CN1018183B - 高溶解性透明聚酰亚胺的制备方法 - Google Patents
高溶解性透明聚酰亚胺的制备方法Info
- Publication number
- CN1018183B CN1018183B CN88102946A CN88102946A CN1018183B CN 1018183 B CN1018183 B CN 1018183B CN 88102946 A CN88102946 A CN 88102946A CN 88102946 A CN88102946 A CN 88102946A CN 1018183 B CN1018183 B CN 1018183B
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- Prior art keywords
- polyimide
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- 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.)
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- 239000004642 Polyimide Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 125000003118 aryl group Chemical group 0.000 claims abstract description 37
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 33
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 7
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- 238000006068 polycondensation reaction Methods 0.000 claims 2
- 150000004985 diamines Chemical class 0.000 abstract description 10
- 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 abstract description 8
- -1 chloro-1-(trifluoromethyl) ethylidene Chemical group 0.000 abstract description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 abstract 1
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- 125000003368 amide group Chemical group 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 48
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 42
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 40
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- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 4
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- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 2
- WCZNKVPCIFMXEQ-UHFFFAOYSA-N 2,3,5,6-tetramethylbenzene-1,4-diamine Chemical compound CC1=C(C)C(N)=C(C)C(C)=C1N WCZNKVPCIFMXEQ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 150000004984 aromatic diamines Chemical class 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical group C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 125000006575 electron-withdrawing group Chemical group 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000005462 imide group Chemical group 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical compound CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- WXNRYSGJLQFHBR-UHFFFAOYSA-N bis(2,4-dihydroxyphenyl)methanone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1O WXNRYSGJLQFHBR-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
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- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
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Classifications
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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
- 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
-
- 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
-
- 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
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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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
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- 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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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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Abstract
本发明公开了一种制备高溶解性且在可见光区高度光学透明的芳香族聚酰亚胺的制备方法。制备此类聚酰亚胺所用的二元酸酐是4,4'-〔2,2,2-三氯-1-(三氟甲基)亚乙基〕双(1,2-苯二甲酸酐),可用1,2,4,5-苯四酸二酐或3,3′,4,4'-二苯酮四酸二酐部分代替上述二酐。制备此类聚酰亚胺所用的二胺是间或对亚苯二胺,在其胺基的邻位上有含1-6个碳原子的伯或仲烷基取代基,最好是甲基或乙基。
Description
本发明涉及由烷基取代的二胺和4,4′-[2,2,2-三氟-1-(三氟甲基)亚乙基]双(1,2-苯二甲酸酐)(6FDA)制备一类全环化的芳香族聚酰亚胺和共聚聚酰亚胺的方法。
欧洲专利申请132,221;141,781;181,837和美国专利4,629,685及4,629,777公开了一些芳香族聚酰亚胺,其中二胺是由烷基取代的,但不包括使用二元酸酐(6FDA)。美国专利4,629,777第6栏第23和51行公开了一些可溶于极性、非质子传递良溶剂的聚酰亚胺。
美国专利3,356,648公开了一种由6FDA和2,2-双(4-氨基苯基)六氟丙烷制备的可溶于丙酮的芳香族聚酰亚胺。
美国专利3,959,350公开了一些由6FDA和各种未经取代的二胺制备的芳香族聚酰亚胺。
美国专利3,546,175公开了一些由1,2,4,5-苯四酸二酐或3,3′,4,4′-二苯酮四酸二酐和2,4-二氨基异丙基苯制备的可溶于非质子传递良溶剂的芳香族聚酰亚胺。
美国专利4,145,522公开了一些由氨基取代的4-叔丁基邻苯二甲酸酐制备的具有改善的溶解性的聚酰亚胺。
美国专利4,588,804公开了一些由6FDA和各种二胺制备的可溶性芳香族聚酰亚胺。
美国专利4,592,925公开了一些由6FDA和2,2-双(2或3-二氨基苯基)六氟丙烷制备的可溶性芳香族聚酰亚胺。
美国国家航空和航天局(NASA)技术备忘录第89016号,美国专利4,595,548和4,603,061公开了一些由各种二元酸酐(包括6FDA)和醚或硫醚桥化多环二胺制备的透明芳香族聚酰亚胺。
本发明涉及制备可溶于比较弱溶剂和/或挥发性溶剂(如丙酮)的芳香族聚酰亚胺的方法。由这些聚酰亚胺制备的膜在可见光范围从具有高度的光学透明性到无色。本发明的聚酰亚胺是由二元酸酐制备的,此二元酸酐可以是6FDA或6FDA与直到50%的1,2,4,5-苯四酸二酐或直到49%的二苯酮四酸二酐的混合物。上述二胺是基于在氨基的邻位带有烷基取代基的间或对-亚苯基二胺。
作为一类聚合物,聚酰亚胺在许多溶剂中都是不溶性的。这种性质加之高的软化温度使得芳香族聚酰亚胺极难加工成有用的产品。将不溶性芳香族聚酰亚胺加工成膜、涂层和其它结构通常需采用复杂的工艺。例如,可通过不溶性聚酰亚胺的可溶性聚酰胺-酸前体制备膜。除去过量的溶剂后,以热和/或化学方式将此膜固化,从而将聚酰亚胺酸前体膜脱水得到环化聚酰亚胺膜。还存在一些其它问题,如在固化过程中由付产物水蒸发造成的孔隙等。
在本技术领域中已经采用全环化可溶性聚酰亚胺而避免了上述缺陷。这些材料大多仅溶于有机良溶剂,典型的是N-甲基吡咯烷酮、N,N-二甲基乙酰胺、二甲基甲酰胺、二甲亚砜、间-甲酚等溶剂。而能溶于象丙酮这样的弱得多的溶剂的全环化聚酰亚胺则极少。在最近一篇有关可溶性聚酰亚胺的综述中(参见F.W.Harris,
W.A.Feld,L.H.Lanier,AM.Chem.Soc.,Polymer Preprints,17,(1976)PP.353-358),能溶于丙酮的例子不到5%。在弱溶剂(如丙酮)中的可溶性可以提供不溶性或溶解性差的聚酰亚胺所不具备的得天独厚的加工性能。弱溶剂(如丙酮)一般比良溶剂(如N-甲基吡咯烷酮)具有更高的挥发性。因此,可溶于丙酮的聚酰亚胺与仅溶于良溶剂的聚酰亚胺相比,可采用较低的温度制备膜、涂层等。
芳香族聚酰亚胺可用作涂层材料,尤其是在那些预期需要耐受高温的场合。采用这类由挥发性、价廉、无毒溶剂的溶液制备的涂层,经济上具有明显的好处。过去已有一些零散的有关芳香族聚酰亚胺在丙酮中溶解性的报道(美国专利3,356,648 WWebster,Advances in Chemistry #129,Am.Chem.Soc.,1973,P61;Webster,Final Repovt NAS8-21401,Marshall Space Flight Center 1973)。其中所述的所有产品都采用了昂贵的部分氟化的芳香族二胺,这些二胺是不易得到的。在某些情况下,这些产品在高温下的应用受到限制。
本发明的产品可以满足对可溶于丙酮的芳香族聚酰亚胺的需要,同时可由更容易得到的二胺制备并保持良好的高温使用性能。
可溶于弱溶剂的聚酰亚胺也使得更易于加工成多层结构。当涂层材料仅溶于基质材料对之敏感的那些溶剂时,是难以制取多层结构的。能够得到可溶于基质材料对之不敏感的弱溶剂的聚酰亚胺,上述问题就迎刃而解了。举例讲,将聚酰亚胺钝化涂层涂装到电子器件上时就会发生上述问题。涂布所述涂层需要芳香族聚酰亚胺或其聚酰胺酸前体的溶液,而它们仅溶于诸如N-甲基吡咯烷酮一类的良溶剂。然而,
所述电子设备的元件通常对这些良溶剂是敏感的,可能受到损害。通过采用可溶于弱得多的溶剂(它们不损害上述元件)的聚酰亚胺,就可以解决这个问题。
本发明克服了上述不足之处,提供了制备可溶于弱溶剂(如丙酮)的全环化聚酰亚胺的方法。这类溶解性更好的聚酰亚胺主要是由邻位烷基取代的芳香族二胺和至少一部分4,4′-[2,2,2-三氟-1-(三氟甲基)亚乙基]双(1,2-苯二甲酸酐)(6FDA)制备的。本发明的聚酰亚胺组合物含有下列重复单元:
其中-Ar-是
或其混合物-Ar′-是
-x、-x1、-x2、-x3和-x4分别是具有1-6个碳原子的伯或仲烷基,最好是甲基或乙基,-z、-z1、-z2、-z3、-z4和-z5分别是-H或-X
r=100%-(t+v)
t=0-50% 当v=0%时
v=0-49%,最好0-25%,当t=0%时
s=100%-u
u=100% 当(t+v)>1%时。
可以推测这类高温芳香族聚酰亚胺所表现出的令人惊异的高溶解性是结合在其中的结构特征的组合的直接结果。如现有技术所述,某些结合有4,4′-〔2,2,2-三氟-1-(三氟甲基)亚乙基〕双(1,2-苯二甲酸酐)(6FDA)的全环化芳香族聚酰亚胺在非质子传递良溶剂(如N-甲基吡咯烷酮)中是可溶的。这种溶解性通常归因于结合在其中的六氟异亚丙基的作用,此基团作为一个插入基团(例如,参见美国专利4,595,548和4,603,061),从而防止聚酰亚胺链中的环发生共轭。这种基团还可以起到干扰聚酰亚胺链
大分子结构的作用,从而阻碍链间排布。然而,将6FDA结合到芳香族聚酰亚胺中在绝大多数情况下并不是提供在弱溶剂(如丙酮)中具有高溶解性的聚合物的充分依据。
二胺基团的邻位烷基取代基具有使二胺基团的芳基部分被排斥于酰亚胺基团及其芳基部分构成的平面之外的倾向。因而,芳香族聚酰亚胺链中的电子环共轭作用大大降低。此外,上述烷基取代基在空间上阻碍了膜和/或涂层中不同聚酰亚胺链之间强烈的电子作用。然而,如现有技术中所述,将邻位烷基取代基结合到芳香族聚酰亚胺中,本身并不是提供在弱溶剂(如丙酮)中具有高溶解性聚合物的充分依据。
上述结构特征的结合就能够起到大大降低链间和链内相互作用的功能。正是由于这种相互作用程度的降低导致这类高温芳香族聚酰亚胺具有令人惊异的高溶解性。无论其机理如何,从现有技术的观点来看,本发明所述的这类芳香族聚酰亚胺在弱溶剂中具有大大提高的溶解性,这一发现是令人惊异的。
这些高溶解性、高温聚酰亚胺的另一个优点是,它们可以形成在可见光范围为高度光学透明到无色的膜。目前很需要在300-600nm电磁谱波段内具有高度光学透明性的高温柔韧聚合物膜和涂层材料。这种材料的潜在用途包括用于天线、太阳能电池和航天元件中的热控涂层系统。芳香族聚酰亚胺膜已广泛应用于航天及需要长期耐受200℃-300℃温度和在短时间接触时超过300℃的一些商业领域。因为这些和其它的优异性能,芳香族聚酰亚胺已表明在航天结构材料方面具有潜在的应用前景。遗憾的是,市售的聚酰亚胺膜通常是高度着色的;例如Kapton膜(E.I.Dn Pont de
Nemours and Company生产)一般是琥珀色的。因而,这些膜在300-600nm电磁谱波段是强烈吸收的。
本发明克服了上述缺点,提供了一类可溶性全环化聚酰亚胺,这类聚酰亚胺可形成在可见光区高度光学透明到无色的膜,同时保持高温性能的优点。本文所给出的大多数实例都能形成透明且基本无色的膜,这些膜韧而柔,折叠时不会破裂。此外,这些膜在500nm或500nm以上的可见光区和紫外吸收谱测量中基本上不吸收。
如上所述,这类芳香族聚酰亚胺的高溶解性与上述光学性质相结合在制备具有潜在用途的膜和/或涂层时具有很大的优越性。现有技术已公开的在可见光区高度光学透明到无色的聚酰亚胺膜(如美国专利4,595,548和4,603,061)需要费用昂贵的加工工艺。由于具有高溶解性,本文公开的这类全环化聚酰亚胺可以容易地溶于高挥发性弱溶剂,并可按本领域的普通技术制备膜或涂层。如现有技术所采用的,延长加热周期以驱除剩余溶剂或将聚酰胺酸前体固化为全环化聚酰亚胺的作法,在本发明中是不需要的。
据信本发明聚酰亚胺膜和/或涂层在可见光区的高度光学透明性到无色性是其化学组成结构的直接结果。二胺基团的邻位烷基取代基倾向于在空间上使酰亚胺键密集化。作为这种作用的直接结果,二胺基团的芳基部分被排斥在酰亚胺基团和二元酸酐基团的芳基部分构成的平面之外。因而,芳香族聚酰亚胺链内的电子环共轭作用被大大削弱。此外,上述烷基取代基还在空间上阻碍膜和/或涂层内不同聚酰亚胺链之间的强烈电子作用。将体积庞大的邻位烷基取代基结合到聚酰亚胺结构的二胺基团中大大削弱了链间和链内强烈的电子作用(如电荷转移配合物),这种电子作用可以在电磁谱的紫外-可见光波段
引起强烈的吸收。无论其机理如何,本文所述的这类聚酰亚胺在可见光区具有高度光学透明性到无色性,这一发现是令人惊异的,因为按照现有技术的观点,这种性质是(至少部分是)在二胺基团的结构中结合了吸电子基团和/或“分隔”基团的结果。本发明的二胺基团既没有结合吸电子基团(在本领域烷基取代基通常被看作给电子基)也没有结合“分隔”基团。
本发明另一个目的是提供由一类高溶解性、在可见光区具有高度光学透明性到无色(如本文所公开的)性、同时保持良好高温性能(这种性能在许多商业应用中具有很高的价值)的芳香族聚酰亚胺制备的膜和/或涂层。
本文所公开的这类芳香族聚酰亚胺中的一小类是可以自动光化学交联的。此小类定义为本发明的这样一些聚酰亚胺,其中结合了3,3′,4,4′-二苯酮四酸二酐。无需添加附加组分(如增感剂、链载体等),上述光化学交联反应即可发生。这避免了在成膜和/或涂层步骤、光化学交联步骤、或使用所得到的膜和/或涂层时可能出现的麻烦。例如,如果光化学交联之后经过萃取或其他工序这些附加组分被损失掉的话,所得到的膜和/或涂层的就可能具有很不同的物理性能。据信此光化学交联反应的机理包括二苯酮生色基团吸收光化学能量、高能量激发态的二苯酮基团从二胺的烷基取代基的苄基上除去氢原子、接着所形成的自由基重新组合形成交联键。这类光化学机理在流行的光化学教科书中有介绍,并且一般为本领域技术人员所接受。运用本文所述光化学交联反应并不是基于上述机理的具体细节,上面提出的反应机理细节不应限制本发明的应用。这种交联作用将大大降低本发明膜和/或涂层对溶剂的敏感性,因而提高了此复合
结构的耐环境性和耐久性。
本文所述这类芳香族聚酰亚胺令人惊异的物理性能的组合,即(1)在弱溶剂(如丙酮)中较高的溶解性,(2)膜和/或涂层在可见光区的高度光学透明到无色性能和(部分地)(3)自动光化学交联性能,加之保持了高温性能,提供了一类芳香族聚酰亚胺它们可以满足一整套特殊的适于很广的应用范围的标准。
本文所公开的这类聚酰亚胺和共聚聚酰亚胺可用于气体分离膜材料和电子领域。这些包括光致抗蚀材料、半导体保护除层、多层集成电路的绝缘层、高温焊接掩膜、粘合多层电路、电子设备上的最后钝化涂层等。在可见光区具有高度光学透明到无色性的芳香族聚酰亚胺膜和/或涂层在许多空间应用中都有潜在的前景,例如用于天线、太阳能电池和航天元件中的热控涂层系统。
本发明的分离膜一般适用于分离气体混合物。这类分离的具体例子包括在石油加工厂和合成氨厂回收氢气,在合成气(Syngas)体系中分离一氧化碳和氢,从烃中分离二氧化碳或硫化氢,从空气中浓集氧和氮分别用于助燃或惰性气流。
实例1
于50℃温度下在氮气惰性气氛中并在搅拌下,将二甲亚砜(500ml)加入到4,4′-〔2,2,2-三氟-1-(三氟甲基)亚乙基〕双(1,2-苯二甲酸酐)(6FDA,88.87g,0.20mol)和2,4,6-三甲基-1,3-亚苯基二胺(30.01g,0.20mol)中。在50℃搅拌2小时后,向其中添加由乙酐(75.8ml,0.8032mol)和三乙胺(112.94ml,0.8104mol)组成的混合物,并在50℃和惰性气氛下再搅拌反应
2小时。在甲醇中沉淀得到的粘稠反应溶液,滤集白色固体,在室温下于真空烘箱中干燥过夜,于110℃干燥2小时,于220℃干燥5小时。得到108.8g灰白色的聚酰亚胺。此聚酰亚胺以大于15%的固体含量(基于聚合物重量)溶于丙酮、二氯甲烷、N,N-二甲基甲酰胺、甲乙酮、N,N-二甲基乙酰胺、乙酸甲酯、四氢呋喃、N-甲基吡咯烷酮、二噁烷、二甲亚砜、碳酸丙烯酯、γ-丁内酯和间甲酚。
使用带有HCB1-S/N00523型料室的990-3型杜邦热分析仪对上述聚合物进行示差扫描量热(DSC)分析,在氮气氛中以10℃/分钟的升温速率进行,基线斜率=5.0。观察到Tg的相应转变温度是起始温度为365℃和中点温度为385℃。
用带有951-5型料室的99-2型杜邦热失重分析仪,在惰性气氛中以10℃/分钟的升温速率,对上述聚合物进行热失重分析(TGA)。在540℃观察到5%的重量损失,在660℃观察到40%的重量损失。
将上述聚合物在N-甲基吡咯烷酮中的10%(重量浓度)溶液,在80℃以15密耳(38×10-5m)的刀隙流延到经杜邦TEFLON干润滑剂处理过的玻璃板上,制成上述聚酰亚胺的膜。此膜在室温下在上述板上进行干燥,然后从板上剥离,并放在真空烘箱中于室温下干燥过夜,接着在真空烘箱中于200℃干燥6小时。
杜邦TEFLON干润滑剂含有碳氟调聚物,它可以降低膜与玻璃板间的粘合性。
这种膜质地韧而柔,折叠时不会破裂。这些膜(它们的厚度约为1.5密耳(3.8×10-5m))基本上是透明无色的。对这些膜
的紫外和可见光吸收谱测量表明,它们在500nm或500nm以上基本上不吸收。
将上述聚合物在丙酮中的15%(重量浓度)溶液,在室温下于干燥罩中在氮气流下,以5密耳(12.67×10-5m)的刀隙,流延到经过杜邦TEFLON干润滑剂处理的玻璃板上,制成上述聚酰亚胺膜。这些膜不到5分钟就变得不粘。将这些膜在板上进行干燥,然后将其从板上剥离。这些基本上透明无色的膜质地韧而柔,折叠时不会破裂。
实例2
在室温下在惰性气氛中并且在搅拌下,向2,3,5,6-四甲基-1,4-亚苯基二胺(16.4g,0.10mol)在N-甲基吡咯烷酮(250ml)中的溶液分批添加4,4′-〔2,2,2-三氟-1-(三氟甲基)亚乙基〕双(1,2-苯二甲酸酐)(6FDA,44.4g,0.10mol,分四份,最后一份加入后用100mlN-甲基吡咯烷酮冲洗)。在室温下将此金色溶液搅拌3小时后,迅速搅拌下添加乙酐(37.9ml,0.4016mol)和三乙胺(56.5ml,0.4052mol)的溶液。在室温下将所得到的橙红色溶液搅拌2小时,然后在甲醇中沉淀。滤集白色固体产物,风干,然后在真空烘箱中于室温下干燥过夜,在100℃干燥3小时,在250℃干燥3小时,得到54.2g产物。
此聚酰亚胺以大于20%的固体含量(基于聚合物重量)溶于丙酮、二氯甲烷、N-甲基吡咯烷酮和间甲酚。
将聚合物在N-甲基吡咯烷酮中的15%(重量浓度)溶液在75℃以15密耳(38.4×10-5m)的刀隙,流延到经过杜
邦TEFLON干润滑剂处理过的玻璃板上制成上述聚酰亚胺膜。此膜在板上于75℃干燥25分钟,在真空烘箱中冷却至室温过夜,然后在120℃干燥4小时,220℃干燥3小时。
此膜质地韧而柔,折叠时不会破裂。这些膜(平均厚度约为1.5密耳(3.8×10-5m))基本是透明无色的。
用带有HCB1-S/N00523型料室的990-3型杜邦热分析仪,在氮气氛中以10℃/分钟的升温速率,基线斜率=5.0对上述聚合物进行示差扫描量热分析(DSC)。直至400℃没有观察到Tg或Tm的相关转变。
用带有951-5型料室的99-2型杜邦热失重分析仪,在氮气氛中以10℃/分钟的升温速度对上述聚合物进行热失重分析(TGA)。在525℃观察5%的重量损失,在640℃观察到40%的重量损失。
实例3
在惰性气氛下在室温下并且在搅拌下,向2,3,5,6-四甲基-1,4-亚苯基二胺(16.43g,0.10mol)和2,4,6-三甲基-1,3-亚苯基二胺(15.02g,0.10mol)在N-甲基吡咯烷酮(300ml)中的溶液分批添加4,4′-〔2,2,2-三氟-1-(三氟甲基)亚乙基〕双(1,2-苯二甲酸酐)(6FDA,88.8g,0.20mol,分9批加入,最后一批加入后用N-甲基吡咯烷酮(166ml)冲洗)。将此透明的黄色溶液在室温下搅拌3小时,变得很粘稠,需补加N-甲基吡咯烷酮(200ml)。在室温下剧烈搅拌添加乙酐(75.8ml,0.8032mol)和三乙胺(112.94ml,0.8104mol)溶液。有
白色固体从溶液中析出,但慢慢地又溶解了,形成一种粘稠橙黄色溶液。室温下搅拌2小时后,反应溶液在甲醇中进行沉淀。收集所得到的灰白色固体,补加甲醇洗涤,风干并在真空烘箱中于室温下干燥过夜,在100℃干燥3小时,250℃干燥3小时,得到109.4g产品。
此聚酰亚胺以大于20%的固体含量(基于聚合物重量)溶于丙酮、二氯甲烷、N-甲基吡咯烷酮和间甲酚。
用带有HCB1-S/N00523型料室的杜邦990-3型热分析仪,在氮气氛中以10℃/分钟的升温速率,基线斜率为5.0,对上述聚合物进行示差扫描量热分析(DSC)。直至400℃未观察到Tg或Tm的相关转变。
用带有951-5型料室的99-2型杜邦热失重分析仪,在氮气氛中以10℃/分钟的升温速率对上述聚合物进行热失重分析((TGA)。在535℃观察到5%的重量损失,在655℃观察到40%的重量损失。
将聚合物在N-甲基吡咯烷酮中的15%(重量浓度)溶液,在80℃以15密耳(38.4×10-5m)的刀隙,流延到经杜邦TEFLON干润滑剂处理过的玻璃板上,制成上述聚酰亚胺膜。此膜在板上于80℃干燥25分钟,冷却至室温,从板上将其剥离,在真空烘箱中于室温下干燥过夜,在120℃干燥4小时。
此膜质地韧而柔,折叠时不会破裂。这些膜(厚度介于1-2密耳)基本是透明无色的。
实例4
在惰性气氛中在搅拌下于50℃向2,4,6-三甲基-1,3
-亚苯基二胺(30.01g,0.20mol)在N-甲基吡咯烷酮(500ml)中的溶液添加1,2,4,5-苯四酸二酐(121.81g0.10mol)。搅拌30分钟后,搅拌下于50℃分批添加4,4′-〔2,2,2-三氟-1-(三氟甲基)亚乙基〕双(1,2-苯二甲酸酐)(44.4g,0.10mol,分两批添加,最后一批加入后用N-甲基吡咯烷酮(250ml)冲洗)。此橙黄色反应溶液在50℃下搅拌过夜。剧烈搅拌下添加乙酐(75.84ml,0.80mol)和三乙胺(112.94ml,0.81mol)的溶液,使反应溶液变成褐色。在50℃搅拌2小时后,在甲醇中将此反应溶液沉淀。滤集得到的灰白色固体,用甲醇洗涤,风干,在真空烘箱中于室温下干燥过夜,在100℃干燥4小时,250℃干燥3小时,得到86.8g产品。
此聚酰亚胺以大于10%的固体含量(基于聚合物重量)溶于丙酮,N,N-二甲基乙酰胺、间甲酚、N-甲基吡咯烷酮、二氯甲烷、乙酸甲酯、甲乙酮、N,N-二甲基甲酰胺、γ-丁内酯、二甲亚砜、和乙二醇二甲醚。
将聚合物在N-甲基吡咯烷酮中的15%(重量浓度)溶液在80℃以15密耳(38.4×10-5m)的刀隙,流延到经杜邦TEFLON干润滑剂处理过的玻璃板上,制备上述聚酰亚胺膜。此膜于80℃在板上干燥25分钟,然后将其从板上剥离,在真空烘箱中于室温干燥过夜,在120℃干燥4小时。
这些膜质地韧而柔,折叠时不会破裂。这些膜(平均厚度约为1.5密耳(3.8×10-5m))是淡黄色透明的。
实例5
在50℃搅拌下向2,4,6-三甲基-1,3-亚苯基二胺(30.01g,0.20mol)在N-甲基吡咯烷酮(600ml)中的溶液中(在惰性气氛下)添加3,3′,4,4′-二苯酮四酸二酐(3.22g,0.01mol)。搅拌半小时后,于50℃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)(84.36g,0.19mol,分8批加入,最后一批加入后用200ml N-甲基吡咯烷酮冲洗)。此黄色溶液在50℃搅拌过夜。迅速添加乙酐(75.8ml,0.80mol)和三乙胺(112.9ml,0.81mol)的溶液并将所得的溶液在甲醇中沉淀。滤集所得的白色固体,用甲醇洗涤,放在真空烘箱中于室温下干燥过夜,在100℃干燥5小时,250℃干燥2小时,得到104.4g白色产物。
此聚酰亚胺以大于10%的固体含量(基于聚合物重量)溶于丙酮、二氯甲烷、二噁烷、乙二醇二甲醚、甲乙酮、N,N-二甲基乙酰胺、N,N-二甲基甲酰胺、乙酸甲酯、γ-丁内酯、碳酸丙烯酯、二甲亚砜、和N-甲基吡咯烷酮。
用带有HCB1-S/N00523型料室的990-3型杜邦热分析仪,在氮气氛中以10℃/分钟的升温速率,基线斜率=5.0,对上述聚合物进行示差扫描量热分析(DSC)。直到400℃未观察到Tg或Tm的相关转变。
用带有951-5型料室的99-2型杜邦热失重分析仪,在氮气氛中以10℃/分钟的升温速率,对上述聚合物进行热失重分析(TGA)。在525℃观察到5%的重量损失,在660℃观察到40%的重量损失。
将上述聚合物在N-甲基吡咯烷酮中的15%(重量浓度)溶液,
在80℃以15密耳(38×10-5m)的刀隙流延到经杜邦干润滑剂处理过的玻璃板上制成膜。此膜于80℃在板上干燥25分钟,冷却至室温,将其从板上剥离,放在真空烘箱中于室温下干燥过夜,在120℃干燥4小时。
这些膜质地韧而柔,折叠时不会破裂。这些膜(平均厚度约为1.5密耳(3.8×10-5m))基本是无色透明的。
在低于50℃的温度下,用450瓦Hanovia中压汞弧光灯将上述膜的两面各辐照15分钟。将此膜的一部分放入N-甲基吡咯烷酮(上述未交联聚合物的良溶剂)。膜的一些部位溶解了,留下一些交联聚合物的长股不溶于此溶液。
实例6
在惰性气氛中搅拌下向2,4,6-三甲基-1,3-亚苯基二胺(30.01g,0.20mol)在N-甲基吡咯烷酮(600ml)的溶液中添加3,3′,4,4′-二苯酮四酸二酐(6.44g,0.02mol,用50ml N-甲基吡咯烷洗涤)。搅拌0.75小时后,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)(79.92g,0.18mol,分7批加入,最后一批加入后用150ml N-甲基吡咯烷酮冲洗),将黄色反应溶液搅拌2小时。向此反应溶液迅速添加乙酐(75.8ml,0.80mol)和三乙胺(112.9ml,0.81mol)的溶液,并将所得的黄色溶液搅拌2小时。在甲醇中沉淀此反应溶液。滤集所产生的白色固体,用甲醇洗涤,放在真空烘箱中于室温下干燥过夜,在100℃干燥3小时,250℃干燥3小时,得到119.5g产物。
此聚酰亚胺以大于20%的固体含量(基于聚合物重量)溶于丙
酮、二氯甲烷、间甲酚,二甲亚砜和N-甲基吡咯烷酮。
将上述聚合物在N-甲基吡咯烷酮中的15%(重量浓度)溶液,在75℃以15密耳(38×10-5m)的刀隙流延到经杜邦TEFLON干润滑剂处理过的玻璃板上制成膜。此膜在板上于75℃干燥25分钟,冷却至室温,将其从板上剥离,放入真空烘箱于室温下干燥过夜,在120℃干燥4小时。
这些膜质地韧而柔,折叠时不会破裂。这些膜(平均厚度约为1.5密耳(3.8×10-5m))是透明的且基本无色。
在低于50℃的温度下用450瓦Hanovia中压汞弧光灯将上述膜的两面各辐照15分钟。将此膜的一部分放入N-甲基吡咯烷酮(上述未交联聚合物的良溶剂)。膜的某些部分溶于溶液中,留下一些不溶的交联聚合物短股。
实例7
在惰性气氛中于50℃搅拌下向2,4,6-三甲基-1,3-亚苯基二胺(30.01g,0.20mol)在N-甲基吡咯烷酮(350ml)中的溶液添加3,3′,4,4′-二苯酮四酸二酐(9.21g,0.03mol)。在50℃搅拌0.3小时后,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)(76.1g,0.17mol,分四批加入,最后一批加入后用150ml N-甲基吡咯烷酮冲洗),所得的反应溶液在50℃搅拌过夜。迅速添加乙酐(78.5ml,0.80mol)和三乙胺(112.9ml,0.81mol)的溶液,所得的黄色溶液在50℃搅拌2小时。在甲醇中沉淀此反应溶液,滤集所得的白色固体,用甲醇洗涤,放入真空烘箱中于室温干燥过夜,在100℃干燥3小时,220℃干燥3小时,
得到104.2g产物。
此聚酰亚胺以大于10%的固体含量(基于聚合物重量)溶于丙酮、二氯甲烷、二甲亚砜、间甲酚、N-甲基吡咯烷酮、氯仿、碳酸丙烯酯和乙酸甲酯。
将上述聚合物在N-甲基吡咯烷酮中的15%(重量浓度)溶液,在90℃下以15密耳(38×10-5m)的刀隙流延到经杜邦TEFLON干润滑剂处理过的玻璃板上制成膜。此膜在板上于90℃干燥25分钟,冷却至室温,放入真空烘箱在室温下干燥过夜。将此膜从板上剥离,放入真空烘箱在120℃进一步干燥4小时。
此膜质地韧而柔,折叠时不会破裂。这些膜(平均厚度约为1.5密耳(3.8×10-5m))是透明的且基本无色。
用450瓦Hanovia中压汞弧光灯在低于50℃温度下将上述膜的两面各辐照15分钟。将此膜放入N-甲基吡咯烷酮(上述未交联聚合物的良溶剂)。该溶剂变得稍有些着色,但膜的大部分没有溶解和溶胀。
实例8
在惰性气氛中在50℃搅拌下,向2,4,6-三甲基-1,3-亚苯基二胺(30.01g,0.20mol)在N-甲基吡咯烷酮(350ml)中的溶液添加3,3′,4,4′-二苯酮四酸二酐(16.1g,0.05mol),将得到的黄色溶液搅拌0.5小时。向其中添加4,4′-〔2,2,2-三氟-1-(三氟甲基)亚乙基〕双(1,2-苯二甲酸酐)(66.6g,0.15mol,分四批加入,最后一批加入后用150ml N-甲基吡咯烷酮冲洗),得到一淡黄色溶液。在50℃搅拌过夜后,迅速添加乙酐(75.8ml,0.80mol)
和三乙胺(112.9ml,0.81mol)的溶液,在50℃将得到的反应溶液搅拌2小时。在甲醇中沉淀上述反应溶液,滤集生成的固体,用甲醇洗涤,放入真空烘箱于室温下干燥过夜,在100℃干燥3小时,200℃干燥3小时。产物是灰白色的固体(102.3g)。
此聚酰胺以大于20%的固体含量(基于聚合物重量)溶于丙酮、二氯甲烷、二甲亚砜、间甲酚、和N-甲基吡咯烷酮。
将上述聚合物在N-甲基吡咯烷酮中的15%(重量浓度)溶液,于90℃以15密耳(38×10-5m)的刀隙,流延到经杜邦TEFLON干润滑剂处理过的玻璃板上制成膜。此膜在板上于90℃干燥25分钟,冷却至室温,放入真空烘箱在室温下干燥过夜。将膜从板上剥离,放入真空烘箱在120℃进一步干燥4小时。
这些膜质地韧而柔,折叠时不会破裂。这些膜(平均厚度约为1.5密耳(3.8×10-5m))是透明的且基本无色。
用450瓦Hanovia中压汞弧光灯在低于50℃的温度下将膜的两面各辐照15分钟。将膜的一部分置于N-甲基吡咯烷酮(上述未交联聚合物的良溶剂)中。膜的大部分不溶解不溶胀,有少量聚合物发生溶胀。
实例9
在惰性气氛中于50℃搅拌下向2,6-二氨基甲苯(12.3g,0.10mol)在N-甲基吡咯烷酮(200ml)中的溶液添加4,4′-〔2,2,2-三氟-1-(三氟甲基)亚乙基〕双(1,2-苯二甲酸酐)(44.4g,0.10mol,最后一批加入后用100ml N-甲基吡咯烷酮洗涤)。得到的反应溶液在50℃搅拌过夜。迅速添加乙酐(37.9ml,0.402mol)和三乙胺(56.5ml,
0.405mol)的溶液,将得到的反应溶液在50℃搅拌2小时。在甲醇中将上述反应溶液沉淀,滤集生成的固体,用甲醇洗涤,在真空烘箱中于室温干燥过夜,在100℃干燥5小时,250℃干燥2小时。产物是灰白色的固体,产量50.0g。
此聚酰亚胺以大于20%的固体含量(基于聚合物重量)溶于丙酮、二氯甲烷、N-甲基吡咯烷酮、二甲亚砜和间甲酚。
用带有HCB1-S/N00523型料室的990-3型杜邦热分析仪,在氮气氛中以10℃/分钟的速率,基线斜率=5.0,对上述聚合物进行示差扫描量热分析(DSC)观察到Tg的相关转变温度是起始温度为339℃和中点温度为345℃。
用带有9Q1-5型料室的99-2型杜邦热失重分析仪,在氮气氛中以10℃/分钟的升温速率,对上述聚合物进行热失重分析(TGA)。在535℃观察5%的重量损失,在575℃观察到40%的重量损失。
将上述聚合物在N-甲基吡咯烷酮中的15%(重量浓度)溶液,在80℃以15密耳(38×10-5m)的刀隙,流延到经杜邦TEFLON干润滑剂处理过的玻璃板上制备膜,此膜在板上于80℃干燥25分钟,冷却至室温,在真空烘箱中于室温干燥过夜。然后从板上剥离此膜,在真空烘箱中于120℃进一步干燥4小时。
此膜质地韧而柔,折叠时不会破裂。这些膜(平均厚度约为1.5密耳(3.8×10-5m))是透明的且基本无色。
Claims (13)
3、权利要求1的方法,其中脱水剂是乙酐和三乙胺的溶液。
4、权利要求2的方法,其中脱水剂是乙酐和三乙胺的溶液。
5、权利要求1的制备方法,其中v=0-25。
6、权利要求5的制备方法,其中-x、-x1、-x2、-x3和-x4是-CH3或-C2H5。
12、权利要求8的制备方法,其中芳香族聚酰亚胺是已交联的。
13、权利要求1的制备方法,其中t、u和v为零,-Z、-Z1和-Z2是-H。
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EP (1) | EP0303774A3 (zh) |
JP (1) | JPH02160832A (zh) |
KR (1) | KR890016084A (zh) |
CN (1) | CN1018183B (zh) |
AU (1) | AU613626B2 (zh) |
BR (1) | BR8802383A (zh) |
DK (1) | DK322988A (zh) |
MA (1) | MA21281A1 (zh) |
NO (1) | NO882141L (zh) |
NZ (1) | NZ224632A (zh) |
OA (1) | OA08847A (zh) |
PT (1) | PT87508A (zh) |
TN (1) | TNSN88060A1 (zh) |
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KR100200199B1 (ko) * | 1994-08-02 | 1999-06-15 | 사또 아끼오 | 광학필터용 폴리이미드수지조성물 |
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KR100351628B1 (ko) * | 2000-08-25 | 2002-09-11 | 한국화학연구원 | 신규 폴리이미드와 이를 이용한 기체 분리막 |
US6451955B1 (en) * | 2000-09-28 | 2002-09-17 | Sumitomo Bakelite Company Limited | Method of making a polyimide in a low-boiling solvent |
US6500233B1 (en) | 2000-10-26 | 2002-12-31 | Chevron U.S.A. Inc. | Purification of p-xylene using composite mixed matrix membranes |
DE10134720A1 (de) * | 2001-01-19 | 2002-07-25 | Bayer Ag | Synergistische Mischungen |
US6737502B2 (en) * | 2002-06-06 | 2004-05-18 | Chung-Shan Institute Of Science & Technology | Method of synthesizing polyimides |
DE102005017195B4 (de) | 2005-04-13 | 2007-02-22 | Gkss-Forschungszentrum Geesthacht Gmbh | Kompositmaterial, insbesondere Kompositmembran und Verfahren zur Herstellung desselben |
US7550194B2 (en) | 2005-08-03 | 2009-06-23 | E. I. Du Pont De Nemours And Company | Low color polyimide compositions useful in optical type applications and methods and compositions relating thereto |
US20090226642A1 (en) * | 2005-08-03 | 2009-09-10 | E. I. Du Pont De Nemours And Company | Low color polyimide compositions useful in optical type applications and methods and compositions relating thereto |
US7572878B2 (en) * | 2005-09-16 | 2009-08-11 | E. I. Du Pont De Nemours And Company | Polycyclic polyimides and compositions and methods relating thereto |
NZ599605A (en) | 2007-02-19 | 2013-11-29 | Marinepolymer Tech Inc | Hemostatic compositions and therapeutic regimens |
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KR101225842B1 (ko) * | 2007-08-27 | 2013-01-23 | 코오롱인더스트리 주식회사 | 무색투명한 폴리이미드 필름 |
WO2009142434A2 (ko) | 2008-05-19 | 2009-11-26 | 한양대학교 산학협력단 | 중공사, 중공사 형성용 도프 용액 조성물 및 이를 이용한 중공사의 제조방법 |
WO2009142433A2 (ko) | 2008-05-19 | 2009-11-26 | 한양대학교 산학협력단 | 중공사, 중공사 형성용 도프 용액 조성물 및 이를 이용한 중공사의 제조방법 |
US8288484B2 (en) * | 2009-03-10 | 2012-10-16 | Samsung Electronics Co., Ltd. | Cross-linked product of metal-containing polyamic acid, cross-linked product of metal-containing polyimide including the cross-linked product of metal-containing polyamic acid, method of manufacturing the cross-linked product of metal-containing polyimide, and polyimide film including the cross-linked product of metal-containing polyimide |
KR101328838B1 (ko) * | 2010-03-30 | 2013-11-13 | 코오롱인더스트리 주식회사 | 폴리이미드 필름 |
US8853723B2 (en) | 2010-08-18 | 2014-10-07 | E. I. Du Pont De Nemours And Company | Light emitting diode assembly and thermal control blanket and methods relating thereto |
NZ732118A (en) | 2011-04-15 | 2018-11-30 | Marine Polymer Tech Inc | Treatment of disease with poly-n-acetylglucosamine nanofibers |
US8614288B2 (en) * | 2011-06-17 | 2013-12-24 | Uop Llc | Polyimide gas separation membranes |
EP2831146A4 (en) * | 2012-03-28 | 2015-11-04 | Basf Se | POLYIMIDE AS DIELECTRIC |
MX2015011418A (es) | 2013-03-14 | 2015-12-16 | Marinepolymer Tech Inc | Tratamiento de enfermedades con nanofibras de poli-n-acetilglucosamina. |
JP6230308B2 (ja) | 2013-07-16 | 2017-11-15 | ソマール株式会社 | 透明ポリイミド共重合体、ポリイミド樹脂組成物及び成形体、並びにこの共重合体の製造方法 |
TWI490274B (zh) * | 2014-10-29 | 2015-07-01 | Mortech Corp | 聚醯亞胺基聚合物、應用聚醯亞胺基聚合物之聚醯亞胺膜與應用聚醯亞胺基聚合物之聚醯亞胺積層板 |
WO2016190105A1 (ja) * | 2015-05-25 | 2016-12-01 | コニカミノルタ株式会社 | ポリイミドフィルム、ポリイミドフィルムの製造方法、フレキシブルプリント基板、フレキシブルディスプレイ用基板、フレキシブルディスプレイ用前面板、led照明装置及び有機エレクトロルミネッセンス表示装置 |
JP6834592B2 (ja) * | 2016-04-01 | 2021-02-24 | 住友金属鉱山株式会社 | ポリイミド樹脂中のオリゴマ量の評価方法 |
CN106832278A (zh) * | 2017-02-08 | 2017-06-13 | 常州市明卓新材料科技有限公司 | 一类高透明共聚型含氟聚酰亚胺膜材料及其制备方法 |
CN106810861A (zh) * | 2017-02-08 | 2017-06-09 | 常州大学 | 一类可溶性共聚型聚芳酰胺膜材料及其制备方法 |
CN110681272B (zh) * | 2018-07-06 | 2022-02-01 | 中国石油化工股份有限公司 | 聚酰亚胺渗透汽化膜及其制备方法 |
KR102152278B1 (ko) | 2018-11-30 | 2020-09-07 | 한국화학연구원 | Bcda 기반의 부분-지환족 폴리이미드 기체분리막 소재 및 이의 제조방법 |
US11007492B2 (en) | 2019-02-27 | 2021-05-18 | Saudi Arabian Oil Company | Aromatic co-polyimide gas separation membranes derived from 6FDA-DAM-type homo-polyimides |
US11007491B2 (en) | 2019-02-27 | 2021-05-18 | Saudi Arabian Oil Company | Aromatic co-polyimide gas separation membranes derived from 6FDA-6FpDA-type homo-polyimides |
EP4298906A1 (en) * | 2022-06-27 | 2024-01-03 | The Procter & Gamble Company | Antimicrobial composition comprising a polyimide |
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US3227510A (en) * | 1958-03-04 | 1966-01-04 | Tee Pak Inc | Dyeing substrates ionically binding in localized areas catalysts for the predyeing olefin polymerization thereon |
US3423491A (en) * | 1964-09-02 | 1969-01-21 | Dow Chemical Co | Permselective hollow fibers and method of making |
US3356648A (en) * | 1966-10-13 | 1967-12-05 | Du Pont | Polyamide-acids and polyimides from hexafluoropropylidine bridged diamine |
FR2050251A1 (en) * | 1969-07-08 | 1971-04-02 | Inst Francais Du Petrole | Sulphonated polyimides (i) used as ion ex- - changes and in electrodialysis |
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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 |
US4629777A (en) * | 1983-05-18 | 1986-12-16 | Ciba-Geigy Corporation | Polyimides, a process for their preparation and their use |
US4705540A (en) * | 1986-04-17 | 1987-11-10 | 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 |
US4717394A (en) * | 1986-10-27 | 1988-01-05 | E. I. Du Pont De Nemours And Company | Polyimide gas separation membranes |
-
1988
- 1988-04-19 US US07/178,092 patent/US4912197A/en not_active Expired - Lifetime
- 1988-05-16 MA MA21522A patent/MA21281A1/fr unknown
- 1988-05-16 NZ NZ224632A patent/NZ224632A/xx unknown
- 1988-05-16 NO NO88882141A patent/NO882141L/no unknown
- 1988-05-16 OA OA59353A patent/OA08847A/xx unknown
- 1988-05-17 BR BR8802383A patent/BR8802383A/pt unknown
- 1988-05-17 KR KR1019880005877A patent/KR890016084A/ko not_active Application Discontinuation
- 1988-05-17 AU AU16323/88A patent/AU613626B2/en not_active Ceased
- 1988-05-18 JP JP63119451A patent/JPH02160832A/ja active Pending
- 1988-05-18 PT PT87508A patent/PT87508A/pt not_active Application Discontinuation
- 1988-05-18 CN CN88102946A patent/CN1018183B/zh not_active Expired
- 1988-05-18 EP EP88107949A patent/EP0303774A3/en not_active Withdrawn
- 1988-06-10 TN TNTNSN88060A patent/TNSN88060A1/fr unknown
- 1988-06-14 DK DK322988A patent/DK322988A/da not_active Application Discontinuation
Also Published As
Publication number | Publication date |
---|---|
BR8802383A (pt) | 1989-02-28 |
DK322988D0 (da) | 1988-06-14 |
CN1031239A (zh) | 1989-02-22 |
AU1632388A (en) | 1989-02-16 |
KR890016084A (ko) | 1989-11-28 |
TNSN88060A1 (fr) | 1990-07-10 |
PT87508A (pt) | 1989-06-30 |
US4912197A (en) | 1990-03-27 |
OA08847A (en) | 1989-03-31 |
EP0303774A3 (en) | 1989-05-31 |
EP0303774A2 (en) | 1989-02-22 |
NO882141L (no) | 1989-02-15 |
JPH02160832A (ja) | 1990-06-20 |
DK322988A (da) | 1989-02-15 |
AU613626B2 (en) | 1991-08-08 |
NZ224632A (en) | 1990-07-26 |
MA21281A1 (fr) | 1988-12-31 |
NO882141D0 (no) | 1988-05-16 |
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