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A composition of and a method of making high performance mixed matrix hollow fiber membranes is described. The membranes have a high resistance to plasticization by use of a predetermined amount of crosslinking. The preferred polymer material for the membrane is a polyimide polymer continuous phase

A composition of and a method of making high performance mixed matrix hollow fiber membranes is described. The membranes have a high resistance to plasticization by use of a predetermined amount of crosslinking. The preferred polymer material for the membrane is a polyimide polymer continuous phase comprising ester crosslinks and a molecular sieve material dispersed within the polymer continuous phase. The resultant mixed matrix hollow fiber membrane exhibits a high permeance of CO 2 in combination with a high CO 2 /CH 4 selectivity. Another embodiment provides a method of making the mixed matrix hollow fiber membrane from a monesterified polymer followed by final crosslinking after hollow fiber formation.

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1. A hollow fiber polymer membrane, comprising:a) a crosslinked polymer continuous phase; andb) a molecular sieve material dispersed within said continuous phase;wherein said membrane has a CO 2 permeance of at least 20 GPU and a CO 2 /CH 4 selectivity of greater than 20, at 35 degrees C. and a p

1. A hollow fiber polymer membrane, comprising:a) a crosslinked polymer continuous phase; andb) a molecular sieve material dispersed within said continuous phase;wherein said membrane has a CO 2 permeance of at least 20 GPU and a CO 2 /CH 4 selectivity of greater than 20, at 35 degrees C. and a pressure of 100 psia. 2. The hollow fiber polymer membrane of claim 1 wherein the molecular sieve material dispersed within said continuous phase has an average particle size of less than about 1 micron. 3. The hollow fiber polymer membrane of claim 1 wherein the molecular sieve material dispersed within said continuous phase has an average particle size of less than about 0.1 micron. 4. A hollow fiber mixed matrix polymer membrane, comprising:a) a continuous phase polymer comprising a polyimide having crosslinkable sites; andb) 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. 5. 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;where X 1 and X 2 are independently a halogenated alkyl group, phenyl or halogen;where R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 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; andwherein the ratio of B to C is between 1:4 and 8:1. 6. The hollow fiber polymer membrane material of claim 5 where X 1 and X 2 are CF 3 . 7. The hollow fiber polymer membrane material of claim 5 where R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are H. 8. The hollow fiber polymer membrane material of claim 5 wherein the dianhydride is 6FDA. 9. The hollow fiber polymer membrane material of claim 5 wherein C is DABA. 10. The hollow fiber polymer membrane material of claim 5 wherein B is a diamino aromatic compound. 11. The hollow fiber polymer membrane material of claim 5 wherein B is a diamino benzene compound having one or more methyl groups attached to the benzene ring. 12. The hollow fiber polymer membrane material of claim 5 wherein the ratio of B to C is between 17:3 and 3:2. 13. The hollow fiber polymer membrane material of claim 5 wherein the ratio of B to C is between 17:3 and 3:1. 14. The hollow fiber polymer membrane material of claim 5 wherein said membrane is subjected to esterification conditions in the presence of a diol selected from the group consisting of ethylene glycol, propylene glycol, 1,3 propanediol, 1,4 butanediol, 1,2 butanediol, benzenedimethanol, and 1,3 butanediol to form a hollow fiber polymer membrane monoester. 15. The hollow fiber polymer membrane material of claim 14 wherein at least 60% of the carboxylic acid functionality is converted to a monoester. 16. The hollow fiber polymer membrane material of claim 14 wherein the hollow fiber membrane monoester is subjected to transesterification conditions to form a crosslinked hollow fiber polymer membrane. 17. The hollow fiber polymer membrane material of claim 5 wherein B is diamino durene. 18. The hollow fiber polymer membrane material of claim 14 wherein at least 80% of the carboxylic acid functionality is converted to a monoester. 19. The hollow fiber polymer membrane of claims 1 , 4 or 5 wherein the molecular sieve is a zeolite. 20. The hollow fiber polymer membrane of claims 1 , 4 or 5 wherein the molecular sieve is carbon molecular sieve. 21. The hollow fiber polymer membrane of claims 1 , 4 or 5 wherein the molecular sieve is an aluminophosphate zeolite. 22. The hollow fiber polymer membrane of claims 1 , 4 or 5 wherein the molecular sieve is a borosilicate. 23. The hollow fiber polymer membrane of claims 1 , 4 or 5 wherein the molecular sieve is a SAPO. 24. A method of makin g 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; andsubjecting the monoesterified hollow fiber to transesterification conditions to form a crosslinked hollow fiber membrane. 25. 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; andsubjecting the monoesterified hollow fiber to transesterification conditions to form a crosslinked hollow fiber membrane.