Crosslinked and crosslinkable hollow fiber mixed matrix membrane and method of making same

A hollow fiber mixed matrix polymer membrane, comprising:

• a) a continuous phase polymer comprising a polyimide having crosslinkable sites;
• and
• b) a molecular sieve material dispersed within said continuous phase polymer;
• wherein the ratio of crosslinkable sites to imide groups is between 3:8 and 1:16.

A hollow fiber mixed matrix polymer membrane material, comprising:

• a molecular sieve dispersed within a continuous polymer phase wherein said continuous polymer phase comprises a polyimide polymer made from the monomers A+B+C;
• where A is a dianhydride of the formula;
• 8
• where
• X1 and X2 are independently a halogenated alkyl group, phenyl or halogen;
• where R1, R2, R3, R4, R5, and R6 are independently H, alkyl, or halogen;
• where B is a diamino cyclic compound without a carboxylic acid functionality;
• where C is a diamino cyclic compound with a carboxylic acid functionality;
• and
• wherein the ratio of B to C is between 1:4 and 8:1.

A method of making a crosslinked hollow fiber membrane, comprising:

• preparing a continuous phase polyimide polymer comprising a predetermined quantity of crosslinkable sites and a molecular sieve material dispersed within said continuous phase polymer;
• forming a hollow fiber from said continuous phase polyimide polymer;
• treating the hollow fiber with a diol selected from the group consisting of ethylene glycol, propylene glycol, 1,3 propanediol, 1,4 butanediol, 1,2 butanediol, and 1,3 butanediol, at esterification conditions, to form a monoesterified hollow fiber;
• and
• subjecting the monoesterified hollow fiber to transeesterification conditions to form a crosslinked hollow fiber membrane.

A method of making a crosslinked hollow fiber membrane, comprising:

• preparing a polyimide polymer comprising a predetermined quantity of crosslinkable sites and a molecular sieve material dispersed within said continuous phase polymer;
• treating the polyimide polymer with a diol selected from the group consisting of ethylene glycol, propylene glycol, 1,3 propanediol, 1,4 butanediol, 1,2 butanediol, and 1,3 butanediol, at esterification conditions, to form a monoesterified membrane material;
• forming a monoesterified hollow fiber from the monoesterified membrane material;
• and
• subjecting the monoesterified hollow fiber to transesterification conditions to form a crosslinked hollow fiber membrane.