CN1016349B - 制备高溶解性芳香聚酰亚胺的方法 - Google Patents
制备高溶解性芳香聚酰亚胺的方法Info
- Publication number
- CN1016349B CN1016349B CN88102914A CN88102914A CN1016349B CN 1016349 B CN1016349 B CN 1016349B CN 88102914 A CN88102914 A CN 88102914A CN 88102914 A CN88102914 A CN 88102914A CN 1016349 B CN1016349 B CN 1016349B
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- polyimide
- bpda
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- 239000004642 Polyimide Substances 0.000 title claims abstract description 85
- 229920001721 polyimide Polymers 0.000 title claims abstract description 85
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 3
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 3
- 238000002360 preparation method Methods 0.000 claims description 20
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 238000007348 radical reaction Methods 0.000 claims 1
- 239000002904 solvent Substances 0.000 description 62
- 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 43
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 25
- 230000005540 biological transmission Effects 0.000 description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 16
- 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 description 16
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 8
- 238000000576 coating method Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
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- -1 amino-phenoxy Chemical group 0.000 description 6
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- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 5
- 238000007605 air drying Methods 0.000 description 4
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- 125000004427 diamine group Chemical group 0.000 description 4
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- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 3
- LFBALUPVVFCEPA-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C(C(O)=O)=C1 LFBALUPVVFCEPA-UHFFFAOYSA-N 0.000 description 3
- CQMIJLIXKMKFQW-UHFFFAOYSA-N 4-phenylbenzene-1,2,3,5-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C1C1=CC=CC=C1 CQMIJLIXKMKFQW-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000000113 differential scanning calorimetry Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
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- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- MSFXHZLKWZHXFL-UHFFFAOYSA-N 2-anthracen-1-ylaniline Chemical compound NC1=CC=CC=C1C1=CC=CC2=CC3=CC=CC=C3C=C12 MSFXHZLKWZHXFL-UHFFFAOYSA-N 0.000 description 1
- JJVKJJNCIILLRP-UHFFFAOYSA-N 2-ethyl-6-methylaniline Chemical compound CCC1=CC=CC(C)=C1N JJVKJJNCIILLRP-UHFFFAOYSA-N 0.000 description 1
- DDTKYVBFPULMGN-UHFFFAOYSA-N 2-methyl-6-propan-2-ylaniline Chemical compound CC(C)C1=CC=CC(C)=C1N DDTKYVBFPULMGN-UHFFFAOYSA-N 0.000 description 1
- VDJBIPLKIGSVRG-UHFFFAOYSA-N 3-chloro-2,6-diethylaniline Chemical compound CCC1=CC=C(Cl)C(CC)=C1N VDJBIPLKIGSVRG-UHFFFAOYSA-N 0.000 description 1
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 description 1
- IPDXWXPSCKSIII-UHFFFAOYSA-N 4-propan-2-ylbenzene-1,3-diamine Chemical compound CC(C)C1=CC=C(N)C=C1N IPDXWXPSCKSIII-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008064 anhydrides Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 230000018044 dehydration Effects 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
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- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
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- NQPDZGIKBAWPEJ-UHFFFAOYSA-N pentanoic acid group Chemical class C(CCCC)(=O)O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920005575 poly(amic acid) Polymers 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
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- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
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- 230000008961 swelling Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
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- 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
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- 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
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- 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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
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- 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
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- 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
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- Separation Using Semi-Permeable Membranes (AREA)
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- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
公开了具有下式结构的高溶解性、光学透明的芳香聚酰亚胺：
其中-X和-X1分别是含有1-6个碳原子的伯烷基或仲烷基，-X与-X1不同，
-Y分别是-H或-Z，
-Z分别是-Cl、-Br或-I，
r＝r+t的0-100%，且
S＝100%
t＝r+t的100%-r。
Description
本发明涉及由烷基取代的4，4′-亚甲基二苯胺和3，3′，4，4′-联苯四甲酸二酐（BPDA）制备可溶于非质子传递溶剂的全环化芳香聚酰亚胺的方法。
美国专利4，378，400公开了BPDA类的聚酰亚胺及其作为气体分离膜的应用。美国专利4，378，400（10栏，19-21行）公开其实例中有一个不溶于二甲基乙酰胺。美国专利4，378，324、4，486，376、4，528，004、4，370，290、4，440，643、4，460，526、4，474，662、4，474，858、4，485，056、4，512，893和4，535，105公开了这类聚酰亚胺的二次加工工艺等，但未公开在非质子传递良溶剂中的溶解性。英国专利申请G.B.2，176，196公开了BPDA类可模塑聚酰亚胺粉末的生产和应用。其生产工艺是基于BPDA类聚酰亚胺在非质子传递良溶剂，例如N-甲基吡咯烷酮中的不溶解性。
日本专利申请公报61-195125公开了由9，10-二（氨基苯基）蒽与BPDA的构造异构体2，3，3′，4′-联苯四甲酸二酐制备的聚酰亚胺，在非质子传递良溶剂，例如N-甲基吡咯烷酮中的溶解性。他们未公开由同样的二胺与BPDA制备的聚酰亚胺在非质子传递良溶剂，例如N-甲基吡咯烷酮中的溶解性。
美国专利4，696，994公开了由BPDA与二（氨基-苯氧基-苯基）砜或二（氨基-苯氧基-苯基）丙烷制备的聚酰亚胺在非质子传递良溶剂，例如N-甲基吡咯烷酮中的溶解性。
欧洲专利申请132，221;141，781和181，837公开了含烷基取代二胺的芳香聚酰亚胺。在这些专利申请的任何实例中均未使用联苯四甲酸二酐。
美国专利4，629，685;4，629，777和4，656，116公开了高级烷基取代的芳香聚酰亚胺，其中有些可溶于非质子传递良溶剂。他们未公开这些聚酰亚胺可溶于较弱溶剂中。在这些专利的任何实例中均未使用BPDA。
美国专利3，356，648公开了由六氟亚丙基桥的二胺和二酐合成的聚酰胺酸和聚酰亚胺可溶于相对较弱的溶剂，例如丙酮中，但不溶于较弱的溶
剂，例如甲苯中。在该专利的任何实例中均未使用BPDA。
美国专利3，959，350叙述了可溶于非质子传递良溶剂中的聚酰亚胺。他们未举例说明其在较弱溶剂中的溶解性。此专利的任何实例中均未使用BPDA。
美国专利3，705，870叙述了由2，4-二氨基二苯胺和2，4-二氨基二苯硫醚制备的可溶性聚酰亚胺。他们未公开其在弱溶剂中的溶解性。在该专利的任何实例中均未使用BPDA。
美国专利3，705，869叙述了由3，3-二（对氨基苯基）-1-苯基羟吲哚制备的可溶性聚酰亚胺。他们未公开其在弱溶剂中的溶解性。在该专利的任何实例中均未使用BPDA。
美国专利3，758，434叙述了可溶于非质子传递良溶剂中的聚酰亚胺。他们未公开其在较弱溶剂中的溶解性。在该专利的任何实例中均未使用BPDA。
美国专利3，787，367叙述了可溶性共聚酰亚胺。他们未公开其在较弱溶剂中的溶解性。在该专利的任何实例中均未使用BPDA。
美国专利3，803，075叙述了由2，6-二氨基-S-三嗪制备的可溶性聚酰亚胺。他们表明其材料不溶于弱溶剂中。在该专利的任何实例中均未使用BPDA。
美国专利3，856，752叙述了由苯基二氢化茚二胺和二酐制备的可溶性聚酰亚胺。他们未公开其在弱溶剂中的溶解性。在该专利的任何实例中均未使用BPDA。
美国专利4，078，142和美国专利4，145，522叙述了已改善溶解性的聚酰亚胺材料。然而未公开其溶解性资料。这些专利的任何实例中均未使用BPDA。
美国专利3，546，175叙述了由2，4-二氨基异丙苯和1，2，4，5-苯四酸二酐和3，3′，4，4′-二苯甲酮四甲酸二酐制备的可溶性聚酰亚胺。发现这些材料只溶于非质子传递良溶剂。在该专利的任何实例中均未使用BPDA。
美国专利3，642，682叙述了由胍胺类二胺制备的可溶性聚酰亚胺。他们公开对于其材料，弱溶剂可用作为非质子传递良溶剂的稀释剂或助溶剂。该专利的任何实例中均未使用BPDA。
美国专利4，588，804叙述了一系列可溶性聚酰亚胺。他们未公开其在弱溶剂中的溶解性。在该专利的任何实例中均未使用BPDA。
美国专利4，607，093叙述了可溶性聚酰亚胺。公开了其材料不溶于弱溶剂。在该专利的任何实例中均未使用BPDA。
NASA-TM-89016叙述了可溶性聚酰亚胺。未公开这些聚酰亚胺可溶于弱溶剂中，并且未使用BPDA。
本发明涉及制备芳香聚酰亚胺的方法，该芳香聚酰亚胺可溶于比以前的聚酰亚胺类所有的更宽的溶剂范围中。由这些聚酰亚胺制成的薄膜基本上是光学透明和无色的。本发明的这些聚酰亚胺是由二酐和4，4′-亚甲基二苯胺制备的，该二酐是联苯四甲酸二酐，该二苯胺在与氨基相邻的位置上被烷基取代并且有时还被卤原子所取代。
芳香聚酰亚胺作为一类化合物，在大多数溶剂中往往不溶解。这种不溶性与高软化温度相结合，已使芳香聚酰亚胺难于二次加工成许多类型的产品。由不溶性芳香聚酰亚胺进行薄膜、涂层和其它构件的二次加工需要复杂的工艺，例如将其制成的粉末聚结。另一种二次加工技术包括由不溶性聚酰亚胺的可溶性聚酰胺酸前体制备薄膜。在脱除过量溶剂后，该薄膜必须经热脱水或化学脱水以使前体薄膜转化为聚酰亚胺薄膜。另外还有一些问题，例如在酰亚胺化步骤的过程中由于副产物水的挥发而造成空隙的形成。
在本技术领域中，已通过可溶性全环化聚酰亚胺的发明克服了上述缺点。在先有技术中已公开了可溶性全环化的3，3′，4，4′-联苯四甲酸二酐（BPDA）类的聚酰亚胺。这些聚酰亚胺通常只溶于氯化的溶剂（例如二氯甲烷）和酚类（例如甲苯酚）溶剂。这些溶剂存在有害健康的问题。例如，甲苯酚接触毒性很大，而吸入二氯甲烷蒸汽引起呼吸混乱。通过使用可溶于较宽范围的非质子传递溶剂的BPDA类聚酰亚胺可解决这些问题，例如N-甲基吡咯烷酮、N，N′-二甲基乙酰胺、二甲基甲酰胺、二甲基亚砜、甲苯等等。
本发明克服了上述缺点并且提供了制备第一种已知类的全环化BPDA类的聚酰亚胺的方法，该聚酰亚胺可溶于宽范围的非质子传递溶剂中，范围从N-甲基吡咯烷酮（NMP）到甲苯。这类聚酰
亚胺主要是由取代的亚甲基二苯胺和3，3′，4，4′-联苯四甲酸二酐（此后表示为BPDA）组合制备的。可溶于宽范围的非质子传递溶剂中的合适的聚酰亚胺组合物，包括具有如下重复单元的聚酰亚胺：
-X和-X1分别为含有1～6个碳原子的伯烷基或仲烷基，最好为甲基、乙基或异丙基。
-X与-X1不同。
-Y分别为-H或-Z。
-Z分别为-Cl、-Br或I，最好是-Cl。
r＝r+t的0-100%
S＝100%
t＝r+t的100%-r
据信这类高温BPDA类聚酰亚胺在宽范围非质子传递溶剂中惊人的溶解性是在其中引入的结构特征相结合的直接结果。如先有技术所述，某些引入了3，3′，4，4′-联苯四甲酸二酐（BPDA）的全环化芳香聚酰亚胺可溶于氧化的溶剂（例如二氯甲烷）和酚类溶剂（例如甲苯酚）。但并未完全理解这种溶解性。通常，BPDA类聚酰亚胺不溶于非质子传递溶剂。例如，当于非质子传递良溶剂，例如N，N-二甲基乙酰胺（美国专利4，378，400;10栏，21行）和N-甲基吡咯烷酮（美国专利4，508，766;7栏，14行）中制备BPDA类聚酰亚胺时，该BPDA类聚酰亚胺以粉末的形式从溶液中沉淀出来。这种在非质子传递溶剂中的不溶性已被用于制备BPDA类可模塑聚酰亚胺粉末（英国专利申请GB2，176，196A）。仅有一种情况，已公开BPDA类聚酰亚胺可溶于非质子传递良溶剂（美国专利4，696，994）。至此，在聚酰亚胺中引入BPDA还不是产生聚合物在宽范围的非质子传递溶剂中的溶解性的充分依据。
二胺基团周围的邻烷基取代基往往空间聚集酰亚胺健。这将导致二胺基团的芳香基被排斥在酰亚胺基团和二酐基团的芳香基组成的平面外。因此，在芳香聚酰亚胺链中的电子环状共轭大大减小。另外，上述烷基取代基对薄膜和/或涂层中不同聚酰亚胺链间的强电子相互作用有空间阻碍。然而，如先有技术和本发明的对比例中所述，引入邻烷基取代基，就其本身而言并不是增大聚合物在非质子传递良溶剂，例如N-甲基吡咯烷酮中的溶解性的充分依据。
在二胺基团中引入结构不同的邻烷基取代基和/或在邻烷基取代的二胺基团中引入间卤代取代基，使聚合物链更加无序。这种聚合物链的无序使聚酰亚胺链的大分子结构更混乱，因此使薄膜和/或涂层中聚酰亚胺链内排列位阻更大。
上述结构特征的结合使链内和链间相互作用大大减弱。据信这种减弱使这类高温BPDA类聚酰亚胺在宽范围的非质子传递溶剂中具有惊人的溶解性。已发现，本发明的实例叙述的聚酰亚胺可溶于极宽范围的非质子传递溶剂中，该范围从非质子传递良溶剂（例如N-甲基吡咯烷酮）到极弱的非质子传递溶剂（例如甲苯）。无论其机理如何，本发明中叙述的这类在非质子传递良溶剂中溶解性大大改善的聚酰亚胺的出现，就先有技术而言是惊人的。
上述类型聚酰亚胺在非质子传递良溶剂中的溶解性大大简化了将BPDA类聚酰亚胺制成许多产品的二次加工。如前所述，用不溶性聚酰亚胺二次加工薄膜、涂层和其它构件需要复杂的工艺。另外，如先有技术中所述，由这类可溶于氯化的溶剂（例如二氯甲烷）和酚类溶剂（例如甲苯酚）中的全环化BPDA类聚酰亚胺二次加工这些产品，也由于这些溶剂有害而复杂化。本发明叙述的这类可溶于非质子传递良溶剂（例如N-甲基吡咯烷酮）中的全环化BPDA类聚酰亚胺的发明，大大简化了生产薄膜、涂层等的二次加工工艺。
已发现可溶于弱非质子传递溶剂（例如甲苯）中的上述类型的BPDA类聚酰亚胺的实例。在较弱溶剂中的溶解性提供了不能用于不溶性或微溶性聚酰亚胺的特有的二次加工机会。当用作涂层的材料只溶于基质材料对其敏感的溶剂时，难于二次加工多层结构。当使用可溶于基质材料对其不敏感的较弱的溶剂的聚酰亚胺材料，可解决这个问题。电子设备上的聚酰亚胺钝化涂层的应用是上述问题的一个实例。
本发明公开的聚酰亚胺可用于气体分离和电子应用方面，例如保护涂层。
实例1
在室温下于惰性气氛中，向搅拌着的4，4′-亚甲基-二（2-甲基-6-异丙基苯胺）（31.0g，0.01mol）于N-甲基吡咯烷酮（250ml）的溶液中，加入3，3′，4，4′-联苯四甲酸二酐（BPDA，29.7g，0.101mol，最后部分用另外的50mlN-甲基吡咯烷酮洗入溶液中）。这种暗橙色溶液于室温下搅拌过夜后，在快速搅拌下加入乙酐（37.7ml，0.4mol）和三乙胺（55.8ml，0.4mol）溶液。所得的淡橙色溶液在室温下搅拌4小时，然后在水中沉淀。过滤收集灰白色固体，用水洗涤两次并用甲醇洗涤两次。将此聚合物在空气中干燥过夜，然后在真空烘箱（20英寸汞柱）中于室温下干燥过夜，在120℃下干燥3小时，在250℃下干燥5小时，得到53.2g产物。
这种聚酰亚胺除了可溶于二氯甲烷和间甲苯酚外，可以大于20%的固体量（基于聚合物重量）溶于非质子传递良溶剂中，例如N-甲基吡咯烷酮、二甲基亚砜和二甲基乙酰胺。
在氮气气氛中，基线斜率＝5.0，以10℃/分的升温速率，用带有HCBl-5/N00523型样品池的990-3型杜邦热分析仪，对上述聚合物进行示差扫描量热（DSC）。用此方法直到400℃未出现相应于Tg的转变。
在空气气氛中，以10℃/分的升温速率，用带有951-5型样品池的99-2型杜邦热重分析仪，对上述聚合物进行热重分析（TGA）。观察到在400℃时失重5%，在515℃时失重40%。
上面制备的聚酰亚胺的薄膜是由15%（以重量计）聚合物的N-甲基吡咯烷酮溶液在100℃下流涎到用TEFLON
干润滑剂处理过的玻璃板上，所用刀隙（Knife gap）为15密耳（38.4×10-5米）。（TEFLON
干润滑剂含有碳氟调聚物，它可减小薄膜与玻璃板的粘结）。该薄膜在玻璃板上于100℃下干燥25分钟，冷至室温然后再在真空烘箱（20英寸汞柱）中于室温下干燥过夜。将该薄膜从玻璃板上剥离并在真空烘箱中于120℃下干燥4小时。
这种透明薄膜坚韧和柔软并且可折叠而不破裂。
实例2
在室温微氮吹扫的条件下，向搅拌着的4，4′-亚甲基-二（3-氯-2，6-二乙基苯胺）（189.5g，0.5mol）于N-甲基吡咯烷酮（1000ml）的溶液中，加入3，3′，4，4′-联苯四甲酸二酐（BPDA，148.6g，0.505mol，最后部分用另外的100mlN-甲基吡咯烷酮洗入溶液中）。将反应液缓慢加热到N-甲基吡咯烷酮的沸点（204℃），同时蒸出挥发份。用3.5小时的时间蒸出300ml水/N-甲基吡咯烷酮溶液后，将残余馏份回流到反应液中。当非常粘稠的反应液在约204℃下反应6.7小时后，将该反应液缓慢冷至室温。用N-甲基吡咯烷酮稀释该溶液，然后将其在水中沉淀。所得的固体依次用水和甲醇洗涤。将灰白色聚合物在空气中干燥过夜，然后在真空烘箱（20英寸汞柱）中于120℃下干燥3小时，在250℃下干燥5小时，得到326.8g产物。
这种聚酰亚胺可溶于弱非质子传递溶剂（例如甲苯）和非质子传递良溶剂，例如N-甲基吡咯烷酮和二甲基乙酰胺以及二氯甲烷和间甲苯酚中。
在氮气气氛中，基线斜率＝5.0，以10℃/分的升温速率，用带有HCB1-5/N00523型样品池的990-3型杜邦热分析仪，对上述聚合物进行示差扫描量热（DSC）。用此方法直到400℃未出现相应于Tg的转变。
在空气中，以10℃/分的升温速率，用带有951-5型样品池的99-2型杜邦热重分析仪，对上述聚合物进行热重分析（TGA）。观察到在400℃时失重5%，在490℃失时重40%。
实例3
在室温下于惰性气氛中，向搅拌着的4，4′-亚甲基-二（2-乙基-6-甲基苯胺）（28.2g，0.10mol）于N-甲基吡咯烷酮（250ml）的溶液
中，加入3，3′4，4′-联苯四甲酸二酐（BPDA，29.7g，0.101mol，最后部分用50mlN-甲基吡咯烷酮洗入溶液中）。这种黄橙色溶液在室温下搅拌过夜后，在快速搅拌下加入乙酐（37.7ml，0.4mol）、三乙胺（55.8ml，0.4mol）和N-甲基吡咯烷酮（150ml）的溶液。得到的黄色溶液在室温下搅拌4小时，然后在水中沉淀。该聚合物用水洗涤两次并用甲醇洗涤两次。在空气中干燥过夜后，将该固体在真空烘箱（20英寸汞柱）中于120℃下干燥3小时，在250℃下干燥5小时，得到55g产物。
这种聚酰亚胺可以大于20%的固体量（基于聚合物重量）溶于非质子传递良溶剂N-甲基吡咯烷酮中以及二氯甲烷和间甲苯酚中。
在氮气气氛中，基线斜率＝5.0，以10℃/分的升温速率，用带HCB1-5/N00523型样品池的990-3型杜邦热分析仪，对上述聚合物进行示差扫描量热（DSC）。用此方法直到400℃未出现相应于Tg的转变。
在空气中，以10℃/分的升温速率，用带有951-5型样品池的99-2型杜邦热重分析仪，对上述聚合物进行热重分析（TGA）。观察到在410℃时失重5%，在510℃时失重40%。
对比例1
在室温下于惰性气氛中，向搅拌着的4，4′-亚甲基-二（2，6-二乙基苯胺）（31.0g，0.10mol）于N-甲基吡咯烷酮（350ml）的溶液中，加入3，3′，4，4′-联苯四甲酸二酐（BPDA，29.7g，0.101mol），最后部分用50mlN-甲基吡咯烷酮洗入溶液中）。此橙色溶液在室温下搅拌过夜后，在快速搅拌下加入乙酐（37.7ml，0.4mol）、三乙胺（55.8g，0.4mol）和N-甲基吡咯烷酮（150ml）的溶液。这种淡黄色溶液在不足5分钟后即凝胶化。该反应混合物在室温下放置4小时后，在水中沉淀。得到的灰白色固体用水洗涤两次，用甲醇洗涤两次。在空气中干燥过夜后，该固体在真空烘箱中（20英寸汞柱）在120℃下干燥3小时，在250℃下干燥5小时，得到55g产物。
这种聚酰亚胺在非质子传递良溶剂，例如N-甲基吡咯烷酮、二甲基乙酰胺和二甲基亚砜中溶胀但不溶解。这种聚酰亚胺溶于二氯甲烷和间甲苯酚。
Claims (7)
1、制备具有通式(Ⅰ)的芳香聚酰亚胺的方法，
其中-X和-X1分别为含有1-6个碳原子的伯烷基或仲烷基，-X与-X1不同，
-Y分别是-H或-Z，
-Z分别是-Cl、-Br或-I，
r=r+t的0-100%，且
t=r+t的100%-r，且
S=100%，
该方法包括使-Ar-或Ar1的至少一种基团与R基团反应，产生上述通式(Ⅰ)的芳香聚酰亚胺。
2、权利要求1中的芳香聚酰亚胺的制备方法，其中r是r+t的100%。
3、权利要求2中的芳香聚酰亚胺的制备方法，其中Y是H。
4、权利要求3中的芳香聚酰亚胺的制备方法，其中-X是甲基并且-X1是异丙基。
5、权利要求3中的芳香聚酰亚胺的制备方法，其中-X是乙基并且-X1是甲基。
6、权利要求1中的芳香聚酰亚胺的制备方法，其中-Z是-Cl。
7、权利要求6中的芳香聚酰亚胺的制备方法，其中t是r+t的100%。
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| US4948400A (en) * | 1988-06-30 | 1990-08-14 | Nippon Steel Chemical Co., Ltd. | Separation membranes and process for preparing the same |
| US4897092A (en) * | 1989-02-27 | 1990-01-30 | Air Products And Chemicals, Inc. | Polyimide membrane having improved flux |
| US4952220A (en) * | 1989-04-11 | 1990-08-28 | Air Products And Chemicals, Inc. | Membranes formed from unsaturated polyimides |
| US5055116A (en) * | 1989-05-22 | 1991-10-08 | Hoechst Celanese Corp. | Gas separation membranes comprising miscible blends of polyimide polymers |
| US4932982A (en) * | 1989-06-01 | 1990-06-12 | E. I. Du Pont De Nemours And Company | Copolyimide gas separation membranes derived from substituted phenylene diamines and substituted methylene dianilines |
| US4932983A (en) * | 1989-06-01 | 1990-06-12 | E. I. Du Pont De Nemours And Company | Copolyimide gas separation membranes derived from substituted methylene dianilines and unsubstituted diamines |
| US4945265A (en) * | 1989-07-13 | 1990-07-31 | National Semiconductor Corporation | ECL/CML pseudo-rail circuit, cutoff driver circuit, and latch circuit |
| US5074891A (en) * | 1989-07-27 | 1991-12-24 | Hoechst Celanese Corp. | Method of gas separation and membranes therefor |
| US4954144A (en) * | 1989-09-12 | 1990-09-04 | Air Products And Chemicals, Inc. | Polyimide membranes and their use for gas separation |
| US4988371A (en) * | 1989-09-12 | 1991-01-29 | The Dow Chemical Company | Novel alicyclic polyimide gas separation membranes |
| US4983191A (en) * | 1989-10-10 | 1991-01-08 | E. I. Du Pont De Nemours And Company | Production of aromatic polyimide membranes |
| US5042992A (en) * | 1990-03-21 | 1991-08-27 | W. R. Grace & Co.-Conn. | Gas separation material |
| US5067970A (en) * | 1990-05-11 | 1991-11-26 | W. R. Grace & Co.-Conn. | Asymmetric polyimide membranes |
| US5061298A (en) * | 1990-06-13 | 1991-10-29 | Air Products And Chemicals, Inc. | Gas separating membranes formed from blends of polyimide polymers |
| US5042993A (en) * | 1990-07-24 | 1991-08-27 | Air Products And Chemicals, Inc. | Gas separating membranes from polyimide polymers |
| US5045093A (en) * | 1990-10-16 | 1991-09-03 | Air Products And Chemicals, Inc. | Gas separating membranes from polyimide polymers and a process for using the same |
| US5178650A (en) * | 1990-11-30 | 1993-01-12 | E. I. Du Pont De Nemours And Company | Polyimide gas separation membranes and process of using same |
| US5391219A (en) * | 1991-04-15 | 1995-02-21 | Nitto Denko Corporation | Method for the separation and concentration of gas using a composite or asymmetric fluorine-containing polyimide membrane |
| US5234471A (en) * | 1992-02-04 | 1993-08-10 | E. I. Du Pont De Nemours And Company | Polyimide gas separation membranes for carbon dioxide enrichment |
| US5266100A (en) * | 1992-09-02 | 1993-11-30 | E. I. Du Pont De Nemours And Company | Alkyl substituted polyimide, polyamide and polyamide-imide gas separation membranes |
| US5248319A (en) * | 1992-09-02 | 1993-09-28 | E. I. Du Pont De Nemours And Company | Gas separation membranes made from blends of aromatic polyamide, polymide or polyamide-imide polymers |
| US5232472A (en) * | 1992-11-03 | 1993-08-03 | E. I. Du Pont De Nemours And Company | Polyimide and polyamide-imide gas separation membranes |
| US5286280A (en) * | 1992-12-31 | 1994-02-15 | Hoechst Celanese Corporation | Composite gas separation membrane having a gutter layer comprising a crosslinked polar phenyl-containing - organopolysiloxane, and method for making the same - |
| US5591250A (en) * | 1993-08-09 | 1997-01-07 | Gas Research Institute | Material and process for separating carbon dioxide from methane |
| US5750633A (en) * | 1994-10-26 | 1998-05-12 | Nitto Denko Corporation | Dope for cast formation and method of manufacturing the same |
| US5690870A (en) * | 1994-10-26 | 1997-11-25 | Nitto Denko Corporation | Method of manufacturing a polyimide-type gas permeation membrane including fluorine |
| US5817165A (en) * | 1995-06-15 | 1998-10-06 | Nitto Denko Corporation | Fluorine-containing polyimide gas separation membrane and method of manufacturing the same |
| US5725633A (en) * | 1995-06-30 | 1998-03-10 | Praxair Technology, Inc. | Sulfonated polyimide gas separation membranes |
| US5618334A (en) * | 1995-06-30 | 1997-04-08 | Praxair Technology, Inc. | Sulfonated polyimide gas separation membranes |
| JPH09122461A (ja) * | 1995-10-31 | 1997-05-13 | Nitto Denko Corp | ポリイミド系半透膜 |
| JPH09225273A (ja) * | 1996-02-23 | 1997-09-02 | Nitto Denko Corp | 積層非対称膜及びその製造方法 |
| JP3361755B2 (ja) | 1998-08-17 | 2003-01-07 | 財団法人石油産業活性化センター | 炭化水素の選択的分離方法 |
| US6500233B1 (en) | 2000-10-26 | 2002-12-31 | Chevron U.S.A. Inc. | Purification of p-xylene using composite mixed matrix membranes |
| US20030126990A1 (en) * | 2001-12-20 | 2003-07-10 | Koros William J. | Crosslinked and crosslinkable hollow fiber membrane and method of making same |
| US20030131731A1 (en) * | 2001-12-20 | 2003-07-17 | Koros William J. | Crosslinked and crosslinkable hollow fiber mixed matrix membrane and method of making same |
| US7507429B2 (en) * | 2004-01-09 | 2009-03-24 | Ecolab Inc. | Methods for washing carcasses, meat, or meat products with medium chain peroxycarboxylic acid compositions |
| US7803214B2 (en) * | 2006-07-21 | 2010-09-28 | Ube Industries, Ltd. | Asymmetric hollow-fiber gas separation membrane, gas separation method and gas separation membrane module |
| AU2008219065B2 (en) | 2007-02-19 | 2014-01-30 | Marine Polymer Technologies, Inc. | Hemostatic compositions and therapeutic regimens |
| ES2466916T3 (es) | 2007-06-27 | 2014-06-11 | Admune Therapeutics Llc | Complejos de IL-15 e IL-15R alfa y usos de los mismos |
| US8221531B2 (en) | 2007-12-31 | 2012-07-17 | Chevron U.S.A. Inc. | Crosslinked polyimide membrane, method for making the same using organic titanate catalysts to facilitate crosslinking and method of using the membrane for fluid separation |
| US8394176B2 (en) * | 2008-02-05 | 2013-03-12 | Ube Industries, Ltd. | Polyimide gas separation membrane and gas separation method |
| WO2010111755A2 (en) | 2009-04-01 | 2010-10-07 | Katholieke Universiteit Leuven - K.U.Leuven R & D | Improved method for making cross-linked polyimide membranes |
| US8366804B2 (en) * | 2010-05-28 | 2013-02-05 | Uop Llc | High permeance polyimide membranes for air separation |
| JP6144254B2 (ja) | 2011-04-15 | 2017-06-07 | マリン ポリマー テクノロジーズ，インコーポレーテッド | ポリ−ｎ−アセチルグルコサミンナノファイバを用いた疾患の治療 |
| US8758491B2 (en) | 2011-06-17 | 2014-06-24 | Honeywell International Inc. | Thin film gas separation membranes |
| ES2704681T3 (es) | 2013-03-14 | 2019-03-19 | Marine Polymer Tech Inc | Tratamiento de enfermedad con nanofibras de poli-N-acetilglucosamina |
| CN104211973B (zh) * | 2014-04-01 | 2015-06-17 | 无锡顺铉新材料有限公司 | 一种聚酰亚胺薄膜 |
| CN108346765B (zh) * | 2018-01-31 | 2020-02-18 | 青岛蓝科途膜材料有限公司 | 一种复合锂离子电池隔膜及其制备方法 |
| CN109865437A (zh) * | 2019-03-11 | 2019-06-11 | 长春工业大学 | 一种具有简易自我调节渗透性和选择性的含氨基聚芳醚酮气体分离膜及其制备方法 |
Family Cites Families (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US30351A (en) * | 1860-10-09 | Piston for steam-engines | ||
| US3423491A (en) * | 1964-09-02 | 1969-01-21 | Dow Chemical Co | Permselective hollow fibers and method of making |
| FR2050251A1 (en) * | 1969-07-08 | 1971-04-02 | Inst Francais Du Petrole | Sulphonated polyimides (i) used as ion ex- - changes and in electrodialysis |
| US3957651A (en) * | 1971-12-16 | 1976-05-18 | Chemical Systems Incorporated | Microporous polyester membranes and polymer assisted phase inversion process for their manufacture |
| US3822202A (en) * | 1972-07-20 | 1974-07-02 | Du Pont | Heat treatment of membranes of selected polyimides,polyesters and polyamides |
| US3816303A (en) * | 1972-12-20 | 1974-06-11 | Us Interior | Poly(n-amido)imides as semipermeable membranes |
| US4113628A (en) * | 1974-06-05 | 1978-09-12 | E. I. Du Pont De Nemours And Company | Asymmetric polyimide membranes |
| US4156597A (en) * | 1977-09-23 | 1979-05-29 | General Electric Company | Ultrathin polyetherimide membrane and gas separation process |
| JPS5471785A (en) * | 1977-11-18 | 1979-06-08 | Nitto Electric Ind Co Ltd | Selectively permeable membrane and production thereof |
| EP0023406B1 (en) * | 1979-07-26 | 1983-04-13 | Ube Industries, Ltd. | Process for preparing aromatic polyimide semipermeable membranes |
| JPS5854841B2 (ja) * | 1980-03-31 | 1983-12-07 | 日東電工株式会社 | 選択性透過膜の製造方法 |
| JPS56159314A (en) * | 1980-05-09 | 1981-12-08 | Ube Ind Ltd | Preparation of polyimide fiber |
| JPS5715819A (en) * | 1980-07-01 | 1982-01-27 | Ube Ind Ltd | Gas separating material |
| JPS57167414A (en) * | 1981-04-03 | 1982-10-15 | Ube Ind Ltd | Production of polyimide hollow fiber |
| JPS57170936A (en) * | 1981-04-14 | 1982-10-21 | Ube Ind Ltd | Preparation of porous polyimide film |
| GB2101137B (en) * | 1981-04-14 | 1984-09-26 | Ube Industries | Producing porous aromatic imide polymer membranes |
| JPS57205517A (en) * | 1981-06-11 | 1982-12-16 | Ube Ind Ltd | Preparation of polyimide hollow fiber |
| JPS57209608A (en) * | 1981-06-22 | 1982-12-23 | Ube Ind Ltd | Preparation of composite polyimide separation film |
| GB2104411B (en) * | 1981-07-08 | 1985-02-20 | Ube Industries | Aromatic polyimide composite separating membrane |
| JPS5811003A (ja) * | 1981-07-10 | 1983-01-21 | Ube Ind Ltd | ポリイミド系気体分離膜 |
| US4532041A (en) * | 1983-05-13 | 1985-07-30 | Exxon Research And Engineering Co. | Asymmetric polyimide reverse osmosis membrane, method for preparation of same and use thereof for organic liquid separations |
| US4629777A (en) * | 1983-05-18 | 1986-12-16 | Ciba-Geigy Corporation | Polyimides, a process for their preparation and their use |
| US4629685A (en) * | 1984-11-16 | 1986-12-16 | Ciba-Geigy Corporation | Process for irradiating polyimides |
| JPS61133118A (ja) * | 1984-11-30 | 1986-06-20 | Ube Ind Ltd | ガス分離ポリイミド膜 |
| US4705540A (en) * | 1986-04-17 | 1987-11-10 | E. I. Du Pont De Nemours And Company | Polyimide gas separation membranes |
| US4746474A (en) * | 1986-10-10 | 1988-05-24 | Hoechst Celanese Corporation | Ultrathin polyimide polymers films and their preparation |
| US4717394A (en) * | 1986-10-27 | 1988-01-05 | E. I. Du Pont De Nemours And Company | Polyimide gas separation membranes |
| US4717393A (en) * | 1986-10-27 | 1988-01-05 | E. I. Du Pont De Nemours And Company | Polyimide gas separation membranes |
-
1988
- 1988-04-13 US US07/175,503 patent/US4838900A/en not_active Expired - Lifetime
- 1988-05-16 OA OA59358A patent/OA08850A/xx unknown
- 1988-05-16 MA MA21520A patent/MA21279A1/fr unknown
- 1988-05-16 NZ NZ224630A patent/NZ224630A/xx unknown
- 1988-05-16 NO NO88882148A patent/NO882148L/no unknown
- 1988-05-17 DK DK269088A patent/DK269088A/da not_active Application Discontinuation
- 1988-05-17 BR BR8802382A patent/BR8802382A/pt unknown
- 1988-05-17 AU AU16335/88A patent/AU608323B2/en not_active Ceased
- 1988-05-17 ZA ZA883479A patent/ZA883479B/xx unknown
- 1988-05-18 AT AT88107946T patent/ATE92511T1/de not_active IP Right Cessation
- 1988-05-18 KR KR1019880005819A patent/KR890016095A/ko not_active Application Discontinuation
- 1988-05-18 EP EP88107946A patent/EP0337001B1/en not_active Expired - Lifetime
- 1988-05-18 DE DE88107946T patent/DE3882973T2/de not_active Expired - Fee Related
- 1988-05-18 CN CN88102914A patent/CN1016349B/zh not_active Expired
- 1988-05-18 CN CN88102904A patent/CN1036964A/zh active Pending
- 1988-05-18 JP JP63119443A patent/JPH01262925A/ja active Granted
- 1988-05-18 PT PT87515A patent/PT87515B/pt not_active IP Right Cessation
- 1988-06-10 TN TNTNSN88061A patent/TNSN88061A1/fr unknown
Also Published As
| Publication number | Publication date |
|---|---|
| KR890016095A (ko) | 1989-11-28 |
| DK269088D0 (da) | 1988-05-17 |
| AU608323B2 (en) | 1991-03-28 |
| TNSN88061A1 (fr) | 1990-07-10 |
| MA21279A1 (fr) | 1988-12-31 |
| NO882148D0 (no) | 1988-05-16 |
| PT87515A (pt) | 1989-11-10 |
| JPH01262925A (ja) | 1989-10-19 |
| OA08850A (en) | 1989-03-31 |
| DE3882973D1 (de) | 1993-09-09 |
| BR8802382A (pt) | 1989-12-05 |
| DK269088A (da) | 1989-10-14 |
| US4838900A (en) | 1989-06-13 |
| CN1036965A (zh) | 1989-11-08 |
| DE3882973T2 (de) | 1994-03-17 |
| CN1036964A (zh) | 1989-11-08 |
| ATE92511T1 (de) | 1993-08-15 |
| EP0337001B1 (en) | 1993-08-04 |
| ZA883479B (en) | 1990-01-31 |
| AU1633588A (en) | 1990-04-12 |
| PT87515B (pt) | 1994-04-29 |
| EP0337001A1 (en) | 1989-10-18 |
| NZ224630A (en) | 1989-11-28 |
| JPH053330B2 (zh) | 1993-01-14 |
| NO882148L (no) | 1989-10-16 |
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