Hybrid crosslinked polymer membrane
A hybrid crosslinked polymeric membrane and a process for fabricating the same are provided. Specifically, the hybrid crosslinked polymer membrane comprises a glassy polymer and a ladder-structured polysilsesquioxane and has a crosslinked structure. The hybrid crosslinked polymer membrane can have an excellent permeability of carbon dioxide by virtue of an increase in the free volume and enhanced plasticization resistance, chemical resistance, and durability.
1. A hybrid crosslinked polymer membrane, which is prepared from a polymer composition comprising 70 to 90% by weight of a glassy polymer having a first functional group and 10 to 30% by weight of a ladder-structured polysilsesquioxane having a second functional group capable of reacting with the first functional group and has a crosslinked structure formed by a reaction of the first functional group and the second functional group,
wherein the glassy polymer is a polyimide obtained by polycondensation of an aromatic carboxylic dianhydride and an aromatic diamine,
the first functional group is a carboxyl group,
the second functional group is an amine group, and
70 to 100% of each of the first functional group and the second functional group participates in the crosslinking reaction.
2. The hybrid crosslinked polymer membrane of claim 1 , wherein the aromatic carboxylic dianhydride is at least one selected from the group consisting of benzophenone-3,3′,4,4′-tetracarboxylic dianhydride (BTDA) having a structure of Formula 1 (a) below, 4′4-oxydiphthalic dianhydride (ODPA) having a structure of Formula 1 (b) below, 3,3′4,4′-biphenyltetracarboxylic dianhydride (BPDA) having a structure of Formula 1 (c) below, and 4,4′-(hexafluoroisopropylidene) diphthalic dianhydride (6FDA) having a structure of Formula 1 (d) below:
3. The hybrid crosslinked polymer membrane of claim 1 , wherein the aromatic diamine is at least one selected from the group consisting of 2,3,5,6-tetramethylene-1,4-phenylenediamine (Durene) having a structure of Formula 2 (a) below, 3,5-diaminobenzoic acid (DABA) having a structure of Formula 2 (b) below, 1,1-bis(4-aminophenyl) cyclohexane (BACH) having a structure of Formula 2 (c) below, and 2,4,6-trimethyl-1,3-diaminobenzene (DAM) having a structure of Formula 2 (d) below:
4. The hybrid crosslinked polymer membrane of claim 1 , wherein the aromatic carboxylic dianhydride is benzophenone-3,3′,4,4′-tetracarboxylic dianhydride (BTDA), and the aromatic diamine is a mixture of 2,3,5,6-tetramethylene-1,4-phenylenediamine (Durene) and 3,5-diaminobenzoic acid (DABA).
5. The hybrid crosslinked polymer membrane of claim 4 , wherein the polyimide is a polyimide (BTDA-Durene: DABA (3:2)) having a structure of Formula 3 below:
in Formula 3, n is an integer selected from 10 2 to 10 4 .
6. The hybrid crosslinked polymer membrane of claim 1 , wherein the ladder-structured polysilsesquioxane has a structure represented by Formula 4 below:
in Formula 4, R 1 , R 2 , and R 3 are each independently an organic functional group selected from the group consisting of aromatic phenyl, heteroaromatic phenyl, aliphatic alkyl, cycloaliphatic alkyl, vinyl, aryl, methacrylate, acrylate, and epoxy, and n, m, and l are each an integer selected from 0 to 100.
7. The hybrid crosslinked polymer membrane of claim 6 , wherein the ladder-structured polysilsesquioxane has a number average molecular weight of 10 2 to 10 8 g/mole.
8. The hybrid crosslinked polymer membrane of claim 6 , wherein the ladder-structured polysilsesquioxane is selected from the group consisting of ladder-structured poly(phenyl-co-3-(2-aminoethylamino)propyl)silsesquioxane, ladder-structured poly(phenyl-co-pyridylethyl) silsesquioxane, ladder-structured poly(cyclohexyl-co-pyridylethyl) silsesquioxane, ladder-structured poly(cyclohexyl-co-phenyl-co-pyridylethyl) silsesquioxane, and a mixture thereof.
9. The hybrid crosslinked polymer membrane of claim 6 , wherein the ladder-structured polysilsesquioxane is at least one selected from the group consisting of ladder-structured poly(phenyl-co-3-(2-aminoethylamino) propyl) silsesquioxane (LPDA64) represented by the following Formula 4a; ladder-structured poly(phenyl-co-pyridylethyl) silsesquioxane (LPPyr64) represented by the following Formula 4d, ladder-structured poly(cyclohexyl-co-pyridylethyl) silsesquioxane (LCPyr64) represented by the following Formula 4e, and ladder-structured poly(cyclohexyl-co-phenyl-co-pyridylethyl) silsesquioxane (LCPPyr334) represented by the following Formula 4f:
10. The hybrid crosslinked polymer membrane of claim 1 , which has a thickness of 5 to 100 μm.