CN1248773C - 共聚酰亚胺气体分离膜 - Google Patents
共聚酰亚胺气体分离膜 Download PDFInfo
- Publication number
- CN1248773C CN1248773C CNB018208320A CN01820832A CN1248773C CN 1248773 C CN1248773 C CN 1248773C CN B018208320 A CNB018208320 A CN B018208320A CN 01820832 A CN01820832 A CN 01820832A CN 1248773 C CN1248773 C CN 1248773C
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- CN
- China
- Prior art keywords
- dianhydride
- film
- gas
- monomer
- hexafluoorpropane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 239000012528 membrane Substances 0.000 title abstract description 26
- 238000000926 separation method Methods 0.000 title abstract description 19
- 239000007789 gas Substances 0.000 claims abstract description 59
- 150000004985 diamines Chemical class 0.000 claims abstract description 45
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 43
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000203 mixture Substances 0.000 claims abstract description 36
- 239000002904 solvent Substances 0.000 claims abstract description 36
- 239000000178 monomer Substances 0.000 claims abstract description 34
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 22
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 22
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 17
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 17
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 16
- OJSPYCPPVCMEBS-UHFFFAOYSA-N 2,8-dimethyl-5,5-dioxodibenzothiophene-3,7-diamine Chemical compound C12=CC(C)=C(N)C=C2S(=O)(=O)C2=C1C=C(C)C(N)=C2 OJSPYCPPVCMEBS-UHFFFAOYSA-N 0.000 claims abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 5
- 229920001721 polyimide Polymers 0.000 claims description 19
- 239000004642 Polyimide Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- -1 3,4-dicarboxyl phenyl Chemical group 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 12
- 238000001764 infiltration Methods 0.000 claims description 9
- 230000008595 infiltration Effects 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 8
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 5
- JVMSQRAXNZPDHF-UHFFFAOYSA-N 2,4-diaminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C(N)=C1 JVMSQRAXNZPDHF-UHFFFAOYSA-N 0.000 claims description 3
- 239000005711 Benzoic acid Substances 0.000 claims description 3
- PCTSMYBTOQYNDS-UHFFFAOYSA-N OC(C)C.NNC(=O)NN Chemical compound OC(C)C.NNC(=O)NN PCTSMYBTOQYNDS-UHFFFAOYSA-N 0.000 claims description 3
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 3
- WPLOVIFNBMNBPD-ATHMIXSHSA-N subtilin Chemical compound CC1SCC(NC2=O)C(=O)NC(CC(N)=O)C(=O)NC(C(=O)NC(CCCCN)C(=O)NC(C(C)CC)C(=O)NC(=C)C(=O)NC(CCCCN)C(O)=O)CSC(C)C2NC(=O)C(CC(C)C)NC(=O)C1NC(=O)C(CCC(N)=O)NC(=O)C(CC(C)C)NC(=O)C(NC(=O)C1NC(=O)C(=C/C)/NC(=O)C(CCC(N)=O)NC(=O)C(CC(C)C)NC(=O)C(C)NC(=O)CNC(=O)C(NC(=O)C(NC(=O)C2NC(=O)CNC(=O)C3CCCN3C(=O)C(NC(=O)C3NC(=O)C(CC(C)C)NC(=O)C(=C)NC(=O)C(CCC(O)=O)NC(=O)C(NC(=O)C(CCCCN)NC(=O)C(N)CC=4C5=CC=CC=C5NC=4)CSC3)C(C)SC2)C(C)C)C(C)SC1)CC1=CC=CC=C1 WPLOVIFNBMNBPD-ATHMIXSHSA-N 0.000 claims description 3
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 claims description 2
- MQAHXEQUBNDFGI-UHFFFAOYSA-N 5-[4-[2-[4-[(1,3-dioxo-2-benzofuran-5-yl)oxy]phenyl]propan-2-yl]phenoxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC2=CC=C(C=C2)C(C)(C=2C=CC(OC=3C=C4C(=O)OC(=O)C4=CC=3)=CC=2)C)=C1 MQAHXEQUBNDFGI-UHFFFAOYSA-N 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 2
- 230000035699 permeability Effects 0.000 abstract description 8
- 238000007334 copolymerization reaction Methods 0.000 abstract description 2
- 239000003345 natural gas Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- APXJLYIVOFARRM-UHFFFAOYSA-N 4-[2-(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(C(O)=O)C(C(O)=O)=C1 APXJLYIVOFARRM-UHFFFAOYSA-N 0.000 abstract 1
- 239000000356 contaminant Substances 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 15
- 230000010148 water-pollination Effects 0.000 description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 8
- 229920005575 poly(amic acid) Polymers 0.000 description 7
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- 235000012489 doughnuts Nutrition 0.000 description 4
- 239000012466 permeate Substances 0.000 description 4
- PJWIPEXIFFQAQZ-PUFIMZNGSA-N 7-phospho-2-dehydro-3-deoxy-D-arabino-heptonic acid Chemical compound OP(=O)(O)OC[C@@H](O)[C@@H](O)[C@H](O)CC(=O)C(O)=O PJWIPEXIFFQAQZ-PUFIMZNGSA-N 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N phthalic anhydride Chemical class C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical class ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 208000012886 Vertigo Diseases 0.000 description 2
- 230000009102 absorption Effects 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- IKJFYINYNJYDTA-UHFFFAOYSA-N dibenzothiophene sulfone Chemical compound C1=CC=C2S(=O)(=O)C3=CC=CC=C3C2=C1 IKJFYINYNJYDTA-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002672 m-cresols Chemical class 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- SXGMVGOVILIERA-UHFFFAOYSA-N (2R,3S)-2,3-diaminobutanoic acid Natural products CC(N)C(N)C(O)=O SXGMVGOVILIERA-UHFFFAOYSA-N 0.000 description 1
- FWBHETKCLVMNFS-UHFFFAOYSA-N 4',6-Diamino-2-phenylindol Chemical compound C1=CC(C(=N)N)=CC=C1C1=CC2=CC=C(C(N)=N)C=C2N1 FWBHETKCLVMNFS-UHFFFAOYSA-N 0.000 description 1
- TWISHTANSAOCNX-UHFFFAOYSA-N 4-(1,1,1,3,3,3-hexafluoropropan-2-yl)phthalic acid Chemical compound OC(=O)C1=CC=C(C(C(F)(F)F)C(F)(F)F)C=C1C(O)=O TWISHTANSAOCNX-UHFFFAOYSA-N 0.000 description 1
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- IRLPACMLTUPBCL-KQYNXXCUSA-N 5'-adenylyl sulfate Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(=O)OS(O)(=O)=O)[C@@H](O)[C@H]1O IRLPACMLTUPBCL-KQYNXXCUSA-N 0.000 description 1
- ZHBXLZQQVCDGPA-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)sulfonyl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(S(=O)(=O)C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 ZHBXLZQQVCDGPA-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- XEVRDFDBXJMZFG-UHFFFAOYSA-N carbonyl dihydrazine Chemical compound NNC(=O)NN XEVRDFDBXJMZFG-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 1
- 239000004914 cyclooctane Substances 0.000 description 1
- 125000006159 dianhydride group Chemical group 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000010512 thermal transition Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
- B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
- C08G73/1082—Partially aromatic polyimides wholly aromatic in the tetracarboxylic moiety
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
一种由共聚酰亚胺形成的气体分离膜，其中所述共聚酰亚胺通过包括o-联甲苯胺砜、至少一种其它的亲水性二胺和2，2-二(3，4-二羧基苯基)六氟代丙烷二酐的单体的共聚反应形成。任选可以包含一种或多种另外的芳族二酐。所述新膜具有优良的组合特性，即对由气体混合物中要分离的气体的高选择性、高渗透性以及对烃类化学物质的强的溶剂耐受性。因此该膜可用于从气体混合物中分离气体，其中在所述气体混合物中存在气态或液态烃杂质，例如在天然气纯化过程中使二氧化碳与甲烷和/或氮分离。
Description
发明领域
本发明涉及含有共聚酰亚胺的气体分离膜以及应用这种膜从气体混合物中分离一种或多种气体的方法。
发明背景
许多工业气体分离方法应用选择性气体可渗透膜。在一些气体分离过程中建议使用芳族共聚酰亚胺作为膜材料。已经开发出一些芳族共聚酰亚胺膜用于提供渗透通过膜的一种气体相对于另一种气体高的相对选择性。但这种膜却具有低的气体渗透速率。另一方面，不同的共聚酰亚胺气体分离膜具有高得多的气体渗透速率，但它们却相应具有较低的相对气体选择性。
除了好的气体分离特性外，工业上的重要过程经常对膜材料具有其它苛刻的要求。例如天然气的纯化涉及在污染所要分离的混合物的液态和气态烃存在时使二氧化碳与甲烷和/或氮分离。这一用途中的膜材料应该对烃杂质的溶剂效应有很强的耐受性。另一个重要的考虑因素是所述材料应该易于制成适合的膜结构。
对于所要分离的气体来说，希望共聚酰亚胺气体渗透膜同时具有高选择性和高气体渗透速率。还希望这种共聚酰亚胺膜另外对烃的溶剂活性具有强的耐受性。还希望共聚酰亚胺材料易于加工形成膜结构，同时保持其高选择性、高气体流量以及对烃的耐受性。
US 4,690,873公开了一种由四羧酸重复单元和由二氨基二甲基二亚苯基砜(“AMPS”)异构体得到的部分形成的共聚酰亚胺气体分离材料，所述异构体包括化合物o-联甲苯胺砜(“TSN”)。在下文表III中可以找到本申请中所指的所选择的化合物的汇编。所述组合物不包括2，2-二(3，4-二羧基苯基)六氟代丙烷二酐(“6FDA”)。所述产品膜具有很高的二氧化碳相对于甲烷的选择性，但二氧化碳的渗透性却非常低。
US 4,705,540公开了一种聚酰亚胺气体分离膜，其中膜组合物由含有芳族二胺和4-4′-(六氟代异亚丙基)-二(邻苯二甲酸酐)的混合物聚合得到。这将产生带有极强刚性链的聚酰亚胺。所述单体混合物不包括o-联甲苯胺砜与其它亲水性二胺的共混物。这种膜具有很高的二氧化碳渗透性，但二氧化碳/甲烷选择性却很少高于25。
US 5,042,992公开了一种气体分离材料，该材料是一种通过4-4′-(六氟代异亚丙基)-二(邻苯二甲酸酐)(“6FDA”)与二氨基-二烷基二亚苯基砜反应而形成的聚酰亚胺。这种材料可以形成具有高的二氧化碳渗透性和高的二氧化碳/甲烷选择性的膜。但该专利没有公开还含有第二种亲水性二胺的单体混合物，并且另外它没有提及是否聚酰亚胺对烃溶剂有耐受性。
US 5,591,250公开了一种应用由单一的二酐6FDA和一种或多种二胺单体反应形成的聚酰亚胺的膜来使二氧化碳与甲烷分离的方法。但没有公开应用o-联甲苯胺砜作为一种二胺。在众多实施例中仅有很少一部分被证实同时具有高的二氧化碳渗透性和高的二氧化碳/甲烷选择性。但没有报道所述膜对烃溶剂的耐受性。
发明概述
现在本发明提供一种共聚酰亚胺组合物的气体分离膜，所述膜有利地提供了用于工业上重要气体混合物的高选择性和高透膜流量的有利的组合特性，同时保持对烃化学品侵蚀的耐受性。所述气体分离膜的共聚酰亚胺通过包含o-联甲苯胺砜、不同于o-联甲苯胺砜的亲水性二胺以及2，2-二(3，4-二羧基苯基)六氟代丙烷二酐的单体共聚反应形成。任选地，在用于成膜的单体中可以包括一种或多种芳族二酐。所述共聚酰亚胺很容易加工成适用于气体分离的膜形式。
还提供了一种分离气体混合物的组分气体的方法，其中包括步骤：
(a)提供一种聚酰亚胺气体分离膜，所述聚酰亚胺通过二胺单体和二酐单体共聚反应形成，其中二胺单体包括o-联甲苯胺砜和不同于o-联甲苯胺砜的亲水性二胺，二酐单体包括2，2-二(3，4-二羧基苯基)六氟代丙烷二酐，
(b)使气体混合物与膜的一侧接触，从而使组分气体选择性透过膜，以及，
(c)由膜的另一侧脱除其中富含更优先渗透通过膜的组分气体的渗透气体组合物。
本发明的方法很适合从气体混合物中分离工业上重要的气体，并且对于天然气纯化中使二氧化碳与甲烷和/或氮分离来说是特别有用的。新的共聚酰亚胺气体分离膜有利地对粗天然气中可能存在的烃杂质具有耐受性，其中所述烃杂质如以环己烷、环庚烷、环辛烷、甲基环己烷、甲基环戊烷和1，2-二甲基环戊烷为代表的环烷烃、以及以苯、甲苯和二甲苯为代表的芳烃。
详细描述
本发明涉及一种由共聚酰亚胺组合物形成的气体分离膜。总体来说，所述共聚酰亚胺通过常规的方法步骤制成，其中二胺和二酐首先进行缩聚反应以形成聚酰胺酸。随后聚酰胺酸脱水得到聚酰亚胺。已经发现由特定选择的二胺和二酐单体生产的共聚酰亚胺提供了一种具有优越的气体分离、流量和烃耐受特性的气体分离膜。
至少应用两种二胺单体。一种是3，7-二氨基-2，8-二甲基二苯基砜，通常称为“o-联甲苯胺砜”，正如所提到的有时也称为“TSN”。至少一种其它二胺单体为亲水性二胺。所述亲水性二胺可以是芳族的、脂族的或这两者的组合。优选地，所述亲水性二胺具有如下通式I的结构：
其中R为6-24个碳原子的芳烃基、3-12个碳原子的脂族烃基或其混合物，并且X为亲水性基团。“亲水性基团”指的是所带的X基团为强极性的。优选的通式I的亲水性二胺中X为-OH、-SO3H、-CO2H、-NHR1、-NR2R3或其混合物，其中各R1、R2和R3均为烷基或芳基。这些亲水性二胺的组合也是所考虑的和优选的。代表性的亲水性二胺包括1，3-二氨基-2-羟基丙烷(“DAHP”)、1，3-二氨基苯-4-磺酸(“HSMPD”)、2，2-二(3-氨基-4-羟基苯氧基)六氟代丙烷(“bisAPAF”)、3，3′-二羟基联苯胺(“HAB”)、L-赖氨酸、1，3-二氨基-5-苯甲酸(“DABA”)及其混合物。
TSN是本发明中所有共聚酰亚胺中均应用的二胺单体组分。虽然不希望被特性理论所束缚，但确信TSN对聚合物结构中形成优化的自由体积有贡献。这一点被认为使共聚酰亚胺具有强的气体可渗透性。所形成的共聚酰亚胺膜的强的烃溶剂耐受性和高的渗透选择性归功于亲水性二胺共聚单体的存在。已经发现优选约20-80mol％，并且更优选为约40-60mol％的全部二胺单体应该是亲水性二胺，并且余量应该为TSN。
一方面，形成共聚酰亚胺的单体混合物包括含氟的芳族二酐2，2-二(3，4-二羧基苯基)六氟丙烷二酐、另外称为4，4′-(六氟异亚丙基)-二(邻苯二甲酸酐)，并且正如所提到的，偶尔亦被称为“6FDA”或“6F”。在一个优选的实施方案中，6FDA是与二胺组分反应形成共聚酰亚胺的唯一的二酐。
另一方面，二酐单体可以包括除了6FDA且与之不同的一种或多种其它芳族二酐。优选至少约30mol％，并且更优选至少约50mol％的二酐单体应该是6FDA。适用于本发明的代表性芳族二酐包括1，2，4，5-苯四羧酸二酐(即苯均四酸二酐或“PMDA”)、3，3′，4，4′二苯甲酮四羧酸二酐(“BTDA”)、3，3′，4，4′二苯基四羧酸二酐(“BPDA”)、二苯基砜二酐(“DSDA”)以及双酚A二酐(“BPADA”)。
共聚酰亚胺可以通过本领域所熟知的方法来制备。在一个优选的方法中，大约等摩尔量的二酐和二胺按常规的缩聚和脱水聚合方式反应。热的酰亚胺化是优选的，因为它会产生更高分子量的聚合物，从而使膜的生产更容易。本发明的共聚酰亚胺的重均分子量为约23,000至约400,000，更优选为约50,000至约280,000。
优选地，首先将二胺溶解在聚合反应溶剂介质中，然后在连续搅拌的条件下逐渐分批加入二酐单体。所应用的溶剂量应该在混合所有单体以后，足以使单体浓度范围为约10wt％至约30wt％，并且优选为约20wt％。如果需要，可以加入溶剂以获得所希望的浓度。
可用于聚合反应过程的溶剂是有机溶剂，并且优选为无水的。所述溶剂不应该与聚合反应过程中涉及的单体、中间体、产物或其它化学物质反应至可察觉的程度。所希望的是二酐或二胺单体的任一部分或优选两者都可溶于溶剂中。适合溶剂的例子为N，N-二甲基乙酰胺(“DMAC”)、N-甲基-2-吡咯烷酮(“NMP”)、γ-丁内酯、m-甲酚、吡啶、二甘醇二甲醚等物质以及这些溶剂的混合物。
在无水条件下进行聚合反应，同时搅拌混合物并保持反应物的温度低于约50℃，优选在约20-35℃的范围内。可以将反应容器浸在冷却浴中以控制温度。聚合反应进行的时间应足以形成具有所希望的分子量的聚酰胺酸。这一过程通常在约2至约20小时内进行。然后所述聚酰胺酸可以通过将聚酰胺酸溶液加热至约150-200℃，直到酰亚胺化过程基本完成，从而热转化为聚酰亚胺。然后可以通过用醇(例如甲醇)或水沉淀以及用附加醇或水洗涤而从溶液中回收聚酰亚胺。
共聚酰亚胺易溶于一些溶剂有助于应用该常规技术使聚合物形成气体分离膜。优选的溶剂是极性非质子溶剂。代表性例子包括NMP和DMAC。
为了制备本发明的膜，将聚合物溶解在适合溶剂中，然后将溶液在载体上浇成薄片，或通过一个喷丝头纺纱以产生中空纤维。然后脱除溶剂。溶剂脱除技术影响所形成的膜的特性。例如通过加热蒸发溶剂会产生致密性不均匀的膜。通过比较可知，当在液体中骤冷膜或纤维膜前体结构会形成不对称的膜，即其密度随与膜表面的垂直距离而变化的膜，其中所述液体不是聚合物的溶剂，并且与聚合物溶液的溶剂相互混溶。
本发明的一些共聚酰亚胺是不能充分溶解于工业处理优选的溶剂中，这些溶剂如无毒、无腐蚀性、不昂贵的液体，它们具有适当的挥发特性，并且易于获取。对于这些共聚酰亚胺来说，新的共聚酰亚胺膜仍然可以通过在适合溶剂中溶解聚酰胺酸前体、形成前面描述的膜结构、并随后通过加热膜结构使聚酰胺酸转化为共聚酰亚胺来制备。
本发明的共聚酰亚胺膜可以形成本领域所公知的多种形状。平膜和中空纤维是优选的。平膜可以在框内自我支撑，或者利用通常多孔的基质进行支撑。所述平膜可以用于平的结构。其它可能的平膜结构包括按螺旋形状缠绕膜或折叠膜以使单位体积产生更高的透膜表面积。中空纤维可以按平行流动方式布置形成一束，并且每一端均装入一个管板内。所述管板***一个通常为圆筒状的容器中以形成本领域已知的中空纤维气体分离膜组件。
所述新膜可以很有利地用于分离气体混合物的气体组分。按常识来讲，这一操作通过使气体混合物与膜的一侧接触并使混合物的组分渗透通过膜来完成的。比其它组分更优先渗透的混合物的组分将更迅速地通过，从而在膜的另一侧形成所谓的“渗透”组合物。因此这种渗透组合物将富含渗透较快的组分。在第一侧、偶尔称为“滞留”侧的气体组合物将会变得贫含渗透较快的组分。通常，从滞留侧的高压到渗透侧的低压在膜的两侧形成压力梯度。这将提高渗透速率。从膜的附近采出渗透和滞留组合物，用于任何具体实际应用所要求的进一步处理、贮存、应用或处置。有关操作气体分离膜装置的考虑对本领域的熟练技术人员来说是充分理解的。
实施例
下面通过其一些代表性实施方案的实施例来描述本发明，其中所有份、比例和百分比如果不特别指出的话均为重量。所有原始得到的不是SI单位的重量和测量单位均已经转化为SI单位。
将一个配有机械搅拌器、氮入口和Deau-Stark捕集器的250mL的三颈圆底烧瓶在氮气气氛下用火焰干燥，并使之冷却至环境温度。将表I所示的二胺混合物(总共0.025摩尔)全部溶解在约80-90mLNMP中。然后将表I中的芳族二酐或二酐混合物(0.025摩尔)和另外10-20mL NMP一起加入。将所述溶液在室温下搅拌2小时。然后加入约30mL o-二氯苯(ODCB)或甲苯，加热溶液并在150-180℃下保持5-25小时，以共沸脱除水。然后使聚合物在水或甲醇中沉淀，在混合器中磨碎，用甲醇洗涤三次，然后用水洗涤两次。将聚合物在室温下空气干燥过夜，然后进一步在一个真空烘箱中在150-220℃干燥至少2小时。测量每一种聚合物在25℃在0.5wt/vol％的NMP中的固有粘度，并在表I中示出。
将上述制备的每种聚酰亚胺分别溶解于NMP或m-甲酚中以形成约20％的溶液。在100-120℃下，由每种溶液在玻璃板上浇成刀隙为38×10-5m(15mil)的膜。在该温度下使所述膜在板上干燥1-2小时。然后从板上脱除膜，冷却至室温，并进一步在空气中干燥过夜。将所述膜进一步在真空烘箱中在约68kPa(20英寸Hg柱)下、在220℃下干燥18小时。这样得到的膜的厚度为2×10-5至5×10-5m(1-2mils)。对每种膜分别测量其在3.45MPa(500psig)及30℃下对纯的二氧化碳和甲烷的渗透性。二氧化碳的渗透性以及由纯组分渗透性的比计算得到的二氧化碳相对于甲烷的膜的选择性列于表I中。
表I
| 实施例 | 二胺1 | 二胺2 | 二胺1/二胺2(mol％/mol％) | 二酐1“DA-1” | 二酐2“DA-2” | DA-1/DA-2(mol％/mol％) | 固有粘度 | CO2渗透率(Barrers) | CO2渗透率CH4渗透率(Barrers/Barrers) |
| 1 | TSN | DAHP | 75/25 | 6FDA | - | 100/0 | 0.46 | 47.9 | 58.9 |
| 2 | TSN | HSNPD | 50/50 | 6FDA | - | 100/0 | 0.76 | 88.8 | 59.2 |
| 3 | TSN | HSMPD | 50/50 | 6FDA | BPDA | 50/50 | 0.69 | 163 | 41.6 |
| 4 | TSN | BisAPAF | 50/50 | 6FDA | - | 100/0 | 0.64 | 46.8 | 56.5 |
| 5 | TSN | BisAPAF | 50/50 | 6FDA | BPDA | 50/50 | 0.85 | 27 | 56.3 |
| 6 | TSN | BisAPAF | 25/75 | 6FDA | - | 100/0 | 0.62 | 30.5 | 54.8 |
| 7 | TSN | HAB | 50/50 | 6FDA | - | 100/0 | 0.77 | 34.3 | 64.4 |
| 比较例1 | TSN | - | 100/0 | BPADA | - | 100/0 | 0.66 | 13.5 | 40.3 |
| 比较例2 | TSN | - | 100/0 | BPDA | - | 100/0 | - | 2.9 | 236a |
| 比较例3 | BisAPAF | - | 100/0 | 6FDA | - | 100/0 | 0.64 | 20.3 | 45.1 |
| 比较例4 | HAB | - | 100/0 | 6FDA | - | 100/0 | - | 5.9 | 76b |
| 比较例5 | TSN | - | 100/0 | 6FDA | - | 100/0 | 1.08 | 109 | 40.0 |
a按照美国专利US 4,690,873中所报道的数据
b按照美国专利US 5,591,250中所报道的数据
实施例1-7表明按本发明制造的多种气体分离膜均能够同时提供高于约25barrer的高二氧化碳渗透性和高于约40的高二氧化碳/甲烷选择性。比较例1和2涉及由TSN、不同于6FDA的二酐以及无附加亲水性二胺制备的聚酰亚胺的膜。比较例3和4涉及无TSN的聚酰亚胺膜。对比较例2和4没有进行实验，但在美国专利US 4,690,873和US 5,591,250中所进行及描述的实验的结果在表I中给出，这两篇专利均作为参考引入本申请。这些比较膜具有高的二氧化碳/甲烷选择性，但二氧化碳通量低。比较例5测试了没有附加亲水性二胺共聚单体的TSN/6FDA聚酰亚胺的膜。所述膜同时具有高的CO2通量和CO2/CH4选择性。但其对烃溶剂的耐受性是不足的，这将在下文进行解释。
将本发明的几种共聚酰亚胺的烃溶剂耐受性与常规聚酰亚胺进行比较。将每个重约1g所要测试的材料的分离膜在室温下在甲苯或己烷中浸渍24小时。然后将样品从溶剂中取出，用一块吸收材料轻擦样品，直到样品从视觉观察来看无表面液体为止并称重。然后计算每个样品浸泡后所保留的溶剂量相对于无溶剂的初始重量的百分比。这些溶剂的吸收结果在表II中给出。
吸收较少溶剂的样品被认为对溶剂有更强的耐受性。表II表明实施例1、4和5的膜具有非常低的溶剂吸收量。虽然如上述制备的对比例6和7的膜对己烷有好的很小的吸收量，但它们吸收大量的甲苯。已经证明比较例5的膜具有高的二氧化碳通量和高的二氧化碳相对于甲烷的选择性，并且它还具有可接受的己烷吸收量。但溶剂的侵蚀非常严重，以致使该样品在甲苯中浸泡后太脆不能进行吸收测量。
总之，这些实施例证明本发明的共聚酰亚胺形成的膜提供了一种独特的组合性质，该组合性质包括透膜通量、高的选择性以及对烃溶剂好的耐受性，而缺少一种或多种新的共聚酰亚胺膜组分的组合物的膜不能达到所有这些所希望的性能特性。
表II
| 实施例 | 二胺1 | 二胺2 | 二胺1/二胺2(mol％/mol％) | 二酐1“DA-1” | 二酐2“DA-2” | DA-1/DA-2(mol％/mol％) | 己烷吸收(％) | 甲苯吸收(％) |
| 1 | TSN | DAHP | 75/25 | 6FDA | - | 100/0 | -0.1 | 7.8 |
| 4 | TSN | BisAPAF | 50/50 | 6FDA | - | 100/0 | 0.5 | 0.5 |
| 5 | TSN | BisAPAF | 50/50 | 6FDA | BPDA | 50/50 | 0.0 | 0.0 |
| 比较例5 | TSN | - | 100/0 | 6FDA | - | 100/0 | 1.0 | 脆 |
| 比较例6 | DAPI | - | 100/0 | BTDA | - | 100/0 | 1.0 | 41.5 |
| 比较例7 | DAM | - | 100/0 | MPD | - | 100/0 | 2.8 | 27.5 |
虽然已经在前面的描述中从具体角度针对全面描述本发明的具体形式而选择本发明的这些形式进行说明，并且对相关领域的普通技术人员来说足够了，但应该理解的是各种带来基本等效或更好的结果和/或操作性能的替换和改进均应认为在下列权利要求的范围和精神实质内。
表III
表III(续)
Claims (9)
1.一种聚酰亚胺气体分离膜，其中所述聚酰亚胺通过包括o-联甲苯胺砜、2，2-二(3，4-二羧基苯基)六氟代丙烷二酐和选自如下物质的二胺的单体的共聚反应形成：1，3-二氨基-2-羟基丙烷、1，3-二氨基苯-4-磺酸、2，2-二(3-氨基-4-羟基苯氧基)六氟代丙烷、3，3′-二羟基联苯胺、L-赖氨酸、1，3-二氨基-5-苯甲酸及其混合物。
2.权利要求1的膜，其中所述单体进一步包括一种不同于2，2-二(3，4-二羧基苯基)六氟代丙烷二酐的芳族二酐。
3.权利要求2的膜，其中不同于2，2-二(3，4-二羧基苯基)六氟代丙烷二酐的芳族二酐选自苯均四酸二酐、3，3′，4，4′-二苯甲酮四羧酸二酐、3，3′，4，4′-二苯基四羧酸二酐、二苯基砜二酐、双酚A二酐及其混合物。
4.权利要求1的膜，其中二胺为o-联甲苯胺砜和二胺单体总和的20-80mol％。
5.一种分离气体混合物的组分气体的方法，包括如下步骤：
(a)提供一种聚酰亚胺气体分离膜，所述聚酰亚胺通过二胺单体和二酐单体的共聚反应形成，其中二胺单体包括o-联甲苯胺砜和选自1，3-二氨基-2-羟基丙烷、1，3-二氨基苯-4-磺酸、2，2-二(3-氨基-4-羟基苯氧基)六氟代丙烷、3，3′-二羟基联苯胺、L-赖氨酸、1，3-二氨基-5-苯甲酸及其混合物的二胺，二酐单体包括2，2-二(3，4-二羧基苯基)六氟代丙烷二酐，
(b)使气体混合物与膜的一侧接触，从而使组分气体选择性透过膜，以及，
(c)由膜的另一侧脱除其中富含更优先渗透通过膜的组分气体的渗透气体组合物。
6.权利要求5的方法，其中二胺为o-联甲苯胺砜和二胺单体总和的20-80mol％。
7.权利要求5的方法，其中二酐单体进一步包括至少一种不同于2，2-二(3，4-二羧基苯基)六氟代丙烷二酐的芳族二酐。
8.权利要求5的方法，其中与膜接触的气体混合物包括为液态或气态的烃溶剂。
9.权利要求5的方法，其中气体混合物包括选自二氧化碳、甲烷、氮及其混合物的气体。
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| US09/740,286 US6383258B1 (en) | 2000-12-19 | 2000-12-19 | Copolyimide gas separation membranes |
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-
2000
- 2000-12-19 US US09/740,286 patent/US6383258B1/en not_active Expired - Lifetime
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2001
- 2001-11-16 CN CNB018208320A patent/CN1248773C/zh not_active Expired - Fee Related
- 2001-11-16 CA CA002431731A patent/CA2431731A1/en not_active Abandoned
- 2001-11-16 AU AU2002226939A patent/AU2002226939A1/en not_active Abandoned
- 2001-11-16 EP EP01995889A patent/EP1351757A2/en not_active Ceased
- 2001-11-16 JP JP2002551079A patent/JP2004516131A/ja active Pending
- 2001-11-16 WO PCT/US2001/043689 patent/WO2002049747A2/en not_active Application Discontinuation
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| CN1482941A (zh) | 2004-03-17 |
| AU2002226939A1 (en) | 2002-07-01 |
| WO2002049747A2 (en) | 2002-06-27 |
| US6383258B1 (en) | 2002-05-07 |
| CA2431731A1 (en) | 2002-06-27 |
| JP2004516131A (ja) | 2004-06-03 |
| WO2002049747A3 (en) | 2003-01-23 |
| EP1351757A2 (en) | 2003-10-15 |
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