CN1036964A - 聚酰亚胺气体分离膜 - Google Patents
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 40
- 239000004642 Polyimide Substances 0.000 title claims abstract description 31
- 125000003118 aryl group Chemical group 0.000 claims abstract description 19
- 239000012528 membrane Substances 0.000 claims abstract description 19
- 238000000926 separation method Methods 0.000 claims abstract description 14
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims description 51
- 239000000126 substance Substances 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 239000000460 chlorine Substances 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims 1
- 229910052740 iodine Inorganic materials 0.000 claims 1
- 239000011630 iodine Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 20
- 238000002360 preparation method Methods 0.000 abstract description 7
- 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 abstract description 6
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 63
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 38
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 36
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 33
- 206010013786 Dry skin Diseases 0.000 description 30
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 28
- 229910052753 mercury Inorganic materials 0.000 description 28
- 238000001291 vacuum drying Methods 0.000 description 27
- 238000003756 stirring Methods 0.000 description 24
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- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 18
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- 238000002347 injection Methods 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
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- 229920006362 Teflon® Polymers 0.000 description 5
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- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 5
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- 125000003277 amino group Chemical group 0.000 description 4
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- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 4
- JJVKJJNCIILLRP-UHFFFAOYSA-N 2-ethyl-6-methylaniline Chemical compound CCC1=CC=CC(C)=C1N JJVKJJNCIILLRP-UHFFFAOYSA-N 0.000 description 3
- 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 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
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- 238000000113 differential scanning calorimetry Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- VDJBIPLKIGSVRG-UHFFFAOYSA-N 3-chloro-2,6-diethylaniline Chemical compound CCC1=CC=C(Cl)C(CC)=C1N VDJBIPLKIGSVRG-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 239000002253 acid Substances 0.000 description 2
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- 150000008064 anhydrides Chemical class 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 125000004427 diamine group Chemical group 0.000 description 2
- 125000006159 dianhydride group Chemical group 0.000 description 2
- 150000002466 imines Chemical group 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- WKBALTUBRZPIPZ-UHFFFAOYSA-N 2,6-di(propan-2-yl)aniline Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N WKBALTUBRZPIPZ-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
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
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- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
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- 210000005069 ears Anatomy 0.000 description 1
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- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
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- 230000004044 response Effects 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000003797 telogen phase Effects 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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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
- 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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- 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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- 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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- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
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Abstract
本发明涉及结构式如下的由烷基取代的二苯氨
基甲烷和各种芳族二酐制备的芳族聚酰亚胺气体分
离膜,式中Ar、R、R、中的R′、R′中的R″、R″
中的X、X1、X2和X3、Ar中的Z和Z1、R′中的n等
的含义见说明书。这种聚酰亚胺膜材料在工业气体
分离中有广泛的用途。
Description
本发明涉及由烷基取代的二苯氨基甲烷和各种芳族二酐制备的芳族聚酰亚胺气体分离膜。
本申请人早期在1986年4月17日提出的申请S.N.853,321中介绍了具有优良的气体渗透性的聚酰亚胺膜材料。这里公开的聚酰亚胺材料,其组成基本上是从邻位烷基取代的芳族苯二胺和刚性结构的芳族二酐制备的。这些材料制成的膜呈现出中等的气体选择性。本发明改进了这种选择性。因此,本申请介绍的聚酰亚胺膜材料在工业气体分离的较大范围内是有用的。
本申请人在1986年10月27日提出的另一早期申请S.N.923,486表明,通过控制增加比前一申请具有较小刚性的链能使气体的产率更大。这可以(部分地)通过使用刚性的和基本上胺基邻位都被取代的二胺和基本上没有取代的二胺的混合物来完成。本发明介绍的聚酰亚胺膜材料,通过使用具有上述二种结构考虑的二苯胺基甲烷能更有效地制备出来。
美国专利4,629,685和4,629,777概括地公开并要求保护类似于这里公开的用在电子工业上的组合物。它们没有公开任何关于气体分离的用途。
美国再公告专利RE.30,351和美国专利3,822,202(Du Pont) 公开了芳族聚酰亚胺气体分离膜,其分子结构使得分子在聚合体中不能紧密的堆集,因此,具有高的气体渗透速率。本发明公开的膜材料可提供更高的气体产率。
美国专利4,113,628公开了由聚酰亚胺酸膜制备的芳族聚酰亚胺气体分离膜。
美国专利4,370,290,美国专利4,460,526,美国专利4,474,662,美国专利4,512,893和英国专利2,102,333公开了微孔芳族聚酰亚胺膜及其制备方法。
美国专利4,486,376公开了由经过改性剂处理的微孔芳族聚酰胺支撑膜制备的气体分离膜。
美国专利4,378,324;4,440,643;4,474,858;4,485,056;4,528,004和英国专利2,104,411公开了由经过芳族聚酰胺酸或芳族聚酰亚胺涂布的微孔芳族聚酰亚胺支撑膜制备的气体分离膜。
美国专利4,378,400公开了芳族聚酰亚胺气体分离膜,其分子结构使得分子在聚合物中能紧密地堆集。
本发明涉及这一发现,即二酐与在所有胺官能团的邻位上都带有取代基的二苯氨基甲烷缩聚,可形成具有优良的气体渗透性的膜。如果结构刚性的二酐与取代的二胺结合使用,则气体渗透性明显加大。这些膜产率的增加确信是由于聚合物结构中高的分子自由体积所致,而这种聚合物结构则由旋转受阻的聚合物链刚性性质造成的。
通常,通过致密的聚合物膜的极高的气体渗透速率仅在高于它们的玻璃化温度[Tg)时出现。硅橡胶和很多烯烃聚合物是这类材料的典型实例。Tg低的材料一般仅在复合膜中作为分离层,而支持多孔膜的亚结构提供结构上的完整性。由这类材料制备的膜对于各渗透气体往往选择性低。
Tg高的聚合材料比上述Tg低的聚合材料一般具有较高的气体选择性。这种性质可用来从二种或多种气体混合物中更有效地分离一种气体。然而,在以往的技术中发现的大多数这类Tg高的聚合材料不具有特别高的气体渗透性。所报导的实例大多涉及未取代的,或部分取代的聚合物,在加工过程中和/或以后的操作中易形成紧密的链堆集。
本发明克服上述缺点,并且提供具有良好的气体选择性和特别高的渗透性的致密膜,它使用带有下列重复单元的高Tg芳族聚酰亚胺,其中-Ar-是 是 或其混合物,-R′-是-O-,-S-, 或 化学式为(CH2)1-3的直链亚烷基基团,或其混合物,其中-R″是-O-,-S-, or -X,-X1,-X2和-X3分别是具有1-6个碳原子的伯或仲烷基,最好是甲基,乙基或异丙基;-Z和-Z1分别是氢或卤素例如碘、溴或氯,最好是氯,其中n=0-4。
在上述结构中,胺官能团邻位的多元取代基在空间上阻碍了围绕亚胺链的自由旋转。这致使二胺官能团的芳基保持在亚胺官能团和二酐官能团的芳基构成的平面外。因此,在芳族聚酰亚胺链内电子环共轭被大大降低。因而,上述烷基取代基和任意的卤化物取代基在空间上阻碍膜内不同的聚酰亚胺链之间强烈的电子相互作用。相信正是这些结构上考虑使本发明的膜内具有较大的分子自由体积,导致所发现的特殊高的气体渗透性。
胺官能团中结合的亚甲基桥接基团起柔性单元的作用,并部分松驰聚酰亚胺链中这种刚性。相信这种部分松驰导致膜内分子自由体积降低,并提高某种气体从多组分气体混合物中通过膜的选择性。采用上面公开的低刚性二酐成分可以实现进一步松驰。
通过改变本发明聚合物的松驰程度,可使膜适于广泛的气体分离并具有优良的气体产率。正是由于结合在二胺基团内的这些独特的结构特征,导致了出乎意料的气体产率。
结合在二胺基团内的上述独特的结构特征使气体渗透速率比已有技术有较大提高。例如,美国再公告专利Re.30,351例举的最好材料之一这里介绍作为对比实例。该对比实例可直接与这里介绍的采用同样二酐成分制备的材料进行比较,该二酐是4,4′〔2,2,2-三氟-1-(三氟甲基)亚乙基〕双(1,2-苯二甲酸酐)(6FDA),(例如,例1和2)。重要的是单独比较从同样的二酐组分制备的那些材料,因为这些组分对独特的结构特征也有贡献。鉴于这种考虑,如同实例1和2中所介绍的本发明材料的氧渗透速率是对比实例(美国再公告专利Re.30,351例举)的3-4倍。
按照上述考虑,采用了3,3′,4,4′一联苯基四羧酸酐的实施例4-6能直接与美国专利4,378,400中例举的材料比较。本发明公开的材料对氧的渗透速率是美国专利4,378,400例举的材料的氧渗透速率的19-93倍。
本发明介绍的聚酰亚胺具有优良的热稳定性。一般在空气或惰性气体中直到400℃它们都是稳定的。这些聚酰亚胺的玻璃化温度一般高于300℃。这些聚酰亚胺的高温特性有助于防止膜压实问题,而其它聚合体甚至在中等温度时也会经常出现此问题。实施例1
在惰性气氛中于室温下把4,4′〔2,2,2-三氟-1-(三氟甲基)亚乙基〕双(1,2-苯二甲酸酐)(6FDA,44.8g,0.101mol,另取50ml N-甲基吡咯烷酮把最后的部分洗入)加至搅拌着的4,4′-亚甲基-双(2-乙基-6-甲基)苯胺(28.2g,0.10mol)的N-甲基吡咯烷酮(250ml)溶液中。淡黄溶液于室温下搅拌过夜。于室温快速搅拌下把乙酐(37.7ml,0.4mol),三乙胺(55.6ml,0.4mol)和N-甲基吡咯烷酮(300ml)的溶液加入。于室温下搅拌4小时后,反应溶液在水中沉淀。生成的淡黄色产物用水和甲醇洗涤。将聚合物风干过夜,然后在真空烘箱中(20英寸汞柱)于120℃干燥3小时,于250℃干燥5小时,生成61.6g产物。
得到的聚酰亚胺能溶于N-甲基吡咯烷酮、二甲基乙酰胺、二氯甲烷和间甲酯,但不溶于丙酮和甲苯。将上述聚合物在N-甲基吡咯烷酮中的15%(重量)溶液于102℃下流延到一块经过Du PontTEFLON干润滑剂处理的玻璃板上制成薄膜,刮刀间隙为15密耳(38×10-5m),(Teflon干润滑剂含有一种能降低膜对玻璃板粘结力的碳氟化合物调聚剂)。将膜在玻璃板上于102℃下干燥30分钟,冷却至室温,并于室温下真空(20英寸汞柱)于燥过夜。将膜从板上剥离,并在真空烘箱中(20英寸汞柱)于120℃进一步干燥4小时。
在500磅/英寸2(34.5×105Pa)表压和25℃下,测试上述膜(膜原=1.6耳,4.1×10-5m)对混合气O2/N2,21/29摩尔比)的了渗透性。所得结果如下:
O2产率:1700厘巴
O2/N2选择性:4.5
厘巴是标准温度和压力下通过膜的气体立方厘米数乘以膜的厚度(厘米)再乘以10-12被膜的渗透面积(Cm2)乘以时间(秒)再乘以膜二侧的分压差(Cm Hg)来除,即,
向搅拌着的1,5-萘二胺(31.6g)在N,N ′-二甲基乙酰胺中的溶液在氮气氛中分批加入4,4′-〔2,2,2-三氟-1-(三氟甲基)亚乙基〕-双-1,2-苯二甲酸酐(88.9g)。该反应液加热至67℃并搅拌1小时。然后,将乙酐(82g)和三乙胺(82g)的混合物尽可能快地加至搅拌着的反应液中。于室温下再搅拌2小时后,在甲醇中使粘滞的反应液沉淀。过滤所生成的白色固体,并于150℃真空烘箱(20英寸汞柱)中干燥1小时,于220℃干燥4小时。将上述聚合物的15%(重量)N-甲基吡咯烷酮溶液于60℃流延到经过TEFLON干润滑油处理的玻璃板上,刮刀间隙15密耳(38×10-5m),制成上述聚酰亚胺膜。膜在板上干燥,冷却至室温,从板上剥离,在真空烘箱(20英寸汞柱)中室温干燥过夜,然后,于110℃干燥3小时,接着在真空烘箱内(20英寸汞柱)于220℃干燥4小时。
在300磅/英寸2(20.7×105Pa)表压和25℃测试上述膜(膜厚=0.5密耳,1.3×10-5m)对O2/N2(21/79,摩尔比)的渗透性。
所得结果如下:
O2产率:560厘巴
O2/N2选择性:4.8实施例2
向搅拌着的4,4′-亚甲基-双(3-氯-2,6-二乙基苯胺(189.7g,0.501mol)的N-甲基吡咯烷酮(100ml)溶液,于室温下,在少量氮气保洁下,添加4,4′-〔2,2,2-三氟-1-(三氟甲基)亚乙基〕-双(1,2-苯二甲酸酐)(6FDA,224.5g,0.505mol,另取250ml N-甲基吡咯烷酮把最后部分洗入)。把反应溶液缓慢加热至沸腾,同时收集馏出液。此馏出液收集到325ml后,使其余的馏出液流回至反应液中。在203℃沸腾8小时后,反应液冷却至室温。另取N-甲基吡咯烷酮稀释此溶液,并在水中沉淀。用水和甲醇洗涤生成的聚合物。得到的白色固体风干过夜,和在真空烘箱(20英寸汞柱)内于120℃干燥3小时,于250℃干燥5小时,得到378.1g产物。
该聚酰亚胺能以大于20%的固体含量(按聚合物重量计)溶于甲苯、丙酮、二氯甲烷、N-甲基吡咯烷酮、二甲基乙酰胺和间甲酚。
采用一台Du Pont 热分析仪(型号990-3,池型号为HC81-5/N00523,基线斜率=5.0,在氮气氛中,升温速度为10℃/分),对上述聚合物进行差示扫描量热(DSC)分析。用此法直至400℃没有观察到与Tg相关的转变。
用Du Pont 热失重分析仪(型号99-2,池型号951-5,在大气中,升温速度为10℃/分)对上述聚合物进行热失重分析(TGA)。在400℃观察到失重5%,并在490℃观察到失重40%。在室温下,把3%(重量)聚合物的二氯甲烷溶液注入放置在一块玻璃板上的直径为9.0cm的环形模子内,溶液高度0.16cm,将上述聚酰亚胺制成薄膜。此膜在玻璃板上于室温下干燥,然后,将其浸泡在水中使从板上脱下。此膜在真空烘箱内(20英寸汞柱)于70℃进一步干燥6小时以上。
在500磅/英寸2(34.5×105Pa)表压和25℃,测试上述膜(膜厚=2.6密耳,6.6×10-5m)对混合气体O2/N2(21/79摩尔比)的渗透性。所得结果如下:
O2产率:2200厘巴
O2/N2选择性:4.1实施例3
用少量氮气保净下,将搅拌着的4,4′-亚甲基-双(3-氯-2,6-二乙苯胺)(113.81g,0.30mol)和1,2,4,5-苯四甲酸酐(66,10g,0.303mol)的N-甲基吡咯烷酮(650ml)溶液慢慢地加热至沸腾,同时收集馏出液。在馏出液收集到110ml后,其余的馏出液令其流回到反应液中。在210℃加热8小时后,将粘滞的反应液冷却至室温。另用N-甲基吡咯烷酮稀释此溶液,并在水中沉淀。生成的固体用水和甲醇分别洗二次。固体风干过夜,并在真空烘箱内(20英寸汞柱)于120℃干燥3小时,并于250℃干燥5小时,生成157.5克产品。
此聚酰亚胺能溶于甲苯,二氯甲烷,间甲酚,二甲基乙酰胺以及N-甲基吡咯烷酮。
用Du Pont热分析仪(型号为990-3,池型号为HC81-5/N00523,基线斜率=5.0,氮气氛中,升温速度10℃/分)对上述聚合物进行差示扫描量热(DSC)分析。用此法直至400℃,未观察到与Tg的相关的转变。
用Du Pont热解重量分析仪(型号99-2,池型号951-5,在大气氛中,升温速度10℃/分)对上述聚合物进行热失重分析(TGA)。在420℃观察到重量减少5%,而在455℃观察到重量减少40%。
在室温下,把2%(重量)聚合物的二氯甲烷溶液注入放置在一块玻璃板上的直径为9.0cm的环形模子内,溶液高度0.11cm,将上述聚酰亚胺制成薄膜。此膜在玻璃板上于室温下干燥,然后,将其浸泡在水中使从板上脱下。该膜在真空烘箱内(20英寸汞柱)于70℃进一步干燥6小时以上。
在500磅/英寸2(34.5×105Pa)表压和25℃测试上述膜(膜厚=1.2密耳)对混合气体O2/N2(21/79摩尔比)的渗透性。所得结果如下
O2产率:1700厘巴
O2/N2选择性:3.9实施例4
于室温下在惰性气氛中向搅拌着的4,4′-亚甲基-双(2-乙基-6-甲基苯胺)(28.2g,0.10mcl)的N-甲基吡咯烷酮(250ml)溶液添加3,3’,4,4′-联苯四羧酸二酐(BPDA,29.7g,0.101mol,另取50mlN-甲基吡咯烷酮把最后的部分洗入)。于室温下将橙黄色溶液搅拌过夜,然后在快速搅拌下添加乙酐(37.7ml,0.4mol)、三乙胺(55.8ml,0.4mol)和N-甲基吡咯烷酮(150ml)的溶液。生成的黄色溶液于室温下搅拌4小时,然后在水中沉淀。分别用水和甲醇各洗聚合物二次。风干过夜后,固体在真空烘箱内(20英寸汞柱)于120℃干燥3小时,并于250℃干燥5小时,生成55g产品。
此聚酰亚胺能以大于20%的固体含量(以聚合物重量计)溶于N-甲基吡咯烷酮,二氯甲烷和间甲酚中。
用Du Pont热分析仪(型号990-3,池型号HC85-5/N00523,基线斜率=5.0,在氮气中,升温速度10℃/分)对上述聚合物进行差示扫描量热(DSC)分析。用此法,直至400℃未观察到与Tg相关的转变。
用Du Pont热解重量分析仪(型号99-2,池型号951-5,在大气中,升温速度10℃/分)对上述聚合物进行热失重分析(TGA)。在410℃观察到失重5%,在510℃观察到失重40%。在室温下,把3%(重量)上述聚合物的二氯甲烷溶液注入放置在一块玻璃板上的直径9.0cm的环形模子内,溶液高度为0.16cm,将上述聚酰亚胺制成薄膜。于室温下,此膜在玻璃板上干燥,然后,将其浸泡在水中使从板上脱下。此膜在真空烘箱内(20英寸汞柱)于70℃进一步干燥6小时以上。
在500磅/英寸2(34.5×105Pa)表压和25℃测试上述膜(膜厚=2.6密耳,6.6×10-5m)对混合气体O2/N2(21/79摩尔比)的渗透性。所得结果如下:
O2产率:900厘巴
O2/N2选择性:4.5实施例5
于室温下,在惰性气体中,向搅拌着的4,4′-亚甲基-双(2-甲基-6-异丙基苯胺)(31.0g,0.10mol)的N-甲基吡咯烷酮溶液(250ml)添加3,3′,4,4′-联苯四羧酸二酐(BPDA,29.7g,0.101mol,最后的部分另用50ml N-甲基吡咯烷酮洗入)。于室温下将深橙色溶液搅拌过夜,然后快速搅拌下添加乙酐(37.7ml,0.4mol)和三乙胺(55.8ml,0.4mol)溶液。生成的淡橙色溶液于室温下搅拌4小时,然后在水中沉淀。过滤,收集得到的白色固体,分别用水和甲醇各洗二次。聚合物干燥过夜,然后,在真空烘箱内(20英寸汞柱)于室温下干燥过夜,于120℃干燥3小时,于250℃干燥5小时,得到53.2g产物。
该聚酰亚胺能以大于20%的固体含量(以聚合物重量计)溶于N-甲基吡咯烷酮,二甲亚砜,二甲基乙酰胺以及二氯甲烷和间甲酚。
用Du Pont热分析仪(型号990-3,池型号HC81-5/N00523,在氮气中,基线斜率=5.0,升温速度10℃/分)对上述聚合物进行差示扫描量热分析。用该法,直至400℃未观察到与Tg有关的转变。
用Du Pont热解重量分析仪(型号99-2,池型号951-5,在大气中,升温速度10℃/分)对上述聚合物进行热失重分析(TGA)。在400℃观察到失重5%,而在515℃观察到失重40%。
上法制得聚酰亚胺的成膜过程是把15%聚合物(重量)的N-甲基吡咯烷酮溶液于100℃流延到经过TEFLON干润滑剂处理的一块玻璃板上,刮刀间隙为15密耳(38.4×10-5m)。膜在板上于100℃干燥25分钟,然后冷却至室温,并在真空烘箱内(20英寸汞柱)进一步于室温下干燥过夜。从板上剥下此膜,并在真空烘箱内(20英寸汞柱)于120℃干燥4小时。
在500磅/英寸2(34.5×105Pa)表压和25℃,测试了上述膜(膜厚=1.7密耳,4.3×10-5m)对混合气O2/N2(21/79摩尔比)的渗透性。
所得结果如下:
O2产率:900厘巴
O2/N2选择性:4.7实施例6
在室温用少量氮气保净下,向搅拌着的4,4′-亚甲基-双-(3-氯-2,6-二乙基苯胺)(189.5g,0.5mol)的N-甲基吡咯烷酮(1000ml)溶液中,添加3,3′,4,4′-联苯四羧酸二酐(BPDA,148.6g,0.505mol,另用100ml N-甲基吡咯烷酮将最后的部分洗入)。将反应液缓慢加热至N-甲基吡咯烷酮的沸点(204℃),使其挥发蒸出。在经过3.5小时蒸出300ml水/N-甲基吡咯烷酮溶液后,使镏出液流回至反应液。在约204℃,非常粘的反应液总搅拌时间达6.7小时后,反应慢慢冷却至室温。另取N-甲基吡咯烷酮稀释此溶液,并在水中沉淀。依次用水和甲醇洗涤得到的固体。分离出的白色聚合物风干过夜,然后在真空烘箱内(20英寸汞柱)于120℃干燥3小时,并于250℃干燥5小时,得到326.8g产物。
此聚酰亚胺能溶于N-甲基吡咯烷酮和二甲基乙酰胺以及二氯甲烷和间甲酚。
用Du Pont热分析仪(型号990-3,池型号HC81-5/N00523,在氮气氛中,升温速度10℃/分,基线斜率=5.0)对上述聚合物进行差示扫描量热(DSC)分析。用此法,直至400℃也未观察到与Tg相关的转变。
用Du Pont热解重量分析仪(型号99-2,池型号951-5,在大气中,升温速度10℃/分)进行上述聚合物的热解重量分析(TGA)。在400℃观察到失重5%,在490℃观察到失重40%。
在室温下,将3%聚合物(重量)二氯甲烷溶液注入玻璃板上直径9.0cm环状模子内,制成上述聚酰亚胺膜。该膜在玻璃板上于室温干燥,然后浸泡在水中,从板上脱膜。膜在真空烘箱内(20英寸汞柱)于70℃进一步干燥6个时以上。
在500磅/英寸2(34.5×105Pa)表压和25℃测试上述膜(膜厚=2.2密耳,5.6×10-5m)对混合气O2/N2(21/79摩比 )的渗透性。结果如下:
O2产率:900厘巴
O2/N2选择性:4.5实施例7
于室温下,在惰性气体中,向搅拌着的4,4′-亚甲基-双(2,6-二乙基苯胺)(31.0g,0.10mol)的N-甲基吡咯烷酮(300ml)溶液中,添加3,3′,4,4′-二苯甲酮四甲酸酐(32.55g,0.101mol)。于室温下,将淡橙色反应液搅拌67小时。于室温迅速搅拌下,添加三乙胺(55.75ml,0.4mol)和乙酐(37.74ml,0.4mol)的N-甲基吡咯烷酮(150ml)溶液。在室温下搅拌4小时后,反应液在水中沉淀。用水和甲醇洗涤生成的固体两次。聚合物风干过夜,然后,在真空烘箱内(20英寸汞柱)于120℃干燥3小时,于250℃干燥5小时,得到54.2g产物。
将聚合物的15%(重量)N-甲基吡咯烷酮溶液于102℃流延到经过TEFLON干润滑剂处理的玻璃板上,刮刀间隙为15密耳(38.4×10-5m)制成上面制备的聚酰亚胺膜。膜在玻璃板上于102℃于燥30分钟,冷却至室温,并在真空烘箱内(20英寸汞柱)于室温进一步干燥过夜。从板上剥离膜,并在真空烘箱内(20英寸汞柱于120℃干燥4小时。
透明的膜质地韧而柔,并且能折皱而不破裂。
在500磅/英寸2(34.5×105Pa)表压和25℃测试上述膜(膜厚=1.7密耳,4.3×10-5m)对混合气体O2/N2(21/79摩尔比)的渗透性。
所得结果如下:
O2产率:400厘巴
O2/N2选择性:4.2实施例8
于室温下,在惰性气体中,向搅拌着的4,4′-亚甲基-双(2-乙基-6-甲基苯胺)(28.2g,0.10mol)的N-甲基吡咯烷酮(300ml)溶液中添加3,3′,4,4′-二苯甲酮四羧酸酐(32.55g,0.101mol)。金色反应液于室温下搅拌16小时。于室温快速搅拌下,添加三乙胺(55.75ml,0.4mol),乙酐(37.74ml,0.4mol)和N-甲基吡咯烷酮(150ml)的溶液。于室温搅拌4小时后,反应液在水中沉淀。得到的固体用水和甲醇洗二次。聚合物风干过夜,然后,在真空烘箱内(20英寸汞柱)于120℃干燥3小时,并于250℃干燥5小时,得到52.1g产物。
用Du Pont热分析仪(型号990-3,池型号HC81-5/N00523,在氮气氛中,升温速度10℃/分,基线斜率=5.0)对上述聚合物进行差示扫描量热分析。用此法,直至400℃也未观察到与Tg相关的转变。
用Du Pont热解重量分析仪(型号99-2,池型号951-5,在大气中,升温速度10℃/分)对上述聚合物进行热失重分析(TGA)。在400℃观察到失重5%,而在510℃观察到失重40%。
在室温下把上述聚合物的2%(重量)二氯甲烷溶液浇注至放置在一块玻璃板上的直径9.0cm环形模子内,溶液高度0.16cm。膜在玻璃板上于室温下干燥,然后,浸泡在水中使其从板上脱下。该膜在真空烘箱内(20英寸汞柱)于70℃干燥6小时以上。
在500磅/英寸2(34.5×105Pa)表压和25℃测试上述膜(膜厚=1.65密耳,4.19×10-5m)对混合气体O2/N2(21/79摩尔比)的渗透性。
结果报告如下:
O2产率:700厘巴
O2/N2选择性:4.7
实施例9
将搅拌着的4,4′-亚甲基-双-(3-氯-2,6-二乙基苯胺)(189.45g,0.5mol)、3,3′,4,4′-二苯甲酮四甲酸酐(162.73g,0.505mol)和N-甲基吡咯烷酮(1100ml)的溶液,在少量氮气保净下慢慢加热至沸腾,同时收集馏出液。在馏出液收集到220ml后,其余的馏出液使返回流入反应液。在204℃加热6小时,然蠼承苑从σ豪淙粗潦椅隆A砣-甲基吡咯烷酮稀释此反应液,并在水中沉淀。生成的固体用水和甲醇洗涤。此固体风干过夜,并放在真空烘箱内(20英寸汞柱)于120℃干燥3小时,并于250℃干燥5小时,得到332.6g产物。
用Du Pont热分析仪(型号990-3,池型号HC81-5/N00523,在氮气氛中,升温速度10℃/分)对上述聚合物进行差示扫描量热分析。用此法,直至400℃未发现与Tg相关的转变。
用Du Pont热解重量分析仪(型号99-2,池型号991-5,在大气中,升温速度10℃/分)对上述聚合物进行热失重分析(TGA)。在425观察到失重5%,在530℃观察到失重40%。
在室温下,将上述聚合体的2%(重量)二氯甲烷溶液注入放置在一块玻璃板上的直径9.0cm园环状模子内,溶液高0.16cm。膜在玻璃板上于室温下干燥,然后浸泡在水中使膜从板上脱下。将膜置于真空烘箱内(20英寸汞柱)于70℃进一步干燥6小时以上。
在500磅/英寸2(34.5×105Pa)表压和25℃测试上述膜(膜厚=1.6密耳,4×10-5m)对混合气O2/N2(21/79摩尔比)的渗透性。所得结果如下:
O2产率:500厘巴
O2/N2选择性:4.7实施例10
将搅拌中的4,4′-亚甲基-双(2,6-二异丙基苯胺(183.3g,0.50mol)、3,3′,4,4′-二苯甲酮四羧酸酐(162.73g,0.505mol)和N-甲基吡咯烷酮(1100ml)溶液,在少量氮气保净下缓慢加热至沸腾,同时收集馏出液。在馏出液收集到200ml后,其余的馏出液使流回反应液。于202℃加热9小时后,粘性反应液冷却至室温。另用N-甲基吡咯烷酮稀释此溶液,并在水中沉淀。用水和甲醇洗涤得到的固体。固体风干过夜,并在真空烘箱内(20英寸汞柱)于120℃干燥3小时,干250℃干燥5小时,得到220.7g产物。
用Du Pont热分析仪(型号990-3,池型号HC81-5/N00523,在氮气氛中,升温速度10℃/分,基线斜率=5.0)对上述聚合物进行差示扫描量热(DSC)分析。用此法,直至400℃未发现与Tg相关的转变。
用Du Pont热解重量分析仪(型号99-2,池型号951-5,在大气中,升温速度10℃/分)对上述聚合物进行热失重分析(TGA)。在405℃观察到失重5%,而在545℃观察到失重40%。
在室温下,将上述聚合体的1%(重量)二氯甲烷溶液注入放置在一块玻璃板上的直径9.0cm园环状模子内,溶液高度0.16cm。此膜在玻璃板上于室温下干燥,然后浸泡在水中使其从板上脱下。该膜在真空烘箱内(20英寸汞柱)于70℃进一步干燥6小时。
在500磅/英寸2(34.5×105Pa)表压和25℃测试上述膜(膜厚=0.75密耳,1.9×10-5m)对混合气体O2/N2(21/79摩尔比)的渗透性。
所得结果如下:
O2产率:1500厘巴
O2/N2选择性:4.6实施例11
在少量氮气保净下。将搅拌着的4,4′-亚甲基-双-(2-甲基-6-异丙基苯胺)(155.24g,0.5mol)和3,3′,4,4′-二苯甲酮四甲酸酐(162.73g,0.505mol)的N-甲基吡咯烷酮(1100ml)溶液,缓慢加热至沸腾,同时收集馏出液,在馏出液收集到182ml后,其余的馏出液使流回反应液。在203℃加热6小时后,粘性反应液冷却至室温,另取N-甲基吡咯烷酮稀释此溶液,并在水中沉淀。用水和甲醇分别洗涤得到的固体二次。固体风干过夜,并在真空烘箱内(20英寸汞柱)于120℃干燥3小时,于250℃干燥5小时。
0℃下,将上述聚合物的15%(重量)N,N′-二甲基乙酰胺溶液,流延到玻璃板上,刮刀间隙为10密耳,制成上述聚酰亚胺膜。此膜在板上于70℃干燥2小时,然后从板上剥下,并于真空烘箱内(20英寸汞柱)于150℃进一步干燥过夜。
在500磅/英寸2(34.5×105Pa)表压和25℃测试上述膜对混合气O2/N2(21/79摩尔比)的渗透性。
所得结果如下:
O2产率:1000厘巴
O2/N2选择性:5.1
Claims (14)
2、权利要求1的气体分离膜,其中-Z和-Z1是氢或氯。
9、权利要求8的方法,其中-Z和-Z1是氢或氯。
10、权利要求8的方法,其中 是
12、权利要求8的方法,其中 是
13、权利要求12的方法,其中-R′-是
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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 |
US4717393A (en) * | 1986-10-27 | 1988-01-05 | E. I. Du Pont De Nemours And Company | Polyimide gas separation membranes |
US4717394A (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 MA MA21520A patent/MA21279A1/fr unknown
- 1988-05-16 OA OA59358A patent/OA08850A/xx unknown
- 1988-05-16 NZ NZ224630A patent/NZ224630A/xx unknown
- 1988-05-16 NO NO88882148A patent/NO882148L/no unknown
- 1988-05-17 BR BR8802382A patent/BR8802382A/pt unknown
- 1988-05-17 AU AU16335/88A patent/AU608323B2/en not_active Ceased
- 1988-05-17 DK DK269088A patent/DK269088A/da not_active Application Discontinuation
- 1988-05-17 ZA ZA883479A patent/ZA883479B/xx unknown
- 1988-05-18 CN CN88102904A patent/CN1036964A/zh active Pending
- 1988-05-18 JP JP63119443A patent/JPH01262925A/ja active Granted
- 1988-05-18 KR KR1019880005819A patent/KR890016095A/ko not_active Application Discontinuation
- 1988-05-18 PT PT87515A patent/PT87515B/pt not_active IP Right Cessation
- 1988-05-18 AT AT88107946T patent/ATE92511T1/de not_active IP Right Cessation
- 1988-05-18 CN CN88102914A patent/CN1016349B/zh not_active Expired
- 1988-05-18 DE DE88107946T patent/DE3882973T2/de not_active Expired - Fee Related
- 1988-05-18 EP EP88107946A patent/EP0337001B1/en not_active Expired - Lifetime
- 1988-06-10 TN TNTNSN88061A patent/TNSN88061A1/fr unknown
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101925398A (zh) * | 2008-02-05 | 2010-12-22 | 宇部兴产株式会社 | 聚酰亚胺气体分离膜和气体分离方法 |
CN101925398B (zh) * | 2008-02-05 | 2013-06-26 | 宇部兴产株式会社 | 聚酰亚胺气体分离膜和气体分离方法 |
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 |
Also Published As
Publication number | Publication date |
---|---|
NZ224630A (en) | 1989-11-28 |
MA21279A1 (fr) | 1988-12-31 |
AU608323B2 (en) | 1991-03-28 |
ZA883479B (en) | 1990-01-31 |
TNSN88061A1 (fr) | 1990-07-10 |
PT87515A (pt) | 1989-11-10 |
DK269088A (da) | 1989-10-14 |
KR890016095A (ko) | 1989-11-28 |
AU1633588A (en) | 1990-04-12 |
EP0337001B1 (en) | 1993-08-04 |
NO882148L (no) | 1989-10-16 |
ATE92511T1 (de) | 1993-08-15 |
CN1036965A (zh) | 1989-11-08 |
DE3882973T2 (de) | 1994-03-17 |
NO882148D0 (no) | 1988-05-16 |
CN1016349B (zh) | 1992-04-22 |
EP0337001A1 (en) | 1989-10-18 |
JPH01262925A (ja) | 1989-10-19 |
DE3882973D1 (de) | 1993-09-09 |
OA08850A (en) | 1989-03-31 |
US4838900A (en) | 1989-06-13 |
JPH053330B2 (zh) | 1993-01-14 |
BR8802382A (pt) | 1989-12-05 |
DK269088D0 (da) | 1988-05-17 |
PT87515B (pt) | 1994-04-29 |
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