• B01D2323/34

  Use of radiation · CPC title

• Y02P20/152

  Cross-Sectional Technologies · mapped topic