Thermally-rearranged polymer blends for gas separation membranes
View Patent ↗Polymer blends comprising an ortho-functionalized polyimide homo or copolymer and a polybenzimidazole homo or copolymer, wherein the ortho-functionalized polyimide thermally rearranges to a polymer comprising a phenylene heterocyclic group, such as, polybenzoxazole, polybenzothiazole, polybenzimidazole and/or other heterocyclic structure upon heating. Also disclosed are method of forming a polymer blend comprising dissolving an ortho-functionalized polyimide homo or copolymer and a polybenzimidazole homo or copolymer in a solvent, and optional compatibilizer, to form a polymer solution; contacting a support with the polymer solution; and evaporating the solvent to provide a thin layer comprising the polymer blend on the support. Further, methods of heat treating these polymer blends to thermally rearrange the disclosed polyimides are disclosed, as are the polymer blends prepared thereby. Methods of using these polymer blends to separate gases are also disclosed.
1. A polymer blend, comprising: a thermally rearranged ortho-functionalized polyimide homo or copolymer and a polybenzimidazole homo or copolymer, wherein the thermally rearranged polyimide homo or copolymer is a polymer comprising a phenylene heterocyclic group, wherein the polymer blend is an immiscible blend comprising a dispersed phase and a continuous phase.
2. The polymer blend of claim 1 , wherein the thermally rearranged polyimide homo or copolymer comprises a polybenzoxazole, polybenzothiazole, and/or polybenzimidazole.
3. The polymer blend of claim 1 , wherein the continuous phase comprises the polybenzimidazole homo or copolymer and the dispersed phase comprises the thermally rearranged polyimide homo or copolymer.
4. The polymer blend of claim 1 , wherein the continuous phase comprises the thermally rearranged polyimide homo or copolymer and the dispersed phase comprises the polybenzimidazole homo or copolymer.
5. The polymer blend of claim 1 , wherein the polybenzimidazole homo or copolymer has a domain represented by Formula I
wherein
n is from 2 to 100,000;
R 7 is or is a moiety that comprises
R 8 is or is a moiety that comprises —(CH 2 ) 1-8 —,
R 9 and R 10 are independently chosen from H, C 1 -C 3 alkyl, —CH 2 Si(CH 3 ) 3 ,
or
and
R 11 is —O—, S(O) 2 —, or
6. The polymer blend of claim 1 , wherein the wherein the polybenzimidazole has the formula
wherein n is an integer from 2 to 100,000.
7. The polymer blend of claim 1 , wherein the thermally rearranged ortho-functionalized polyimide homo or copolymer has a domain before thermal rearrangement represented by Formula II
wherein
n is from 2 to 100,000;
R 1 is or is a moiety that comprises
R 2 is or is a moiety that comprises
R 3 is chosen from —O—, —S—, —C(O)—, —S(O)—, —S(O) 2 —, —CH 2 —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —,
R 4 and R 5 are each independently chosen from —OH, —SH, —OC(O)C 1 -C 6 alkyl, —OC(O)C 1 -C 6 haloalkyl, —OC(O)C 1 -C 6 cycloalkyl, or NH 2 ; and
R 6 is chosen from —O—, —S—, —C(O)—, —S(O)—, —S(O) 2 —, —CH 2 —, —C(CH 3 ) 2 —, or —C(CF 3 ) 2 —.
8. The polymer blend of claim 7 , wherein R 4 and R 5 are each independently chosen from
9. The polymer blend of claim 1 , wherein the thermally rearranged ortho-functionalized polyimide homo or copolymer has, before thermal rearrangement, a formula
wherein n is an integer from 2 to 100,000.
10. The polymer blend of claim 1 , wherein the thermally rearranged ortho-functionalized polyimide homo or copolymer has, before thermal rearrangement, a formula
wherein n is an integer from 2 to 100,000.
11. The polymer blend of claim 1 , wherein the thermally rearranged ortho-functionalized polyimide homo or copolymer has, before thermal rearrangement, a formula
wherein n is an integer from 2 to 100,000.
12. The polymer blend of claim 1 , wherein the thermally rearranged ortho-functionalized polyimide homo or copolymer has, before thermal rearrangement, a formula
wherein n is an integer from 2 to 100,000.
13. The polymer blend of claim 1 , wherein the thermally rearranged ortho-functionalized polyimide homo or copolymer is present in the blend at from 1 wt % to 99 wt %.
14. The polymer blend of claim 1 , wherein the polybenzimidazole homo or copolymer is present in the blend at from 1 wt % to 99 wt %.
15. The polymer blend of claim 1 , wherein the thermally rearranged ortho-functionalized polyimide homo or copolymer is present in the blend at from 5 wt % to 45 wt %, and the polybenzimidazole homo or copolymer is present in the blend at from 95 wt % to 55 wt %.
16. The polymer blend of claim 1 , further comprising an organic compatibilizer having Formula III
wherein R 12 , R 13 , R 14 , and R 15 are independently chosen from C 1 -C 6 alkyl, aryl, or arylalkyl.
17. The polymer blend of claim 1 , further comprising an organic compatibilizer chosen from 1-methylimidazole, 2-methylimidazole, 1-ethylimidazole, 2-ethylimidazole, 1-propylimidazole, 2-propylimidazole, 1-butylimidazole, 2-butylimidazole, 1-phenylimidazole, 2-phenylimidazole, 1-benzylimidazole, or 2-benzylimidazole.
18. The polymer blend of claim 1 , further comprising an organic compatibilizer chosen from pyrrolines, pyrroles, pyrazolidines, imidazolidines, pyrazolines, pyrazoles, imidazolines, triazoles, tetrazoles, furans, dioxolanes, thiophenes, oxazoles, isoxazoles, isothiazoles, thiazoles, oxathiolanes, oxadiazoles, thiadiazoles, pyridines, piperazines, pyridazines, pyrimidines, pyrazines, triazines, pyrans, pyryliums, dioxanes, dioxines, thiopyrans, dithianes, trithianes, morpholines, oxazines, thiomorpholines, thiazines, indoles, isoindoles, indolizines, indazoles, benzimidazoles, azaindoles, azaindazoles, purines, benzofurans, isobenzofurans, benzothiophenes, benzoisoxazoles, benzoisothiazoles, benxoxazoles, benzothiazoles, benzothiadiazoles, adenines, guanines, hydroquinolines, quinolones, isoquinolines, quinolizines, quinoxalines, phthalazines, quinazolines, cinnolines, naphthyridines, pyridopyrimidines, pyridopyrazines, pteridines, chromenes, isochromenes, chromenones, benzooxazines, quinolinones, isoquinolinones, carbazoles, dibenzofurans, acridines, phenazines, phenoxazines, phenothiazines, phenoxathiines, azepines, diazepines, dihydroazepines, thiepines, thiazepines, azocines, azecines, or imidazolium-based ionic liquids.
19. The polymer blend of claim 1 , further comprising an inorganic compatibilizer.
20. The polymer blend of claim 19 , wherein the inorganic compatibilizer is chosen from lithium chloride, lithium bromide, sodium chloride, sodium bromide, potassium chloride, potassium bromide, calcium chloride, calcium bromide, copper chloride, a metal organic framework, or a zeolitic imidazolate framework.
21. The polymer blend of claim 16 , wherein the compatibilizer is present at from 0.5 to 99 wt % of the blend.
22. A method of forming a polymer blend, comprising: dissolving an ortho-functionalized polyimide homo or copolymer and a polybenzimidazole homo or copolymer in a solvent to form a polymer solution; contacting a support with the polymer solution; and evaporating the solvent to provide a thin layer comprising the polymer blend on the support, and wherein the formed polymer blend is an immiscible blend comprising a dispersed phase and a continuous phase.
23. A method of separating a target gas from a gas stream, comprising: contacting the polymer blend of claim 1 with the gas stream, such that the target gas selectively permeates the polymer blend, thereby being separated the gas stream.
24. A method of dehydrating a gas stream, comprising contacting the polymer blend of claim 1 with the gas stream, such that water permeates the polymer blend, thereby being separated from the gas stream.