JPH03247623A - Polyimide resin and its manufacture - Google Patents
Polyimide resin and its manufactureInfo
- Publication number
- JPH03247623A JPH03247623A JP2044578A JP4457890A JPH03247623A JP H03247623 A JPH03247623 A JP H03247623A JP 2044578 A JP2044578 A JP 2044578A JP 4457890 A JP4457890 A JP 4457890A JP H03247623 A JPH03247623 A JP H03247623A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- represented
- polyimide resin
- tetraphenylpyrrole
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920001721 polyimide Polymers 0.000 title claims abstract description 48
- 239000009719 polyimide resin Substances 0.000 title claims abstract description 40
- 238000004519 manufacturing process Methods 0.000 title description 10
- 150000004985 diamines Chemical class 0.000 claims abstract description 24
- IEZVMRGFNUNABR-UHFFFAOYSA-N 2,3,4,5-tetraphenyl-1h-pyrrole Chemical compound C1=CC=CC=C1C1=C(C=2C=CC=CC=2)C(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)N1 IEZVMRGFNUNABR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims description 18
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 7
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 7
- 150000000000 tetracarboxylic acids Chemical class 0.000 claims description 7
- 239000002904 solvent Substances 0.000 abstract description 15
- -1 tetracarboxylic acid dianhydride Chemical class 0.000 abstract description 13
- ZUMJXLDDCLRIPJ-UHFFFAOYSA-N 4-[4-(4-aminophenyl)-2,5-diphenyl-1h-pyrrol-3-yl]aniline Chemical compound C1=CC(N)=CC=C1C1=C(C=2C=CC=CC=2)NC(C=2C=CC=CC=2)=C1C1=CC=C(N)C=C1 ZUMJXLDDCLRIPJ-UHFFFAOYSA-N 0.000 abstract description 2
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 28
- 238000006243 chemical reaction Methods 0.000 description 22
- 238000006116 polymerization reaction Methods 0.000 description 16
- 229920005575 poly(amic acid) Polymers 0.000 description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 10
- 230000009477 glass transition Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 7
- 229940100630 metacresol Drugs 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 6
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 5
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000004642 Polyimide Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 229930003836 cresol Natural products 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 239000012770 industrial material Substances 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- GWHLJVMSZRKEAQ-UHFFFAOYSA-N 3-(2,3-dicarboxyphenyl)phthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C(=C(C(O)=O)C=CC=2)C(O)=O)=C1C(O)=O GWHLJVMSZRKEAQ-UHFFFAOYSA-N 0.000 description 1
- AVCOFPOLGHKJQB-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)sulfonylphthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1S(=O)(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 AVCOFPOLGHKJQB-UHFFFAOYSA-N 0.000 description 1
- IWXCYYWDGDDPAC-UHFFFAOYSA-N 4-[(3,4-dicarboxyphenyl)methyl]phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1CC1=CC=C(C(O)=O)C(C(O)=O)=C1 IWXCYYWDGDDPAC-UHFFFAOYSA-N 0.000 description 1
- APXJLYIVOFARRM-UHFFFAOYSA-N 4-[2-(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(C(O)=O)C(C(O)=O)=C1 APXJLYIVOFARRM-UHFFFAOYSA-N 0.000 description 1
- 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 1
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 1
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 241001428214 Polyides Species 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000006210 cyclodehydration reaction Methods 0.000 description 1
- XSBSXJAYEPDGSF-UHFFFAOYSA-N diethyl 3,5-dimethyl-1h-pyrrole-2,4-dicarboxylate Chemical compound CCOC(=O)C=1NC(C)=C(C(=O)OCC)C=1C XSBSXJAYEPDGSF-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はポリイミド樹脂、特に各種有機溶媒に可溶でな
おかつ高いガラス転移温度を有する新規ポリイミド樹脂
およびその製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a polyimide resin, particularly a novel polyimide resin that is soluble in various organic solvents and has a high glass transition temperature, and a method for producing the same.
（従来の技術）
従来芳香族ポリイミド樹脂は優れた耐熱性とともに優れ
た電気的、機械的特性を有し、広く工業材料として使用
されてきた。しかしこれら多（のポリイミド樹脂は各種
有機溶媒および鉱酸のいずれにも不溶であり、また熱的
に不融でもあるので、その成形を行なうことは極めて困
難であった。(Prior Art) Conventionally, aromatic polyimide resins have excellent heat resistance as well as excellent electrical and mechanical properties, and have been widely used as industrial materials. However, since many of these polyimide resins are insoluble in various organic solvents and mineral acids, and are also thermally infusible, it has been extremely difficult to mold them.
（発明が解決しようとする課題）
上記のような従来の芳香族ポリイミド樹脂においては、
高いガラス転移温度を有し耐熱性に優れていて、しかも
同時に有機溶媒に対する良好な熔解性を有するものはほ
とんどなく、このような耐熱性と加工性とをともに具備
する芳香族ポリイミド樹脂がないことがこの樹脂の商業
的利用の上で大きな問題点であった。したがって、本発
明は、各種有機溶媒に可溶で、なおかつ高いガラス転移
温度を有する新規なポリイミド樹脂およびその製造方法
を提供することを目的とする。(Problem to be solved by the invention) In the conventional aromatic polyimide resin as described above,
There are few aromatic polyimide resins that have a high glass transition temperature, excellent heat resistance, and good solubility in organic solvents, and that have both such heat resistance and processability. This has been a major problem in the commercial use of this resin. Therefore, an object of the present invention is to provide a novel polyimide resin that is soluble in various organic solvents and has a high glass transition temperature, and a method for producing the same.
（課題を解決するための手段）
本発明者らは各種有機溶剤や鉱酸に可溶で、なおかつ高
いガラス転移点を有するポリイミド樹脂を製造するべく
鋭意努力し、本発明を完成した。(Means for Solving the Problems) The present inventors have worked diligently to produce a polyimide resin that is soluble in various organic solvents and mineral acids and has a high glass transition point, and have completed the present invention.
本発明の第一の発明は、
一般式
（式中、Ｒは四価の芳香族基、Ａｒは二価のテトラフェ
ニルピロール基、ｎは１０〜２００の整数を示す）
で表わされるポリイミド樹脂である。The first invention of the present invention is a polyimide resin represented by the general formula (wherein R is a tetravalent aromatic group, Ar is a divalent tetraphenylpyrrole group, and n is an integer from 10 to 200). be.
本発明の第二の発明は、
一般式
％式％（）
（式中、Ａｒは二価のテトラフェニルピロール基を示す
）
で表わされるジアミンと
一般式
％式％
（式中、Ｒは四価の芳香族基を示す）
で表わされるテトラカルボン酸二無水物を有機溶媒中で
反応させることにより、−数式
（式中、Ｒは四価の芳香族基、Ａｒは二価のテトラフェ
ニルピロール基、ｎは１０〜２００の整数を示す）
で表わされるポリイミド樹脂の製造方法である。The second invention of the present invention is a diamine represented by the general formula % formula % (in the formula, Ar represents a divalent tetraphenylpyrrole group) and a diamine represented by the general formula % formula % (in the formula, R is a tetravalent tetraphenylpyrrole group). By reacting a tetracarboxylic dianhydride represented by the following (representing an aromatic group) in an organic solvent, , n is an integer from 10 to 200).
本発明の第三の発明は、
−数式
Ｈ２Ｎ−Ａｒ−ＮＨ２’ （ＩＩ）（式
中、Ａｒは二価のテトラフェニルピロール基を示す）
で表わされるジアミンと
一般式
％式％
（式中、Ｒは四価の芳香族基を示す）
で表わされるテトラカルボン酸二チオ無水物を有機溶媒
中で反応させることにより、−数式（式中、Ｒは四価の
芳香族基、Ａｒは二価のテトラフェニルピロール基、ｎ
は１０〜２００の整数ヲ示す）
で表わされるポリイミド樹脂の製造方法である。The third invention of the present invention provides a diamine represented by the formula H2N-Ar-NH2' (II) (wherein Ar represents a divalent tetraphenylpyrrole group) and a diamine represented by the general formula % formula % (wherein, R represents a tetravalent aromatic group) By reacting tetracarboxylic acid dithioanhydride represented by tetraphenylpyrrole group, n
is an integer from 10 to 200).
（作 用） 以下、本発明の構成をその作用とともに更に詳述する。(for production) Hereinafter, the structure of the present invention will be explained in further detail along with its operation.
上記−数式（１）で表わされるポリイミド樹脂は上記−
数式（ＩＩ）で表わされるジアミンと上記−数式（Ｉ［
［）で表わされるテトラカルボン酸二無水物、または上
記−数式（Ｉ［）で表わされるジアミンと上記−数式（
ＩＶ）で表わされるテトラカルボン酸二チオ無水物から
製造されるが、ジアミンとしては二価のテトラフェニル
ビロール基からなるジアミンを単独で使用することもで
きるし、あるいは一種または二種以上の二価の芳香族基
からなるジアミンを混合して使用することもできる。The polyimide resin represented by the above formula (1) is the above-
A diamine represented by formula (II) and the above-mentioned formula (I[
A tetracarboxylic dianhydride represented by [), or a diamine represented by the above-mentioned formula (I[) and the above-mentioned formula (I[)]
It is produced from the tetracarboxylic acid dithioanhydride represented by IV), but as the diamine, a diamine consisting of a divalent tetraphenylpyrrole group can be used alone, or one or more diamines can be used. It is also possible to use a mixture of diamines consisting of aromatic groups.
上記−数式（ＩＩ）で表わされる二価のテトラフェニル
ビロール基からなるジアミンとは、３，４−ビス（４−
アミノフェニル） −２，５−ジフェニルビロールを指
す、このジアミンは１．２−ビス（４ニトロフエニル）
−１，２−ジベンゾイルエタンを出発原料として、脱水
環化（ｋｎｏｒｒのピロール合成法）および還元の二段
階の合成経路より容易に製造できる。The diamine consisting of a divalent tetraphenylpyrrole group represented by the above-mentioned formula (II) is 3,4-bis(4-
(aminophenyl) -2,5-diphenylvirol, this diamine is 1,2-bis(4-nitrophenyl)
Using -1,2-dibenzoylethane as a starting material, it can be easily produced through a two-step synthetic route of cyclodehydration (knorr's pyrrole synthesis method) and reduction.
本発明で使用する上記−数式（ＩＩ［）で表わされるテ
トラカルボン酸二無水物誘導体としては、例えば、ピロ
メリト酸二無水物、２．３．６．７−ナフタレンテトラ
カルボン酸二無水物、３．４．３’４′−ビフェニルテ
トラカルボン酸二無水物、２゜３、２’ 、 ３’−ビ
フェニルテトラカルボン酸二無水物、ビス（３，４−ジ
カルボキシフェニル）メタンニ無水物、２，２−ビス（
３，４−ジカルボキシフェニル）プロパンニ無水物、ビ
ス（３，４−ジカルボキシフェニル）エーテルニ無水物
、ビス（３，４−ジカルボキシフェニル）スルホンニ無
水物、３゜４、３’ 、 ４’−ベンゾフェノンテトラ
カルボン酸二無水物、２，２−ビス（３，４−ジカルボ
キシフェニル）へキサフルオロプロパンニ無水物などを
例示することができる。Examples of the tetracarboxylic dianhydride derivatives represented by the above formula (II[) used in the present invention include pyromellitic dianhydride, 2.3.6.7-naphthalenetetracarboxylic dianhydride, 3 .4.3'4'-biphenyltetracarboxylic dianhydride, 2゜3,2', 3'-biphenyltetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, 2, 2-bis(
3,4-dicarboxyphenyl)propanihydride, bis(3,4-dicarboxyphenyl)ether dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, 3゜4,3',4'- Examples include benzophenone tetracarboxylic dianhydride and 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride.
本発明で使用する上記−数式（ＩＶ）で表わされるテト
ラカルボン酸二チオ無水物誘導体としては、ピロメリト
酸二チオ無水物、２．３．６．７−ナフタレンテトラカ
ルボン酸二チオ無水物、３．４．３’４′−ビフェニル
テトラカルボン酸チオニ無水物、２、３．２’ 、３
’ −ビフェニルテトラカルボン酸二チオ無水物、ビス
（３，４−ジカルボキシフェニル）メタンニチオ無水物
、２，２−ビス（３，４−ジカルボキシフェニル）プロ
パンニチオ無水物、ビス（３１４−ジカルボキシフェニ
ル）エーテルニチオ無水物、ビス（３，４−ジカルボキ
シフェニル）スルホンニチオ無水物、３．４．３’ 、
４’−ベンゾフェノンテトラカルボン酸二チオ無水物
、２，２−ビス（３，４−ジカルボキシフェニル）へキ
サフルオロブロバンニチオ無水物等を例示することがで
きる。これらテトラカルボン酸二チオ無水物は、相当す
るテトラカルボン酸二無水物と硫化ナトリウムとの反応
により容易に合成することができる。The tetracarboxylic acid dithioanhydride derivatives represented by the above-mentioned formula (IV) used in the present invention include pyromellitic acid dithioanhydride, 2.3.6.7-naphthalenetetracarboxylic acid dithioanhydride, 3 .4.3'4'-Biphenyltetracarboxylic acid thioni anhydride, 2,3.2',3
' -Biphenyltetracarboxylic acid dithioanhydride, bis(3,4-dicarboxyphenyl)methanethioanhydride, 2,2-bis(3,4-dicarboxyphenyl)propanethioanhydride, bis(314-dicarboxylic acid dithioanhydride) phenyl)ethernitioanhydride, bis(3,4-dicarboxyphenyl)sulfonenitioanhydride, 3.4.3',
Examples include 4'-benzophenonetetracarboxylic acid dithioanhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluorobrobannithioanhydride, and the like. These tetracarboxylic dithioanhydrides can be easily synthesized by reacting the corresponding tetracarboxylic dianhydride with sodium sulfide.
上記−数式（ｎ）で表わされるジアミンと、上記−数式
（１）で表わされるテトラカルボン酸二無水物からの上
記−数式（Ｉ）で表わされるポリイミド樹脂の製造方法
は、有機溶媒中、実質的に無水の条件下で、上記−数式
（ＩＩ）で表わされるジアミンと、上記−数式（Ｉ［［
）で表わされるテトラカルボン酸二無水物誘導体を０〜
１００°Ｃで数十分から数日間反応させた後、８０〜４
００°Ｃで数十分から数日間反応させることにより行な
われるものである。The method for producing the polyimide resin represented by the above-mentioned formula (I) from the diamine represented by the above-mentioned formula (n) and the tetracarboxylic dianhydride represented by the above-mentioned formula (1) comprises substantially under anhydrous conditions, the diamine represented by the above-mentioned formula (II) and the above-mentioned formula (I[[
) of the tetracarboxylic dianhydride derivative represented by 0 to
After reacting at 100°C for several tens of minutes to several days, 80-4
This is carried out by reacting at 00°C for several tens of minutes to several days.
ここで、−数式（Ｉ）で表わされるポリイミド樹脂の重
合度ｎは、−数式（ＩＩ）で表わされるジアミンと、−
数式（ＩＩ［）で表わされるテトラカルボン酸二無水物
誘導体の仕込量によって制限され、これらの反応成分を
等モル量使用すると高重合度の上記−数式（１）で表わ
されるポリイミド樹脂を製造することができる。−数式
（１）のポリイミド樹脂においてｎを１０〜２００の整
数に限定した理由は、ｎが１０より小ではフィルム等に
成形した成形品の機械的特性や耐熱性などの特性が十分
でなく、ｎが２００を越えると有機溶剤などへの溶解性
や成形性が悪くなるからである。Here, the degree of polymerization n of the polyimide resin represented by the formula (I) is determined by the degree of polymerization n of the polyimide resin represented by the formula (II) and the diamine represented by the formula (II).
It is limited by the amount of the tetracarboxylic dianhydride derivative represented by the formula (II[), and if equimolar amounts of these reaction components are used, a polyimide resin represented by the above-mentioned formula (1) with a high degree of polymerization can be produced. be able to. - The reason why n is limited to an integer of 10 to 200 in the polyimide resin of formula (1) is that if n is smaller than 10, the mechanical properties and heat resistance of the molded product, such as a film, will not be sufficient. This is because when n exceeds 200, solubility in organic solvents and moldability deteriorate.
この方法に使用できる有機溶媒としては、Ｎ、 Ｎジメ
チルホルムアミド、Ｎ、 Ｎ−ジメチルアセトアミド、
Ｎ−メチル−２−ピロリドン等のアミド系溶媒、ジメチ
ルスルホキシド、テトラメチレンスルホン等のイオウ系
溶媒、アニソール、ジフェニルエーテル、ニトロベンゼ
ン、ヘンジニトリル、クレゾール、フェノール等のヘン
ゼン系溶媒などを例示することができる。特にクレゾー
ル、ニトロベンゼン等の水と共沸することのできる溶媒
を使用すると、これらの溶媒の沸点で後期の反応を行な
わせ、そのとき同時に溶媒を蒸留により除去する等の操
作を行なえばさらに高い効率で反応を進行させることが
できる。またこのとき、イソキノリン等の添加物を加え
て反応を行なっても差支えない。Organic solvents that can be used in this method include N,N-dimethylformamide, N,N-dimethylacetamide,
Examples include amide solvents such as N-methyl-2-pyrrolidone, sulfur solvents such as dimethyl sulfoxide and tetramethylene sulfone, and henzene solvents such as anisole, diphenyl ether, nitrobenzene, hendinitrile, cresol, and phenol. In particular, when using a solvent that can azeotrope with water, such as cresol or nitrobenzene, the latter stage of the reaction can be carried out at the boiling point of these solvents, and if the solvent is removed at the same time by distillation, even higher efficiency can be obtained. The reaction can proceed. Moreover, at this time, there is no problem even if the reaction is carried out by adding an additive such as isoquinoline.
本発明においては、上記−数式（ＩＩ）で表わされるジ
アミンと、上記−数式（ＩＩ［）で表わされるテトラカ
ルボン酸二無水物誘導体を反応させ、−数式
（式中、Ｒは四価の芳香族基、Ａｒは二価のテトラフェ
ニルピロール基、ｎは１０〜２００の整数を示す）
で表わされるポリアミド酸誘導体を製造し、従来より用
いられている脱水環化法（例えば、Ｃ，Ｅ。In the present invention, the diamine represented by the above-mentioned formula (II) is reacted with the tetracarboxylic dianhydride derivative represented by the above-mentioned formula (II[), Ar is a divalent tetraphenylpyrrole group, n is an integer of 10 to 200).
Ｓｒｏｏｇ、 Ｍａｃｒｏｍｏｌｅｃｕｌａｒ ５ｙｎ
ｔｈｅｓｅｓ ＣｏＣｏ１１ｅｃｔｉｖｅＶｏｌｕ
第１巻、第２９５頁（１９７７年）に記載された方法）
により、−数式（Ｉ）で表わされる本発明のポリイミド
樹脂を製造することもできる。上記−数式（Ｖ）で表わ
されるポリアミド酸誘導体は、上記−数式（ＩＩ）で表
わされるジアミン、上記−数式（Ｉ［Ｉ）で表わされる
テトラカルボン酸二無水物誘導体を実質的に無水の条件
下において反応させることにより容易に得られるもので
ある。Sroog, Macromolecular 5yn
theses CoCo11activeVolu
(method described in Vol. 1, p. 295 (1977))
Accordingly, the polyimide resin of the present invention represented by formula (I) can also be produced. The polyamic acid derivative represented by the above-mentioned formula (V) is prepared by preparing the diamine represented by the above-mentioned formula (II) and the tetracarboxylic dianhydride derivative represented by the above-mentioned formula (I[I) under substantially anhydrous conditions. It can be easily obtained by the reaction described below.
上記−数式（Ｖ）で表わされるポリアミド酸誘導体の重
合度は、上記−数式（ＩＩ）で表わされるジアミンと上
記−数式（Ｉ［［）で表わされるテトラカルボン酸二無
水物誘導体の仕込量によって制限され、これらの反応成
分を等モル量使用すると高重合度の上記−数式（Ｖ）で
表わされるポリアミド酸誘導体を製造することができる
。上記−数式（Ｖ）で表わされるポリアミド酸誘導体を
製造する際の反応温度は、０〜３００°Ｃの間で選択す
ることができるが、高温での反応物はさらに反応が進行
したポリイミド構造を含む可能性があり、６０°Ｃ以下
に反応温度を制御することが好ましい。また、この反応
に使用可能な有機溶媒としては一般式（Ｖ）で表わされ
るポリアミド酸誘導体を経由せずにポリイミド樹脂の製
造を行なう前記の場合と同様な有機溶媒を例示すること
ができる。The degree of polymerization of the polyamic acid derivative represented by the above formula (V) is determined by the amount of the diamine represented by the above formula (II) and the tetracarboxylic dianhydride derivative represented by the above formula (I[[)]. If these reaction components are used in equimolar amounts, it is possible to produce a polyamic acid derivative represented by formula (V) with a high degree of polymerization. The reaction temperature when producing the polyamic acid derivative represented by the above-mentioned formula (V) can be selected between 0 and 300°C, but the reaction product at a high temperature will form a polyimide structure that has undergone further reaction. It is preferable to control the reaction temperature to 60°C or less. Further, examples of organic solvents that can be used in this reaction include the same organic solvents as those used in the above case in which the polyimide resin is produced without using the polyamic acid derivative represented by the general formula (V).
かくして得られた上記−数式（Ｖ）で表わされるポリア
ミド酸誘導体の上記−数式（１）で表わされるポリイミ
ド樹脂への転化方法の一つは、上記−数式（Ｖ）で表わ
されるポリアミド酸誘導体を１５０°Ｃ〜４００°Ｃの
温度に加熱する方法である。One method for converting the thus obtained polyamic acid derivative represented by formula (V) into the polyimide resin represented by formula (1) is to convert the polyamic acid derivative represented by formula (V) above into polyimide resin represented by formula (1). This is a method of heating to a temperature of 150°C to 400°C.
この加熱時間は前記加熱温度によって異なるが、一般に
数分から数十時間の間である。別法としては、上記−数
式（Ｖ）で表わされるポリアミド酸誘導体を例えば酢酸
、プロピオン酸、酪酸、安息香酸等の酸無水物で処理す
る如き化学処理を行なうことによっても容易にポリイミ
ド樹脂への環化を達成し得る。ここで、環化反応を促進
する物質としてピリジン等を併用することができる。This heating time varies depending on the heating temperature, but is generally between several minutes and several tens of hours. Alternatively, the polyamic acid derivative represented by formula (V) above can be easily converted into polyimide resin by chemical treatment such as treatment with an acid anhydride such as acetic acid, propionic acid, butyric acid, or benzoic acid. Cyclization can be achieved. Here, pyridine or the like can be used in combination as a substance that promotes the cyclization reaction.
さらに、上記−船人（Ｉ）で表わされるポリイミド樹脂
を製造する方法の別法としては、上記−船人（Ｖ）で表
わされるポリアミド酸誘導体を製造する方法と同一の方
法により反応を進行させ、その後期において上記−船人
（Ｖ）で表わされるポリアミド酸誘導体を単離すること
なく無水酢酸等の添加剤を加え、さらに０℃〜３００℃
の温度で数分から数十時間反応させるものである。この
反応に使用される添加剤には、前記−船人（Ｖ）で表わ
されるポリアミド酸誘導体の化学処理により前記−船人
（１）で表わされるポリイミド樹脂を製造するときと同
様な添加剤を使用することができる。Furthermore, as an alternative method for producing the polyimide resin represented by -Funenin (I) above, the reaction is allowed to proceed by the same method as the method for producing the polyamic acid derivative represented by -Funenin (V) above. In the latter stage, additives such as acetic anhydride are added without isolating the polyamic acid derivative represented by Funato (V) above, and further heated at 0°C to 300°C.
The reaction is carried out at temperatures ranging from several minutes to several tens of hours. The additives used in this reaction include the same additives used when producing the polyimide resin represented by -Funenin (1) above by chemical treatment of the polyamic acid derivative represented by -Funenin (V). can be used.
上記−船人（Ｉ［）で表わされるジアミンと上記−船人
（ＩＶ）で表わされるテトラカルボン酸二チオ無水物か
らの上記−船人（Ｉ）で表わされるポリイミド樹脂の製
造方法は、有機溶媒中、実質的に無水の条件下で上記−
船人（ｎ）で表わされるジアミンと上記−船人（ＩＶ）
で表わされるテトラカルボン酸二チオ無水物誘導体を０
〜２００°Ｃで数十分から数日間反応させることにより
行なわれるものである。この反応においては硫化水素の
発生を伴うため、もはや硫化水素の発生が認められなく
なった点をもって反応終了と見なすことができる。この
方法において一般式（Ｉ）で表わされるポリイミド樹脂
の重合度ｎは、−船人（ＩＩ）で表わされるジアミンと
、−船人（ＩＶ）で表わされるテトラカルボン酸二チオ
無水物誘導体の仕込量によって制限され、これらの反応
成分を等モル量使用すると高重合度の上記−船人（１）
で表わされるポリイミド樹脂を製造することができる。The method for producing the polyimide resin represented by the above-mentioned shipman (I) from the diamine represented by the above-mentioned shipman (I[) and the tetracarboxylic acid dithioanhydride represented by the above-mentioned shipman (IV) is an organic in a solvent under substantially anhydrous conditions -
Diamine represented by Funer (n) and the above - Funer (IV)
The tetracarboxylic acid dithioanhydride derivative represented by 0
This is carried out by reacting at ~200°C for several tens of minutes to several days. Since this reaction involves the generation of hydrogen sulfide, the reaction can be considered to have ended when the generation of hydrogen sulfide is no longer observed. In this method, the degree of polymerization n of the polyimide resin represented by the general formula (I) is determined by the preparation of the diamine represented by -Funenin (II) and the tetracarboxylic acid dithioanhydride derivative represented by -Funenin (IV). When equimolar amounts of these reaction components are used, the above-mentioned degree of polymerization is limited by the amount of
A polyimide resin represented by can be manufactured.
−船人ＣＩ）のポリイミド樹脂においてｎがｌＯより小
ではフィルム等に成形した成形品の機械的特性や耐熱性
等の特性が十分でなく、ｎが２００を越えると有機溶剤
等への溶解性や成形性が悪くなる。- If n is smaller than 1O in the polyimide resin of Shipman CI), the mechanical properties and heat resistance of the molded product formed into a film etc. will not be sufficient, and if n exceeds 200, the solubility in organic solvents etc. will be poor. or the moldability deteriorates.
この方法に使用できる有機溶媒としては、Ｎ、 Ｎ−ジ
メチルホルムアミド、Ｎ、 Ｎ−ジメチルアセトアミド
、Ｎ−メチル−２−ピロリドン等のアミド系溶媒、ジメ
チルスルホキシド、テトラメチレンスルホン等の硫黄系
溶媒、アニソール、ジフェニルエーテル、ニトロベンゼ
ン、ベンゾニトリル、クレゾール、フェノール等のベン
ゼン系溶媒等を例示することができる。Organic solvents that can be used in this method include amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, sulfur solvents such as dimethyl sulfoxide and tetramethylene sulfone, and anisole. , diphenyl ether, nitrobenzene, benzonitrile, cresol, phenol, and other benzene-based solvents.
有機溶媒の使用量は反応成分の一方を溶解するに十分な
量であればよい。通常、反応成分を０．０５〜５０％含
む程度に用いれば高重合度のポリイミドを得ることがで
きる。The organic solvent may be used in an amount sufficient to dissolve one of the reaction components. Usually, polyimide with a high degree of polymerization can be obtained by using the reaction component in an amount of 0.05 to 50%.
重合反応は溶液状態で進行することもあれば、反応系か
ら重合体が析出してくることもある。この重合溶液から
、直接、ポリイミド樹脂のフィルム等の成形品を成形す
ることができる。The polymerization reaction may proceed in a solution state, or the polymer may precipitate from the reaction system. Molded articles such as polyimide resin films can be directly formed from this polymerization solution.
か（して製造された一般式（Ｉ）で表わされるポリイミ
ド樹脂は、使用した製造方法、−船人（ＩＩ）で表わさ
れるジアミンと併用し得る他のジアミンの種類並びに使
用量、使用した一般式（ＩＩＩ）で表わされるテトラカ
ルボン酸二無水物誘導体、および−船人（ＩＶ）で表わ
されるテトラカルボン酸二チオ無水物誘導体の種類によ
り特にその溶解性が変化するが、多くのポリイミド樹脂
において硫酸等の鉱酸に可溶となる。また、一部の樹脂
においては、Ｎ−メチル−２−ピロリドン、ジメチルイ
ミダゾリトン、ジメチルスルホキシド、メタクレゾール
、オルトクロロフェノール、ピリジン等の溶剤の全てに
、または一部に可溶となる。上記−船人（１）で表わさ
れるポリイミド樹脂の多くは、３００°Ｃ以上の高いガ
ラス転移点を有し、熱的に安定で５００°Ｃ付近まで加
熱しても熱分解は認められない。The polyimide resin represented by general formula (I) produced by The solubility varies depending on the type of the tetracarboxylic dianhydride derivative represented by formula (III) and the tetracarboxylic dithioanhydride derivative represented by -Funenin (IV), but in many polyimide resins, It becomes soluble in mineral acids such as sulfuric acid.In addition, some resins are soluble in all solvents such as N-methyl-2-pyrrolidone, dimethylimidazolitone, dimethyl sulfoxide, metacresol, orthochlorophenol, and pyridine. Many of the polyimide resins represented by Shipin (1) above have a high glass transition point of 300°C or higher, are thermally stable, and can be heated to around 500°C. However, no thermal decomposition is observed.
（実施例） 以下、本発明を実施例によりさらに詳細に説明する。(Example) Hereinafter, the present invention will be explained in more detail with reference to Examples.
夫旌汎上
３．４−ビス（４−アミノフェニル） −２，５−ジフ
ェニルピロール０．８０３ｇ （２，０ｍｍｏｌ）と０
．０８ｇのイソキノリンを１３．３ｍＬの精製したメタ
クレゾールに溶解し、窒素気流下で４０°Ｃに加熱した
。この溶液に０．６４４ ｇ （２，Ｏｍｍｏｌ）の３
．４．３’ 、 ４ ’−ベンゾフェノンテトラカルボ
ン酸二無水物を加えた。この溶液を４５°Ｃで３時間、
１５０℃で３時間撹拌しながら反応させた。反応装置に
蒸留装置を取り付け、油浴温度を２４０°Ｃで溶媒のメ
タクレゾールを窒素気流下に留去した。このとき、反応
装置内の反応物を一定した液量に保つように０．５％の
イソキノリンを含むメタクレゾールを加えた。3,4-bis(4-aminophenyl)-2,5-diphenylpyrrole 0.803g (2,0mmol) and 0
．． 08 g of isoquinoline was dissolved in 13.3 mL of purified metacresol and heated to 40° C. under nitrogen flow. Add 0.644 g (2, Ommol) of 3 to this solution.
．． 4.3',4'-benzophenone tetracarboxylic dianhydride was added. This solution was heated at 45°C for 3 hours.
The reaction was carried out at 150° C. for 3 hours with stirring. A distillation device was attached to the reaction apparatus, and the solvent metacresol was distilled off under a nitrogen stream at an oil bath temperature of 240°C. At this time, metacresol containing 0.5% isoquinoline was added to keep the reactant in the reactor at a constant liquid volume.
この操作を５時間行なった後、窒素気流下室温に冷却し
、黄色のポリイミド樹脂溶液を得た。この溶液の一部を
３００ｍＬのメタノールに投入しポリイド樹脂の沈殿を
得、ろ別後１００℃で真空乾燥した。After performing this operation for 5 hours, the mixture was cooled to room temperature under a nitrogen stream to obtain a yellow polyimide resin solution. A portion of this solution was poured into 300 mL of methanol to obtain a polyide resin precipitate, which was filtered and dried under vacuum at 100°C.
残りの重合溶液は、ガラス板上にキャストし、これを１
００℃、ついで１８０°Ｃで真空乾燥してポリイミドフ
ィルムを得た。The remaining polymerization solution was cast onto a glass plate and 1
A polyimide film was obtained by vacuum drying at 00°C and then at 180°C.
固有粘度： ０．４２ｄＬ／ ｇ （Ｎ−メチルピロリ
ドン中、濃度０．５ｇ／ｄＬ、３０°Ｃで測定）赤外吸
収スペクトル（フィルム） ： １７８２．１７２５゜
１３７０、７２８ ｃｍ−’ （いずれもイミド結合の
特性吸収）元素分析値
炭素 水素 窒素
計算値（％） ７８．５９ ３．６６ ６．１
１実測値（％） ７７．２１ ３．５４ ６．
０２ガラス転移温度：３０６°Ｃ
１０％重量重量減変温空気中で５４０ ’Ｃ１窒素中で
５８０ ”Ｃであった。Intrinsic viscosity: 0.42 dL/g (measured in N-methylpyrrolidone at a concentration of 0.5 g/dL at 30°C) Infrared absorption spectrum (film): 1782.1725° 1370, 728 cm-' (both imide Bond characteristics Absorption) Elemental analysis values Carbon Hydrogen Nitrogen Calculated values (%) 78.59 3.66 6.1
1 Actual value (%) 77.21 3.54 6.
02 Glass transition temperature: 306°C 10% weight loss 540'C in air and 580'C in nitrogen.
溶解性：硫酸、メタクレゾール、オルトクロロフェノー
ル、ピリジン、ジメチルイミダゾリジドン、Ｎ−メチル
ピロリドン等に可溶であった。Solubility: Soluble in sulfuric acid, metacresol, orthochlorophenol, pyridine, dimethylimidazolizidone, N-methylpyrrolidone, etc.
１施■又
３．４−ビス（４−アミノフェニル−２，５−ジフェニ
ルピロール０．８０３ ｇ （２，０ｍｍｏｌ）を３．
３ｍＬの精製したＮ−メチルピロリドンに溶解した。こ
の溶液に０．４３６ ｇ （２，０＋ｗｍｏｌ）の無水
ピロメリト酸を窒素気流下で加え、２０°Ｃで３時間反
応させた。得られた重合溶液の一部を３００ｍＬのメタ
ノールに投入し、ポリアミド酸を沈殿させ、ろ過後室温
で真空乾燥した（固有粘度０．４５ｄＬ／ ｇ、ジメチ
ルアセトアミド中、濃度０．５ｇ／ｄＬ、３０°Ｃで測
定）。一方、残りの重合溶液をガラス板上にキャストし
、これヲ８０℃で乾燥してポリアミド酸のフィルムを得
た。1. Also, 0.803 g (2.0 mmol) of 3.4-bis(4-aminophenyl-2,5-diphenylpyrrole) was added to 3.
Dissolved in 3 mL of purified N-methylpyrrolidone. To this solution, 0.436 g (2.0+wmol) of pyromellitic anhydride was added under a nitrogen stream, and the mixture was reacted at 20°C for 3 hours. A portion of the obtained polymerization solution was poured into 300 mL of methanol to precipitate polyamic acid, which was filtered and then vacuum dried at room temperature (intrinsic viscosity 0.45 dL/g, concentration 0.5 g/dL in dimethylacetamide, 30% (measured in °C). On the other hand, the remaining polymer solution was cast onto a glass plate and dried at 80°C to obtain a polyamic acid film.
このフィルムを１００℃、２００°Ｃ，２８０℃で順次
１時間づつ熱処理してポリイミドフィルムを得た。This film was heat treated at 100°C, 200°C and 280°C for 1 hour each to obtain a polyimide film.
赤外吸収スペクトル（フィルム） ： １７８０．１７
２８゜１３６５、７２０ ｒ：ｍ−’ （いずれもイミ
ド結合の特性吸収）固有粘度： ０．４７ｄＬ／ ｇ
（硫酸中、濃度０．５ｇ／ｄＬ、 ３０℃で測定）
元素分析値
炭素 水素 窒素
計算値（％’） ７８．２１ ３．６３ ７．
２０実測値（％） ７６．８６ ３．５０ ７
．０６ガラス転移温度：３５９°Ｃ
１０％重量重量減変温空気中で５２５℃、窒素中で５８
５℃であった。Infrared absorption spectrum (film): 1780.17
28゜1365, 720 r:m-' (both characteristic absorption of imide bond) Intrinsic viscosity: 0.47 dL/g
(Measured in sulfuric acid at a concentration of 0.5 g/dL at 30°C) Elemental analysis values Carbon Hydrogen Nitrogen Calculated values (%') 78.21 3.63 7.
20 Actual value (%) 76.86 3.50 7
．． 06 Glass transition temperature: 359°C 10% weight loss 525°C in air, 58°C in nitrogen
The temperature was 5°C.
溶解性：硫酸にのみ可溶であった。Solubility: Soluble only in sulfuric acid.
１施■又
３．４−ビス（４−アミノフェニル−２，５−ジフェニ
ルビロール
製したＮ，Ｎ−ジメチルアセトアミドに溶解した。Once again, 3,4-bis(4-aminophenyl-2,5-diphenylvirol) was dissolved in N,N-dimethylacetamide.
この溶液に０．５９ ｇ （２．０ｍｍｏｌ）の３．
４． ３’ 、 ４’ビフエニルテトラカルボン酸二無
水物を窒素気流下で加え、２０゛Ｃで３時間反応させた
。得られた重合溶液の一部を３００ｍＬのメタノールに
投入し、ポリアミド酸を沈殿させ、ろ過後室温で真空乾
燥した（固有粘度０．４８ｄＬ／ ｇ 、ジメチルアセ
トアミド中、濃度０．５ｇ／ｄＬ、３０°Ｃで測定）。To this solution was added 0.59 g (2.0 mmol) of 3.
4. 3', 4'biphenyltetracarboxylic dianhydride was added under a nitrogen stream, and the mixture was reacted at 20°C for 3 hours. A part of the obtained polymerization solution was poured into 300 mL of methanol to precipitate polyamic acid, which was filtered and then vacuum dried at room temperature (intrinsic viscosity 0.48 dL/g, concentration 0.5 g/dL in dimethylacetamide, 30 (measured in °C).
一方、残りの重合溶液をガラス板上にキャストし、これ
を８０°Ｃで乾燥してポリアミド酸のフィルムを得た。On the other hand, the remaining polymerization solution was cast onto a glass plate and dried at 80°C to obtain a polyamic acid film.
このフィルムを１００°Ｃ、２００°Ｃ、２８０°Ｃで
順次１時間づつ熱処理してポリイミドフィルムを得た。This film was heat treated at 100°C, 200°C and 280°C for 1 hour each to obtain a polyimide film.
固有粘度： ０．４３ｄＬ／ ｇ （硫酸中、濃度０
．５ｇ／ｄＬ， ３０℃で測定）
元素分析値
水素 窒素
３、８２ ６．３７
３、６４ ６．０２
炭素
計算値（％） ８０．１１
実測値（％） ７８．８６
ガラス転移温度：３２８°Ｃ
１０％重量重量減変温空気中で５４０
５８０ ”Ｃであった。Intrinsic viscosity: 0.43dL/g (in sulfuric acid, concentration 0
．． 5g/dL, measured at 30°C) Elemental analysis value Hydrogen Nitrogen 3,82 6.37 3,64 6.02 Carbon calculated value (%) 80.11 Actual value (%) 78.86 Glass transition temperature: 328°C 10% weight loss in variable temperature air of 540 580''C.
°Ｃ、窒素中で
溶解性：硫酸、メタクレゾール、オルトクロロフェノー
ル、ピリジン、ジメチルイミダゾリトン、Ｎ−メチルピ
ロリドン等に可溶であった。Soluble in °C and nitrogen: Soluble in sulfuric acid, metacresol, orthochlorophenol, pyridine, dimethylimidazolitone, N-methylpyrrolidone, etc.
１旅■↓
３．４−ビス（４−アミノフェニル） −２，５−ジフ
ェニルピロール０．８０３ ｇ （２ｍｍｏｌ）を１０
ｗＬのＮ−メチルビロリドンに溶解した。これに、３，
４゜３’ 、 ４’−ベンゾフェノンテトラカルボン酸
二チオ無水物０．７０９ ｇ （２ｍｍｏｌ）を加え、
１２０ ’Ｃで１０時間窒素気流下で反応させた。重合
溶液の一部をガラス板上に流延し、１００°Ｃ１ついで
１８０°Ｃで真空乾燥することによりポリイミドフィル
ムを得た。残りの重合液は、３００ｍＬのメタノールに
投入し、ポリイミドを沈殿させ、ろ過後１００°Ｃで減
圧乾燥してポリイミドを得た。1 journey■↓ 3.4-bis(4-aminophenyl)-2,5-diphenylpyrrole 0.803 g (2 mmol) 10
Dissolved in wL of N-methylpyrrolidone. To this, 3,
4゜3', 0.709 g (2 mmol) of 4'-benzophenone tetracarboxylic acid dithioanhydride was added,
The reaction was carried out at 120'C for 10 hours under nitrogen flow. A part of the polymerization solution was cast onto a glass plate and vacuum dried at 100°C and then at 180°C to obtain a polyimide film. The remaining polymerization solution was poured into 300 mL of methanol to precipitate polyimide, which was filtered and dried under reduced pressure at 100°C to obtain polyimide.
赤外吸収スペクトル： １７８０．１７２５．１３７０
．７２５ｃｍ−’（いずれもイミド結合の特性吸収）固
有粘度： ｏ、４ｏｄｔ、、／ ｇ （Ｎ−メチルピロ
リドン中、濃度０．５ｇ／ｄＬ、３０°Ｃで測定）元素
分析値
炭素 水素 窒素
計算値（％） ７８．５９ ３．６６ ６．１
１実測値（％） ７６．９５ ３．２８ ６．
３２ガラス転移温度＝３０５°Ｃ
１０％重量重量減変温空気中で５３５℃、窒素中で５８
０ ’Ｃであった。Infrared absorption spectrum: 1780.1725.1370
．． 725 cm-' (both characteristic absorption of imide bonds) Intrinsic viscosity: o, 4 odt, / g (Measured in N-methylpyrrolidone at a concentration of 0.5 g/dL at 30°C) Elemental analysis values Carbon Hydrogen Nitrogen Calculated values (%) 78.59 3.66 6.1
1 Actual value (%) 76.95 3.28 6.
32 Glass transition temperature = 305°C 10% weight loss 535°C in air, 58 in nitrogen
It was 0'C.
溶解性：硫酸、メタクレゾール、オルトクロロフェノー
ル、ピリジン、ジメチルイミダゾリトン、Ｎ−メチルピ
ロリドン等に可溶であった。Solubility: Soluble in sulfuric acid, metacresol, orthochlorophenol, pyridine, dimethylimidazolitone, N-methylpyrrolidone, etc.
（発明の効果）
本発明は、−数式（Ｉ）で表わされるポリイミド樹脂お
よびポリイミド樹脂の有利な製造方法を提供する。従来
のポリイミド樹脂の多くは、有機溶媒に対して低い溶解
性を有するために成形が困難であったのに対して、本発
明のポリイミド樹脂は、有機溶媒に可溶であり、本発明
の製造方法によって有機溶媒溶液として得・られる特徴
を有し、この溶液より容易にポリイミド樹脂のフィルム
等の成形品を成形することができ、しかも優れた耐熱性
を有するので工業材料としての価値が大きい。(Effects of the Invention) The present invention provides a polyimide resin represented by formula (I) and an advantageous method for producing the polyimide resin. Most conventional polyimide resins have low solubility in organic solvents and are therefore difficult to mold, whereas the polyimide resin of the present invention is soluble in organic solvents, and the production method of the present invention It has the characteristics that it can be obtained as an organic solvent solution by a method, and molded products such as polyimide resin films can be easily molded from this solution. Moreover, it has excellent heat resistance, so it has great value as an industrial material.
Claims (1)
ニルピロール基、ｎは１０〜２００の整数を示す） で表わされるポリイミド樹脂。 ２、一般式 Ｈ＿２Ｎ−Ａｒ−ＮＨ＿２ （式中、Ａｒは二価のテトラフェニルピロール基を示す
） で表わされるジアミンと 一般式 ▲数式、化学式、表等があります▼ （式中、Ｒは四価の芳香族基を示す） で表わされるテトラカルボン酸二無水物を有機溶媒中で
反応させることを特徴とする一般式 ▲数式、化学式、表等があります▼ （式中、Ｒは四価の芳香族基、Ａｒは二価のテトラフェ
ニルピロール基、ｎは１０〜２００の整数を示す） で表わされるポリイミド樹脂の製造方法。 ３、一般式 Ｈ＿２Ｎ−Ａｒ−ＮＨ＿２ （式中、Ａｒは二価のテトラフェニルピロール基を示す
） で表わされるジアミンと、 一般式 ▲数式、化学式、表等があります▼ （式中、Ｒは四価の芳香族基を示す） で表わされるテトラカルボン酸二チオ無水物を有機溶媒
中で反応させることを特徴とする一般式 ▲数式、化学式、表等があります▼ （式中、Ｒは四価の芳香族基、Ａｒは二価のテトラフェ
ニルピロール基、ｎは１０〜２００の整数を示す） で表わされるポリイミド樹脂の製造方法。[Claims] 1. General formula▲ Numerical formula, chemical formula, table, etc.▼ (In the formula, R is a tetravalent aromatic group, Ar is a divalent tetraphenylpyrrole group, and n is an integer from 10 to 200. Polyimide resin represented by 2. Diamine represented by the general formula H_2N-Ar-NH_2 (in the formula, Ar represents a divalent tetraphenylpyrrole group) and the general formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (in the formula, R represents a tetravalent tetraphenylpyrrole group) There are general formulas ▲ mathematical formulas, chemical formulas, tables, etc. that are characterized by reacting tetracarboxylic dianhydride represented by (representing an aromatic group) in an organic solvent. Ar is a divalent tetraphenylpyrrole group, and n is an integer of 10 to 200. 3. Diamine represented by the general formula H_2N-Ar-NH_2 (in the formula, Ar represents a divalent tetraphenylpyrrole group) and the general formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (in the formula, R is tetraphenylpyrrole) The general formula is characterized by reacting tetracarboxylic acid dithioanhydride (representing a valent aromatic group) in an organic solvent. Ar is a divalent tetraphenylpyrrole group, and n is an integer of 10 to 200.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2044578A JPH03247623A (en) | 1990-02-27 | 1990-02-27 | Polyimide resin and its manufacture |
| KR1019900008832A KR0150203B1 (en) | 1990-02-27 | 1990-06-15 | Polyimide resin and process for its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2044578A JPH03247623A (en) | 1990-02-27 | 1990-02-27 | Polyimide resin and its manufacture |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03247623A true JPH03247623A (en) | 1991-11-05 |
Family
ID=12695385
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2044578A Pending JPH03247623A (en) | 1990-02-27 | 1990-02-27 | Polyimide resin and its manufacture |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPH03247623A (en) |
| KR (1) | KR0150203B1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103173229A (en) * | 2011-12-26 | 2013-06-26 | Jsr株式会社 | Liquid crystal matching agent, liquid crystal matching film, liquid crystal display element, polymer and compound |
| CN105324384A (en) * | 2013-07-02 | 2016-02-10 | 阿卜杜拉国王科技大学 | Dianhydrides, polyimides, and their respective methods of preparation and use |
| JP2021101023A (en) * | 2016-01-22 | 2021-07-08 | 日産化学株式会社 | Liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display element using the same |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102377963B1 (en) | 2020-02-13 | 2022-03-24 | 주식회사 네오나인스 | System and method for managing raising seedling area |
-
1990
- 1990-02-27 JP JP2044578A patent/JPH03247623A/en active Pending
- 1990-06-15 KR KR1019900008832A patent/KR0150203B1/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103173229A (en) * | 2011-12-26 | 2013-06-26 | Jsr株式会社 | Liquid crystal matching agent, liquid crystal matching film, liquid crystal display element, polymer and compound |
| CN105324384A (en) * | 2013-07-02 | 2016-02-10 | 阿卜杜拉国王科技大学 | Dianhydrides, polyimides, and their respective methods of preparation and use |
| US9840514B2 (en) | 2013-07-02 | 2017-12-12 | King Abdullah University Of Science And Technology | Dianhydrides, polyimides, methods of making each, and methods of use |
| JP2021101023A (en) * | 2016-01-22 | 2021-07-08 | 日産化学株式会社 | Liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display element using the same |
| KR20240090617A (en) * | 2016-01-22 | 2024-06-21 | 닛산 가가쿠 가부시키가이샤 | Liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display element using same |
Also Published As
| Publication number | Publication date |
|---|---|
| KR910015623A (en) | 1991-09-30 |
| KR0150203B1 (en) | 1998-10-15 |
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