JPH01188528A - Terminal-modified imide oligomer and elastic molded article produced therefrom - Google Patents
Terminal-modified imide oligomer and elastic molded article produced therefromInfo
- Publication number
- JPH01188528A JPH01188528A JP1058488A JP1058488A JPH01188528A JP H01188528 A JPH01188528 A JP H01188528A JP 1058488 A JP1058488 A JP 1058488A JP 1058488 A JP1058488 A JP 1058488A JP H01188528 A JPH01188528 A JP H01188528A
- Authority
- JP
- Japan
- Prior art keywords
- terminal
- oligomer
- unsaturated
- imide oligomer
- modified imide
- 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
- 150000003949 imides Chemical class 0.000 title claims description 58
- -1 diamine compound Chemical class 0.000 claims abstract description 20
- 238000002844 melting Methods 0.000 claims abstract description 12
- 230000008018 melting Effects 0.000 claims abstract description 12
- 150000001991 dicarboxylic acids Chemical class 0.000 claims abstract description 9
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 7
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 7
- NBAUUNCGSMAPFM-UHFFFAOYSA-N 3-(3,4-dicarboxyphenyl)phthalic acid Chemical class C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=CC(C(O)=O)=C1C(O)=O NBAUUNCGSMAPFM-UHFFFAOYSA-N 0.000 claims abstract description 5
- LFBALUPVVFCEPA-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)phthalic acid Chemical class C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C(C(O)=O)=C1 LFBALUPVVFCEPA-UHFFFAOYSA-N 0.000 claims abstract 3
- 239000002904 solvent Substances 0.000 claims description 23
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 20
- 239000003960 organic solvent Substances 0.000 claims description 8
- 238000005259 measurement Methods 0.000 claims description 3
- 238000004132 cross linking Methods 0.000 claims description 2
- 239000002253 acid Substances 0.000 abstract description 19
- 150000001875 compounds Chemical class 0.000 abstract description 17
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 6
- 229920001971 elastomer Polymers 0.000 abstract description 6
- 125000003277 amino group Chemical group 0.000 abstract description 5
- JKANAVGODYYCQF-UHFFFAOYSA-N prop-2-yn-1-amine Chemical compound NCC#C JKANAVGODYYCQF-UHFFFAOYSA-N 0.000 abstract description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 abstract description 2
- 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 abstract 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 abstract 1
- 239000000806 elastomer Substances 0.000 abstract 1
- 239000003495 polar organic solvent Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 17
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 15
- 239000000203 mixture Substances 0.000 description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 10
- 239000002798 polar solvent Substances 0.000 description 10
- 229920001721 polyimide Polymers 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-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
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000004642 Polyimide Substances 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 239000009719 polyimide resin Substances 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000012783 reinforcing fiber Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 2
- 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 2
- FYYYKXFEKMGYLZ-UHFFFAOYSA-N 4-(1,3-dioxo-2-benzofuran-5-yl)-2-benzofuran-1,3-dione Chemical compound C=1C=C2C(=O)OC(=O)C2=CC=1C1=CC=CC2=C1C(=O)OC2=O FYYYKXFEKMGYLZ-UHFFFAOYSA-N 0.000 description 2
- VILWHDNLOJCHNJ-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)sulfanylphthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1SC1=CC=C(C(O)=O)C(C(O)=O)=C1 VILWHDNLOJCHNJ-UHFFFAOYSA-N 0.000 description 2
- KNDQHSIWLOJIGP-UHFFFAOYSA-N 826-62-0 Chemical compound C1C2C3C(=O)OC(=O)C3C1C=C2 KNDQHSIWLOJIGP-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-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
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 125000006159 dianhydride group Chemical group 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 description 1
- KNDQHSIWLOJIGP-UMRXKNAASA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound O=C1OC(=O)[C@@H]2[C@H]1[C@]1([H])C=C[C@@]2([H])C1 KNDQHSIWLOJIGP-UMRXKNAASA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- KBLZUSCEBGBILB-UHFFFAOYSA-N 2,2-dimethylthiolane 1,1-dioxide Chemical compound CC1(C)CCCS1(=O)=O KBLZUSCEBGBILB-UHFFFAOYSA-N 0.000 description 1
- MFGALGYVFGDXIX-UHFFFAOYSA-N 2,3-Dimethylmaleic anhydride Chemical compound CC1=C(C)C(=O)OC1=O MFGALGYVFGDXIX-UHFFFAOYSA-N 0.000 description 1
- GTCLFEMMPGBNOI-UHFFFAOYSA-N 2-phenylethynamine Chemical group NC#CC1=CC=CC=C1 GTCLFEMMPGBNOI-UHFFFAOYSA-N 0.000 description 1
- CDKIJDCCEJTBLH-UHFFFAOYSA-N 3,4-di(propan-2-yl)furan-2,5-dione Chemical compound CC(C)C1=C(C(C)C)C(=O)OC1=O CDKIJDCCEJTBLH-UHFFFAOYSA-N 0.000 description 1
- AGULWIQIYWWFBJ-UHFFFAOYSA-N 3,4-dichlorofuran-2,5-dione Chemical compound ClC1=C(Cl)C(=O)OC1=O AGULWIQIYWWFBJ-UHFFFAOYSA-N 0.000 description 1
- OLQWMCSSZKNOLQ-UHFFFAOYSA-N 3-(2,5-dioxooxolan-3-yl)oxolane-2,5-dione Chemical compound O=C1OC(=O)CC1C1C(=O)OC(=O)C1 OLQWMCSSZKNOLQ-UHFFFAOYSA-N 0.000 description 1
- IFSSSYDVRQSDSG-UHFFFAOYSA-N 3-ethenylaniline Chemical compound NC1=CC=CC(C=C)=C1 IFSSSYDVRQSDSG-UHFFFAOYSA-N 0.000 description 1
- FGSUUFDRDVJCLT-UHFFFAOYSA-N 3-methylazepan-2-one Chemical compound CC1CCCCNC1=O FGSUUFDRDVJCLT-UHFFFAOYSA-N 0.000 description 1
- HUAHZCFLLQRNRO-UHFFFAOYSA-N 3-prop-1-en-2-ylaniline Chemical compound CC(=C)C1=CC=CC(N)=C1 HUAHZCFLLQRNRO-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
- LBSXSAXOLABXMF-UHFFFAOYSA-N 4-Vinylaniline Chemical compound NC1=CC=C(C=C)C=C1 LBSXSAXOLABXMF-UHFFFAOYSA-N 0.000 description 1
- JXYITCJMBRETQX-UHFFFAOYSA-N 4-ethynylaniline Chemical group NC1=CC=C(C#C)C=C1 JXYITCJMBRETQX-UHFFFAOYSA-N 0.000 description 1
- CQMIJLIXKMKFQW-UHFFFAOYSA-N 4-phenylbenzene-1,2,3,5-tetracarboxylic acid Chemical class OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C1C1=CC=CC=C1 CQMIJLIXKMKFQW-UHFFFAOYSA-N 0.000 description 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
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZWXPDGCFMMFNRW-UHFFFAOYSA-N N-methylcaprolactam Chemical compound CN1CCCCCC1=O ZWXPDGCFMMFNRW-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- XSBPYGDBXQXSCU-UHFFFAOYSA-N but-3-yn-1-amine Chemical compound NCCC#C XSBPYGDBXQXSCU-UHFFFAOYSA-N 0.000 description 1
- ZZRMYOZQUCUWFT-UHFFFAOYSA-N but-3-yn-2-amine Chemical compound CC(N)C#C ZZRMYOZQUCUWFT-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003733 fiber-reinforced composite Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- ATNZRYIKSXYJKY-UHFFFAOYSA-N pent-4-yn-2-amine Chemical compound CC(N)CC#C ATNZRYIKSXYJKY-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920005575 poly(amic acid) Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
この発明は、各種の有機極性溶媒に可溶性であり、しか
も、融点が１００℃以下と極めて低く（特に、常温で実
質的に液状であり）、さらに、付加重合性（架橋性）の
末端基およびイミド主鎖結合を有する特定の末端変性イ
ミドオリゴマー、およびその加熱硬化物である弾性成形
体に係るものであり、この発明の末端変性イミドオリゴ
マーは、種々の材料を接合することができる耐熱性接着
剤、種々の充填材、補強材などを含有する複合材料に使
用するマトリックス樹脂、あるいは、各種の熱硬化弾性
成形品などの原材料としての用途を有し、この発明のイ
ミドオリゴマーを加熱硬化して得られた各種の弾性成形
品は、耐熱性が５極めて良好である。[Detailed Description of the Invention] [Field of Industrial Application] This invention is soluble in various organic polar solvents, and has an extremely low melting point of 100°C or less (particularly, it is substantially liquid at room temperature). , and further relates to a specific terminal-modified imide oligomer having an addition-polymerizable (cross-linkable) terminal group and an imide main chain bond, and an elastic molded product that is a heat-cured product thereof, and the terminal-modified imide oligomer of the present invention is used as a heat-resistant adhesive that can join various materials, as a matrix resin used in composite materials containing various fillers, reinforcing materials, etc., or as a raw material for various thermosetting elastic molded products. The various elastic molded products obtained by heating and curing the imide oligomer of the present invention have an extremely good heat resistance of 5.
低分子量のポリイミド樹脂は、優れた耐熱性を有するこ
とから、成形品や繊維強化複合材料のマトリックス樹脂
として従来から使用されている。Low molecular weight polyimide resins have excellent heat resistance and have traditionally been used as matrix resins for molded products and fiber-reinforced composite materials.
しかし、従来公知のポリイミド樹脂（特に芳香族ポリイ
ミド）は、一般に有機溶媒に対する溶解性が低いので、
ポリイミド前駆体であるポリアミック酸の溶液として種
々の用途に使用されていたが、そのポリアミック酸は、
縮合タイプのポリマーであり、製品の製造におけるポリ
マーの硬化時の生成水（反応水）などの脱ガスのために
種々の問題が生じていた。However, conventionally known polyimide resins (especially aromatic polyimides) generally have low solubility in organic solvents, so
Polyamic acid, a polyimide precursor, was used for various purposes as a solution.
It is a condensation type polymer, and various problems have arisen due to degassing of generated water (reaction water) during the curing of the polymer during product manufacturing.
それらの問題を解決するために、最近、例えば、（ａ）
ヒロメリット酸二無水物、ヘンシフエノンテトラカルボ
ン酸二無水物などの芳香族テトラカルボン酸二無水物と
、（ｂ）芳香族ジアミンと、（、（ｃ）不飽和型の反応
性化合物とを反応させて得られた、不飽和末端基を有す
る付加型のポリイミド樹脂が、特開昭５９−１６７５６
９号公報、特開昭６０−２５００３０号公報、特開昭６
０−２６０６２４号公報、特開昭６０−２６０６２５号
公報、特開昭６１−２４７７３３号公報、特開昭６２−
２９５８４号公報などにおいて、提案された。In order to solve those problems, recently, for example, (a)
An aromatic tetracarboxylic dianhydride such as hyromellitic dianhydride and hensifhenonetetracarboxylic dianhydride, (b) an aromatic diamine, and (c) an unsaturated reactive compound. The addition type polyimide resin having unsaturated end groups obtained by the reaction was disclosed in Japanese Patent Application Laid-Open No. 59-16756.
9, JP-A-60-250030, JP-A-6
0-260624, JP 60-260625, JP 61-247733, JP 62-
This was proposed in Publication No. 29584, etc.
しかしながら、前記の公知のポリイミド樹脂は、特殊で
高価な特定のジアミン化合物を使用して製造しなければ
ならなかったり、そのポリマーの有機溶媒への溶解性が
必ずしも高くないものであったり、また、ポリイミド溶
液の調製において特殊な高沸点の有機溶媒を使用しなけ
ればならなかったり、あるいは、ポリイミド樹脂の融点
が高くなり過ぎて製品の製造時に製品を劣化させてしま
ったりとの問題を有していたのである。However, the above-mentioned known polyimide resins must be manufactured using special and expensive specific diamine compounds, or the solubility of the polymer in organic solvents is not necessarily high, and There are problems such as having to use a special high-boiling point organic solvent in preparing the polyimide solution, or the melting point of the polyimide resin becoming too high, resulting in product deterioration during manufacturing. It was.
すなわち、例えば、高い融点のポリイミドを低い濃度で
含有されている溶液を使用して、強化繊維に含浸させて
、複合材料を製造する場合には、強化繊維への含浸を数
回繰り返さないと所望の含浸樹脂量にならなかったり、
高い温度で成形する必要がある。That is, for example, when manufacturing a composite material by impregnating reinforcing fibers with a solution containing a low concentration of high melting point polyimide, it is desirable not to repeat the impregnation of the reinforcing fibers several times. If the amount of impregnated resin is not reached,
It is necessary to mold at high temperatures.
また、前記の公知の高沸点溶媒を使用したポリイミド溶
液を接着剤として使用する場合、高沸点溶媒を完全に溜
去することが困難であり、結果として、接着性が不良と
なり接着剤として実用的ではないのである。In addition, when using a polyimide solution containing the above-mentioned known high-boiling point solvent as an adhesive, it is difficult to completely distill off the high-boiling point solvent, and as a result, the adhesion is poor and it is not practical as an adhesive. It is not.
本発明の目的は、前述の種々の問題点を有さない、極め
て低融点であって実質的に常温で液状であるか、比較的
低い温度で溶融しうるような実用性の高い芳香族テトラ
カルボン酸系の付加重合型イミドオリゴマー、並びにそ
の加熱硬化物である新規な弾性成形体を、新たに提供す
ることである。The object of the present invention is to provide highly practical aromatic tetracarbons which do not have the various problems described above and which have an extremely low melting point and are substantially liquid at room temperature or can be melted at a relatively low temperature. An object of the present invention is to newly provide a carboxylic acid-based addition-polymerizable imide oligomer and a novel elastic molded product that is a heat-cured product thereof.
この出願の第１の発明は、（ａ） ２，３，３”、４
”−ビフェニルテトラカルボン酸類および／または３．
３’ 、４゜４”−ビフェニルテトラカルボン酸類と、
（ｂ） α、ω−ジメチルポリシロキサン系ジアジア
ミン化合
物、（ｃ） 不飽和ジカルボン酸類および／または不
飽和モノアミンとを、
有機溶媒中で反応させて得られた、オリゴマー末端に不
飽和末端基およびオリゴマー内部にイミド結合を有する
末端変性イミドオリゴマーであり、該イミドオリゴマー
は、対数粘度（濃度；０．５ｇ／１００ｍｌ溶媒、溶媒
；Ｎ−メチル−２−ピロリドン、測定温度、３０”、（
ｃ）が１．０以下であり、しかも、融点が１００℃以下
であることを特徴とする末端変性イミドオリゴマーに関
する。The first invention of this application is (a) 2,3,3'', 4
”-biphenyltetracarboxylic acids and/or 3.
3', 4°4''-biphenyltetracarboxylic acids,
(b) an α,ω-dimethylpolysiloxane-based diadiamine compound, (c) an unsaturated terminal group and an oligomer obtained by reacting an unsaturated dicarboxylic acid and/or an unsaturated monoamine in an organic solvent. It is a terminal-modified imide oligomer having an imide bond inside, and the imide oligomer has a logarithmic viscosity (concentration: 0.5 g/100 ml solvent, solvent: N-methyl-2-pyrrolidone, measurement temperature: 30",
The present invention relates to a terminal-modified imide oligomer characterized in that c) is 1.0 or less and has a melting point of 100°C or less.
そして、第２の発明は、前記末端変性イミドオリゴマー
を加熱硬化して得られた弾性成形体に関する。A second invention relates to an elastic molded article obtained by heating and curing the terminal-modified imide oligomer.
この発明の末端変性イミドオリゴマーは、前述の（ａ）
〜（、（ｃ）成分を、各成分の酸基の当量の合計と各成
分のアミノ基の当量の合計とが概略等量となるようにし
て、有機溶媒中で反応させて得られたイミドオリゴマー
であって、そのイミドオリゴマーの末端にエチレン基な
どの付加重合可能な不飽和末端基およびイミドオリゴマ
ーの内部（主鎖）に多数のイミド結合を有する末端変性
イミドオリゴマーであり、しかも、対数粘度が、１．０
以下、好ましくは０．０１〜０．８程度、特に好ましく
は０．０３〜０．７程度であって比較的低分子量である
と共に、融点が１００℃以下、好ましくは８０℃以下で
ある、最も好ましくは６０℃以下であって、常温で実質
的に液状である末端変性イミドオリゴマーである。The terminal-modified imide oligomer of this invention has the above-mentioned (a)
~(, imide obtained by reacting component (c) in an organic solvent such that the sum of the equivalents of acid groups of each component and the sum of equivalents of amino groups of each component are approximately equal. It is a terminally modified imide oligomer that has an unsaturated end group capable of addition polymerization such as an ethylene group at the end of the imide oligomer and a large number of imide bonds inside the imide oligomer (main chain), and has a logarithmic viscosity. But 1.0
Below, the most preferable is about 0.01 to 0.8, particularly preferably about 0.03 to 0.7, has a relatively low molecular weight, and has a melting point of 100°C or lower, preferably 80°C or lower. Preferably, it is a terminal-modified imide oligomer that is 60° C. or lower and is substantially liquid at room temperature.
前記の２．３．３”、４゛−ビフェニルテトラカルボン
酸類は、２，３．３”、４”−ビフェニルテトラカルボ
ン酸、２．３．３°、４゛−ビフェニルテトラカルボン
酸二無水物（ａ−ＢＰＤＡ） 、それらの酸化合物の低
級アルコールエステル又は塩などの酸誘導体であればよ
く、特に、２，３．３’、４“−ビフェニルテトラカル
ボン酸二無水物が最適であり、また、
前記の３．３°、４．４’−ビフェニルテトラカルボン
酸類は、３，３”、４．４’−ビフェニルテトラカルボ
ン酸、３．３’、４．４’−ビフェニルテトラカルボン
酸二無水物（ｓ−ＢＰＤＡ） 、あるいは、それらの酸
化合物の低級アルコールエステル又は塩などの酸誘導体
であればよく、特に、３．３’ 、４．４”−ビフェニ
ルテトラカルボン酸二無水物が最適である。The above-mentioned 2.3.3", 4"-biphenyltetracarboxylic acids include 2,3.3", 4"-biphenyltetracarboxylic acid, 2.3.3", 4"-biphenyltetracarboxylic dianhydride. (a-BPDA), any acid derivatives such as lower alcohol esters or salts of these acid compounds, and 2,3.3',4"-biphenyltetracarboxylic dianhydride is particularly suitable; , The above-mentioned 3.3°, 4.4'-biphenyltetracarboxylic acids include 3,3'', 4.4'-biphenyltetracarboxylic acid, 3.3', 4.4'-biphenyltetracarboxylic dianhydride. (s-BPDA), or acid derivatives such as lower alcohol esters or salts of these acid compounds; in particular, 3.3', 4.4''-biphenyltetracarboxylic dianhydride is most suitable. be.
この発明においては、前記２，３．３’、４’−ビフェ
ニルテトラカルボン酸類および／または３．３’、４．
４’−ビフェニルテトラカルボン酸類の一部（好ましく
は３０モル％以下、特に好ましくは２０モル％以下、さ
らに好ましくは１０モル％以下）が、他の芳香族テトラ
カルボン酸類、例えば、３．３’ 、４．４’−ヘンシ
フエノンテトラカルボン酸二無水物（ＢＴＤＡ）、ピロ
メリット酸二無水物（ＰＭＤ八） 、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）メタン二＝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）チオエー
テルニ無水物、ビス（３，４−ジカルボキシフェニル）
ホスフィンニ無水物、ビス（３，４−ジカルボキシフェ
ニル）スルホンニ無水物など、あるいは、脂肪族テトラ
カルボン酸類、例えば、ブタンテトラカルボン酸二無水
物などと置換されていてもよい。In this invention, the 2,3.3',4'-biphenyltetracarboxylic acids and/or 3.3', 4.
A portion of the 4'-biphenyltetracarboxylic acids (preferably 30 mol % or less, particularly preferably 20 mol % or less, and even more preferably 10 mol % or less) contains other aromatic tetracarboxylic acids, such as 3.3' , 4.4'-hensiphenotetracarboxylic dianhydride (BTDA), pyromellitic dianhydride (PMD8), 2.2-bis(3
', 4°-dicarboxyphenyl)propanihydride,
Bis(3,4-dicarboxyphenyl)methane dihydride, bis(3,4-dicarboxyphenyl)ether dianhydride, bis(3,4-dicarboxyphenyl)thioether dianhydride, bis(3,4-dicarboxyphenyl)thioether dianhydride -dicarboxyphenyl)
It may be substituted with phosphine dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, or aliphatic tetracarboxylic acids such as butanetetracarboxylic dianhydride.
前記のα、ω−ジメチルポリシロキサン系ジアミンとし
ては、次ぎに示す一般式
（但し、ｎはＯ〜８０、特に２〜５０の整数である）で
示されるポリシロキサン系ジアミン化合物を好適に使用
することができる。As the α,ω-dimethylpolysiloxane diamine, a polysiloxane diamine compound represented by the following general formula (where n is an integer of 0 to 80, particularly 2 to 50) is preferably used. be able to.
前記の不飽和ジカルボン酸類は、
（１）炭素−炭素二重結合（エチレン基）または炭素−
炭素三重結合（アセチレン基）等からなる不飽和基（架
橋基）、および
（ｉｉ）隣接する炭素原子などに結合している一対のカ
ルボキシル基（ジカルボキシル基）またはその酸モノ無
水基を、同時に分子内に有しており、しかも、
（ｉｉｉ）アミノ基を有する化合物と反応してイミド結
合を形成しうる反応性有機化合物である。The unsaturated dicarboxylic acids mentioned above have (1) a carbon-carbon double bond (ethylene group) or a carbon-carbon double bond (ethylene group);
An unsaturated group (crosslinking group) consisting of a carbon triple bond (acetylene group), etc., and (ii) a pair of carboxyl groups (dicarboxyl group) or their acid monoanhydride groups bonded to adjacent carbon atoms, etc., at the same time. (iii) It is a reactive organic compound that can react with a compound having an amino group to form an imide bond.
そのような不飽和ジカルボン酸類め好適な例としては、
（ａ） 無水マレイン酸、またはその誘導体（例えば
、ジメチル無水マレイン酸、ジイソプロピル無水マレイ
ン酸、ジクロロ無水マレイン酸など）、（ｂ） テト
ラヒドロ無水フタル酸、またはその誘導体（例えば、メ
チルテトラヒドロ無水フタル酸など）、
（、（ｃ） 無水ナジック酸（ＮＡ） 、またはその
誘導体（例えば、メチル無水ナジック酸、オキシ無水ナ
ジック酸、メチルオキシ無水ナジック酸、ジメチルオキ
シ無水ナジック酸、エチル無水ナジック酸、ヘキサクロ
ロ無水ナジック酸など）
を好適に挙げることができ、この発明では、それらの不
飽和ジカルボン酸類が単独で使用されていても、あるい
は複数の不飽和ジカルボン酸類が併用されていてもよい
。Suitable examples of such unsaturated dicarboxylic acids include (a) maleic anhydride or its derivatives (e.g., dimethyl maleic anhydride, diisopropyl maleic anhydride, dichloromaleic anhydride, etc.), (b) tetrahydrophthalic anhydride. (c) nadic anhydride (NA), or a derivative thereof (such as methyl nadic anhydride, oxynadic anhydride, methyloxynadic anhydride, (dimethyloxy nadic anhydride, ethyl nadic anhydride, hexachloro nadic anhydride, etc.), and in the present invention, even if these unsaturated dicarboxylic acids are used alone or a plurality of unsaturated dicarboxylic acids are used, Acids may be used in combination.
また、不飽和モノアミン化合物としては、前述と同様の
不飽和基、および、モノアミノ基（第１級アミノ基）を
同時に有しており、隣接する一対のカルボキシル基と反
応してイミド結合を形成しうる反応性不飽和モノアミン
化合物である。In addition, as an unsaturated monoamine compound, it simultaneously has the same unsaturated group as mentioned above and a monoamino group (primary amino group), and reacts with a pair of adjacent carboxyl groups to form an imide bond. It is a reactive unsaturated monoamine compound.
その不飽和モノアミン化合物の例として、例えば、
（ａ） プロパルギルアミン（ＰＡ） 、３−アミノ
ブチン、４−アミノブチン、５−アミノブチン、６−ア
ミノヘキシン、７−アミノヘプチン、４−アミノ−３−
メチルフ゛チン、４−アミノペンチン、アリルアミン（
Ａ八）などの脂肪族モノアミノ化合物、あるいは、（ｂ
） ｍ−アミノスチレン、ｐ−アミノスチレン、ｍ−ア
ミノ−α−メチルスチレン、１−イソプロペニル−３−
（２−アミノイソプロピル）ベンゼン、１−イソプロペ
ニル−４−（２−アミノイソプロピル）ベンゼン、３−
アミノフェニルアセチレン、４−アミノフェニルアセチ
レンなどの芳香族モノアミノ化合物を好適に挙げること
ができ、この発明では、前記の不飽和モノアミン化合物
が単独で使用されてもよく、また、それらのモノアミノ
化合物が複数種類併用されていてもよい。Examples of the unsaturated monoamine compounds include (a) propargylamine (PA), 3-aminobutyne, 4-aminobutyne, 5-aminobutyne, 6-aminohexine, 7-aminoheptine, 4-amino-3-
Methylphutine, 4-aminopentyne, allylamine (
Aliphatic monoamino compounds such as A8), or (b
) m-aminostyrene, p-aminostyrene, m-amino-α-methylstyrene, 1-isopropenyl-3-
(2-aminoisopropyl)benzene, 1-isopropenyl-4-(2-aminoisopropyl)benzene, 3-
Aromatic monoamine compounds such as aminophenylacetylene and 4-aminophenylacetylene can be preferably mentioned, and in the present invention, the above-mentioned unsaturated monoamine compounds may be used alone, or a plurality of these monoamino compounds may be used. A combination of types may be used.
本発明の末端変性イミドオリゴマーは、常温で液状であ
るものが多種類あるので、単離された末端変性イミドオ
リゴマーの液状物をそのまま使用したり、または常温で
固体であっても融点が１５０℃以下であるのでそのイミ
ドオリゴマーの固体を約１５０℃まで加温することによ
って容易に液状となすことができ、種々の成形品を成形
する用途に容易に使用することができる。Since there are many types of terminal-modified imide oligomers of the present invention that are liquid at room temperature, it is possible to use isolated liquid terminal-modified imide oligomers as they are, or even if they are solid at room temperature, their melting point is 150°C. Since the solid imide oligomer can be easily made into a liquid by heating it to about 150° C., it can be easily used for molding various molded products.
この発明の末端変性イミドオリゴマーは、特に、前述の
末端変性イミドオリゴマーの製造に使用した反応溶媒、
例えば、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、Ｎ−
メチルカプロラクタムなどのアミド系有機極性溶媒、ジ
メチルスルホキシド、ジメチルスルホンなどの硫黄原子
を存する有機極性溶媒、フェノール、クレゾール、ハロ
ゲン化フェノールなどのフェノール系溶媒などに充分に
溶解するので、そのオリゴマー濃度が３〜８０重量％、
特に５〜６０重量％である溶液組成物を容易に調製する
ことができる。The terminal-modified imide oligomer of this invention is particularly suitable for the reaction solvent used in the production of the terminal-modified imide oligomer described above.
For example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-
It is sufficiently soluble in amide-based organic polar solvents such as methyl caprolactam, organic polar solvents containing sulfur atoms such as dimethyl sulfoxide and dimethyl sulfone, and phenolic solvents such as phenol, cresol, and halogenated phenols, so that the oligomer concentration is 3. ~80% by weight,
In particular, a solution composition having a concentration of 5 to 60% by weight can be easily prepared.
前記の本発明の末端変性イミドオリゴマーが溶解されて
いる溶液組成物は、２５℃での溶液粘度（２０重量％）
が０．１〜１００ボイス、特に０．２〜７０ボイズてい
どであることが好ましい。The solution composition in which the terminal-modified imide oligomer of the present invention is dissolved has a solution viscosity (20% by weight) at 25°C.
is preferably 0.1 to 100 voices, particularly 0.2 to 70 voices.
また、この発明の末端変性イミドオリゴマーは、さらに
前述の反応に使用する有機極性溶媒と共に、さらに、ジ
オキサン、メチルエチルケトン（ＭＥＫ）、モノグライ
ム、ジグライムなどの酸素原子を分子内に有する有機極
性溶媒も、溶液組成物を調製するために使用できるもの
として好適に挙げることができ、溶液組成物の調製用の
溶媒としては、前述の各溶媒と共に、必要であれば、ベ
ンゼン、トルエン、キシレンなどの芳香族炭化水素系の
溶媒、ソルヘントナフザ、ベンゾニトリル、アセトン、
メタノールのような他の種類の有機溶媒を併用すること
もできる。In addition, the terminal-modified imide oligomer of the present invention can be used in solution with an organic polar solvent having an oxygen atom in its molecule, such as dioxane, methyl ethyl ketone (MEK), monoglyme, diglyme, etc., in addition to the organic polar solvent used in the above-mentioned reaction. Examples of solvents that can be used to prepare the composition include, in addition to the above-mentioned solvents, aromatic carbonized solvents such as benzene, toluene, and xylene, if necessary. Hydrogen solvents, solhent naphza, benzonitrile, acetone,
Other types of organic solvents such as methanol can also be used in combination.
前記の本発明の末端変性イミドオリゴマーが溶解されて
いる溶液組成物は、２５℃での溶液粘度（２０重重量）
が０．１〜１００ポイス、特に０．２〜７０ポイズてい
どであることが好ましい。The solution composition in which the terminal-modified imide oligomer of the present invention is dissolved has a solution viscosity (20 wt.) at 25°C.
is preferably 0.1 to 100 poise, particularly 0.2 to 70 poise.
この発明の末端変性イミドオリゴマーは、例えば、前述
のような２，３．３”、４”−ビフェニルテトラカルボ
ン酸類および／または３．３’ 、４．４’−ビフェニ
ルテトラカルボン酸類（特に、この酸二無水物）と、ジ
アミン化合物（特に、芳香族ジアミン化合物）と、不飽
和ジカルボン酸類（特に酸二無水物）および／または不
飽和モノアミンとが、全成分の酸無水基（または隣接す
るジカルボン酸基）の当量の全量と全成分のアミノ基の
当量の全量とがほぼ等量となるように使用して、各成分
を、前述の有機極性溶媒中で、約１００ ’Ｃ以下、特
に８０’Ｃ以下の反応温度で反・応させて「アミド−酸
結合を有するオリゴマー」を生成し、次いで、そのアミ
ド−酸オリゴマー（アミック酸オリゴマーともいう）を
、約０〜１４０℃の低温でイミド化剤を添加する方法に
よるか、あるいは１４０〜２５０℃の高温に加熱する方
法によるかして、脱水・環化させて、末端に付加重合性
（特にエチレン性）の不飽和基を有するイミドオリゴマ
ーを生成する方法で得ることができる。The terminal-modified imide oligomer of the present invention can be, for example, 2,3.3", 4"-biphenyltetracarboxylic acids and/or 3.3', 4,4'-biphenyltetracarboxylic acids (especially this acid dianhydrides), diamine compounds (especially aromatic diamine compounds), unsaturated dicarboxylic acids (especially acid dianhydrides), and/or unsaturated monoamines, the acid anhydride groups (or adjacent dicarboxylic Each component is heated in the above-mentioned organic polar solvent at a temperature of about 100'C or less, especially at 80 The reaction is carried out at a reaction temperature of 'C or less to produce an "oligomer having an amide-acid bond", and then the amide-acid oligomer (also referred to as an amic acid oligomer) is converted into an imide at a low temperature of about 0 to 140 °C. An imide oligomer having an addition-polymerizable (especially ethylenic) unsaturated group at the end by dehydration and cyclization by adding a curing agent or by heating at a high temperature of 140 to 250°C. It can be obtained by the method of generating .
本発明のイミドオリゴマーを製造する際に使用される有
機極性溶媒は、例えば、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（ＮＭＰ ） 、Ｎ−メチルカプロラクタムな
どのアミド系溶媒、ジメチルスルホキシド、ヘキサメチ
ルフオスホルアミド、ジメチルスルホン、テトラメチレ
ンスルホン、ジメチルテトラメチレンスルホンなどの硫
黄原子を含有する溶媒、クレゾール、フェノールなどの
フェノール系溶媒、ピリジン、エチレングリコール、テ
トラメチル尿素などの其の他の溶媒を挙げることができ
る。Examples of the organic polar solvent used in producing the imide oligomer of the present invention include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone (NMP), and N-methylcaprolactam. amide solvents, solvents containing sulfur atoms such as dimethyl sulfoxide, hexamethylphosphoramide, dimethyl sulfone, tetramethylene sulfone, dimethyltetramethylene sulfone, phenolic solvents such as cresol, phenol, pyridine, ethylene glycol, tetramethyl Mention may be made of other solvents such as urea.
末端変性イミドオリゴマーの特に好ましい製法は、例え
ば、まず、２，３．３°、４゛−および／または３゜３
”、４．４’−ビフェニルテトラカルボン酸二無水物と
、ジアミン化合物と、不飽和酸モノ無水物または不飽和
モノアミン化合物とを前述のアミド系の有機極性溶媒中
に均一に溶解し、約５〜６０℃の反応温度で１〜１２０
分間撹拌しながら反応させてアミック酸オリゴマーを生
成した後、その反応液を１４０〜２５０℃１特に好まし
くは１５０〜２００℃の温度まで昇温させて、その温度
で５〜１８０分間撹拌して、前記のアミック酸オリゴマ
ーをイミド化反応させてイミドオリゴマーを生成させ、
最後に、反応液を室温付近まで冷却する方法を挙げるこ
とができる。前記の反応において、全反応工程を窒素ガ
ス、アルゴンガスなどの不活性ガスの雰囲気で行うこと
が好適である。A particularly preferred method for producing terminally modified imide oligomers includes, for example, firstly
4. 4'-Biphenyltetracarboxylic dianhydride, a diamine compound, and an unsaturated acid monoanhydride or an unsaturated monoamine compound are uniformly dissolved in the above-mentioned amide-based organic polar solvent, and about 5 1-120 at a reaction temperature of ~60°C
After reacting with stirring for minutes to produce an amic acid oligomer, the reaction solution is heated to a temperature of 140 to 250°C, preferably 150 to 200°C, and stirred at that temperature for 5 to 180 minutes, The above amic acid oligomer is subjected to an imidization reaction to generate an imide oligomer,
Finally, a method of cooling the reaction solution to around room temperature can be mentioned. In the above reaction, it is preferred that all reaction steps be carried out in an atmosphere of an inert gas such as nitrogen gas or argon gas.
前述のようにして生成した末端変性イミドオリゴマーは
、その反応液を濃縮して、液状又は固体の生成物を単離
するか、反応液を水等に注ぎ込んで、液状の生成物とし
て相分離したり、固体として沈澱させて単離することが
でき、この液状または固体の生成物をそのまま種々の用
途に使用してもよく、前述のように有機極性溶媒などに
溶解して液状組成物を調製して使用してもよい。The terminal-modified imide oligomer produced as described above can be obtained by concentrating the reaction solution to isolate a liquid or solid product, or by pouring the reaction solution into water or the like to phase-separate the product as a liquid. The liquid or solid product can be used as it is for various purposes, or as mentioned above, it can be dissolved in an organic polar solvent to prepare a liquid composition. You may also use it as
さらに、前述の反応液を、そのまま、あるいは、適宜濃
縮または希釈して、末端変成イミドオリゴ７−の溶液組
成物として使用してもよい。Furthermore, the above-mentioned reaction solution may be used as it is, or after being appropriately concentrated or diluted, as a solution composition of the terminal-modified imide oligo 7-.
この発明の末端変成イミドオリゴマーは、例えば、次ぎ
に示す一般式（１）及び（ＩＩ）で示されるイミドオリ
ゴマーを挙げることができる。Examples of the terminal-modified imide oligomer of the present invention include imide oligomers represented by the following general formulas (1) and (II).
（ただし、χは、不飽和基を有するモノアミン化合物の
アミノ基を除いた一価の基であり、また、Ｙは、不飽和
基を有するジカルボン酸化合物またはその酸モノ無水物
のジカルボキシル基または酸モノ無水基を除いた基であ
る。！、又はｍは、１〜８０、特に１〜５０の整数であ
る。さらに、Ｒはジアミン化合物のアミノ基を除いた二
価の残基である。）
前述の末端変成イミドオリゴマーの製法によって得られ
る生成物は、反応原料の組成などによって、上記の一般
式（１）〜（Ｉｆ）で示されるイミドオリゴマーが、種
々の組成比で混合されてし）るものとなる。(However, χ is a monovalent group excluding the amino group of a monoamine compound having an unsaturated group, and Y is a dicarboxyl group of a dicarboxylic acid compound having an unsaturated group or its acid monoanhydride or ! or m is an integer of 1 to 80, particularly 1 to 50. Furthermore, R is a divalent residue of the diamine compound excluding the amino group. ) The products obtained by the above-mentioned method for producing terminal-modified imide oligomers include imide oligomers represented by the above general formulas (1) to (If) mixed in various composition ratios depending on the composition of the reaction raw materials. ).
この発明の末端変性イミドオリゴマーまたはその溶液組
成物は、成形品の製造、積層品の製造などにおける原料
として使用したり、接着剤として使用したり、あるいは
、適当な強化繊維材料に含浸させて複合材料を製造する
ための原料として使用することができる。The terminal-modified imide oligomer or its solution composition of the present invention can be used as a raw material in the production of molded products, laminate products, etc., used as an adhesive, or impregnated into a suitable reinforcing fiber material to form a composite. It can be used as a raw material for producing materials.
この発明の末端変性イミドオリゴマー（液状物または固
体）またはその溶液組成物は、金型内に充填したり、あ
るいは、基材に含浸させたり、基材上に塗布又は流延し
たりして、次いで、（必要であれば、溶媒を除去した後
、または溶媒を除去しながら）好ましくは１５０〜４５
０℃１特に好ましくは２００〜４００℃の温度で、約１
〜３０時間、特に１．５〜２５時間、高温熱処理するこ
とによって、加熱硬化された弾性成形体を得ることがで
きる。The terminal-modified imide oligomer (liquid or solid) of the present invention or its solution composition is filled into a mold, impregnated into a base material, applied or cast onto a base material, Then (after or while removing the solvent if necessary) preferably from 150 to 45
0°C 1, particularly preferably at a temperature of 200 to 400°C, about 1
A heat-hardened elastic molded body can be obtained by performing high-temperature heat treatment for ~30 hours, particularly for 1.5 to 25 hours.
この発明の末端変性イミドオリゴマーまたはその溶液組
成物から成形され加熱硬化された弾性成形体は、熱分解
開始温度が３００℃以上であり、高い耐熱性と共に優れ
たゴム弾性を有する新規なものである。The elastic molded article formed from the terminal-modified imide oligomer or its solution composition and heat-cured according to the present invention has a thermal decomposition initiation temperature of 300°C or higher, and is a novel product having high heat resistance and excellent rubber elasticity. .
なお、この発明の末端変性イミドオリゴマーは、加熱硬
化する際に、ラジカル重合触媒、カチオン重合触媒また
は有機金属触媒の存在下に加熱硬化させることもできる
。The terminal-modified imide oligomer of the present invention can also be heat-cured in the presence of a radical polymerization catalyst, cationic polymerization catalyst, or organometallic catalyst.
以下、実施例を示し、この発明をさらに詳しく説明する
。EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples.
以下の実施例において、対数粘度（ηｉｎｈ ）はポリ
マー濃度が０．５重量％となるように、試料ポリマーを
Ｎ−メチル−２−ピロリドンに均一に？８解してポリマ
ー溶液を調整し、その溶液の溶液粘度および溶媒のみの
粘度を３０℃で測定し、下記の弐 〇で算出される。In the following examples, the logarithmic viscosity (ηinh) was calculated by uniformly dissolving the sample polymer into N-methyl-2-pyrrolidone so that the polymer concentration was 0.5% by weight. 8 to prepare a polymer solution, measure the solution viscosity of the solution and the viscosity of only the solvent at 30°C, and calculate it using the following 2〇.
実施例１
１０００ｍｆｆ１のフラスコに、
（ａ）２，３．３’、４’−ビフェニルテトラカルボン
酸二無水物（ａ−ＢＰＤＡ）１４．６２ｇ （０，０５
モル）、（ｂ）α、ω−ジメチルポリシロキサンジアミ
ン（信越化学社製、Ｘ−２−１６１ＡＳ、分子量：９０
０）９０ｇ（０，１モル）、
（、（ｃ）無水ナジック酸（ＮＡ） １６．４２ ｇ
（０，１モル）および、
（ｄ）Ｎ−メチル−２−ピロリドン（ＮＭＰ） ５５０
ｇを仕込み、窒素気流中、５０℃で１時間撹拌して、
アミック酸オリゴマーを生成させ、次いで、その反応液
を１８５℃に昇温し、その温度で１時間撹拌してイミド
オリゴマーを生成させた。Example 1 In a 1000 mff1 flask, (a) 14.62 g of 2,3.3',4'-biphenyltetracarboxylic dianhydride (a-BPDA) (0,05
mole), (b) α,ω-dimethylpolysiloxane diamine (manufactured by Shin-Etsu Chemical Co., Ltd., X-2-161AS, molecular weight: 90
0) 90 g (0.1 mol), (, (c) Nadic anhydride (NA) 16.42 g
(0.1 mol) and (d) N-methyl-2-pyrrolidone (NMP) 550
g and stirred at 50°C for 1 hour in a nitrogen stream,
An amic acid oligomer was produced, and then the reaction solution was heated to 185° C. and stirred at that temperature for 1 hour to produce an imide oligomer.
その反応液をロータリエバポレーターで濃縮し、さらに
真空乾燥機で１０時間乾燥して、液状の末端変性イミド
オリゴマーを単離した。The reaction solution was concentrated using a rotary evaporator and further dried for 10 hours using a vacuum dryer to isolate a liquid terminal-modified imide oligomer.
このイミドオリゴマーは、Ｎ−メチル−２−ピロリトン
、ジオキサン、メチルエチルケトンなどの溶媒に良好に
溶解する。This imide oligomer dissolves well in solvents such as N-methyl-2-pyrrolitone, dioxane, and methyl ethyl ketone.
このイミドオリゴマーの物性（対数粘度、融点、回転粘
度など）を第１表に示す。Table 1 shows the physical properties (logarithmic viscosity, melting point, rotational viscosity, etc.) of this imide oligomer.
前述のようにして得られた末端変性イミドオリゴマーを
、箱型の金型（長さ；１００ｍｍ、幅；２０ｍ＋ｎ）に
入れ、２５０℃に加熱し、１０ｋｇ／ｃＪで加圧し、そ
の加圧下に３３０”Ｃまで昇温し、１５分間その温度に
維持して熱処理してから冷却して、成形品（長さ；１０
０ｍｍ、幅；２０陶、厚さ；０゜３肛）を取り出した。The terminal-modified imide oligomer obtained as described above was placed in a box-shaped mold (length: 100 mm, width: 20 m+n), heated to 250°C, and pressurized at 10 kg/cJ. The temperature was raised to "C", maintained at that temperature for 15 minutes for heat treatment, and then cooled to form a molded product (length: 10
A piece (0 mm, width: 20 mm, thickness: 0°3 mm) was taken out.
この成形品の熱分解開始温度および二次転移温度などを
第１表に示す。Table 1 shows the thermal decomposition initiation temperature, secondary transition temperature, etc. of this molded article.
実施例２〜６
第１表に示す種類の（ａ）酸二無水物と（ｂ）ジアミン
化合物と（、（ｃ）不飽和モノ無水物または不飽和モノ
ミン化合物とを使用し、それらの各使用量をそれぞれ第
１表に示すようにしたほかは、実施例１と同様にして、
末端変性イミドオリゴマーを製造した。Examples 2 to 6 Using (a) acid dianhydride, (b) diamine compound, and (c) unsaturated monoanhydride or unsaturated monomine compound shown in Table 1, each use of In the same manner as in Example 1, except that the amounts were as shown in Table 1,
A terminally modified imide oligomer was produced.
これらのイミドオリゴマーは、Ｎ−メチル−２−ピロリ
ドン、ジオキサン、メチルエチルケトンなどの溶媒に良
好に溶解する。These imide oligomers dissolve well in solvents such as N-methyl-2-pyrrolidone, dioxane, and methyl ethyl ketone.
それらのイミドオリゴマーの物性を第１表に示す。Table 1 shows the physical properties of these imide oligomers.
また、各実施例で得られたイミドオリゴマーを使用した
ほかは、実施例１と同様にして成形品を成形した。それ
らの成形品は、それぞれゴム弾性を示す。それらの成形
品の熱分解開始温度を第１表に示す。Further, molded articles were molded in the same manner as in Example 1, except that the imide oligomers obtained in each Example were used. Each of these molded products exhibits rubber elasticity. Table 1 shows the starting temperature of thermal decomposition of these molded products.
この発明の末端変性イミドオリゴマーは、融点が１００
℃以下であり、種々の有機極性溶媒を使用しなくとも、
そのままで、接着剤、複合材料用のマトリックスなどと
して使用できるので、複合材料の製造の際の溶媒の蒸発
による除去に伴う種々の工程（脱法、乾燥など）の問題
を生じることがなく、その結果、種々の用途に非常に好
適に使用することができる。また、この発明の末端変性
イミドオリゴマーを加熱硬化して得られた成形物は、耐
熱性の優れた新規なゴム弾性体である。The terminal-modified imide oligomer of this invention has a melting point of 100
℃ or less, without using various organic polar solvents,
Since it can be used as it is as an adhesive, a matrix for composite materials, etc., there are no problems associated with the removal of solvents by evaporation during the production of composite materials (e.g., removal, drying, etc.). , can be used very suitably for various purposes. Furthermore, the molded product obtained by heating and curing the terminally modified imide oligomer of the present invention is a novel rubber elastic body with excellent heat resistance.
この発明の末端変性イミドオリゴマーは、種々の溶媒に
溶液に容易に溶解するので、必要であれば、安定な種々
の溶液組成物を調製することも容易に可能であり、しか
も、その溶液組成物から得られた成形物は、前述のよう
にゴム弾性体であり、種々の弾性成形体の製造、接着剤
、繊維改質材などの調製など種々の用途に好適に使用す
ることができる。Since the terminal-modified imide oligomer of the present invention is easily dissolved in solutions in various solvents, it is easily possible to prepare various stable solution compositions if necessary, and the solution compositions As mentioned above, the molded product obtained is a rubber elastic body, and can be suitably used for various purposes such as the production of various elastic molded products, the preparation of adhesives, fiber modifiers, etc.
特許出願人 宇部興産株式会社Patent applicant: Ube Industries Co., Ltd.
Claims (2)
ルボン酸類および／または３，３’，４，４’−ビフェ
ニルテトラカルボン酸類と、 （ｂ）α，ω−ジメチルポリシロキサン系ジアミン化合
物、 （ｃ）不飽和ジカルボン酸類および／または不飽和モノ
アミンとを、 有機溶媒中で反応させて得られた、オリゴマー末端に不
飽和末端基およびオリゴマー内部にイミド結合を有する
末端変性イミドオリゴマーであり、該イミドオリゴマー
は、対数粘度（濃度；０．５ｇ／１００ｍｌ溶媒、溶媒
；Ｎ−メチル−２−ピロリドン、測定温度；３０℃）が
１．０以下であり、しかも、融点が１００℃以下である
ことを特徴とする末端変性イミドオリゴマ−。(1) (a) 2,3,3',4'-biphenyltetracarboxylic acids and/or 3,3',4,4'-biphenyltetracarboxylic acids, and (b) α,ω-dimethylpolysiloxane system A terminal-modified imide oligomer having an unsaturated terminal group at the oligomer end and an imide bond inside the oligomer obtained by reacting a diamine compound, (c) unsaturated dicarboxylic acids and/or unsaturated monoamine in an organic solvent. Yes, the imide oligomer has a logarithmic viscosity (concentration: 0.5 g/100 ml solvent, solvent: N-methyl-2-pyrrolidone, measurement temperature: 30°C) of 1.0 or less, and a melting point of 100°C or less. A terminal-modified imide oligomer characterized by:
ルボン酸類および／または３，３’，４，４’−ビフェ
ニルテトラカルボン酸類と、 （ｂ）α、ω−ジメチルポリシロキサン系ジアミン化合
物、 （ｃ）不飽和ジカルボン酸類および／または不飽和モノ
アミンとを、 有機溶媒中で反応させて得られた、オリゴマー末端に不
飽和末端基およびオリゴマー内部にイミド結合を有する
末端変性イミドオリゴマーであり、該イミドオリゴマー
は、対数粘度（濃度；０．５ｇ／１００ｍｌ溶媒、溶媒
；Ｎ−メチル−２−ピロリドン、測定温度；３０℃）が
１．０以下であり、しかも、融点が１００℃以下である
末端変性イミドオリゴマーを、加熱架橋して得られた弾
性成形体。(2) (a) 2,3,3',4'-biphenyltetracarboxylic acids and/or 3,3',4,4'-biphenyltetracarboxylic acids; (b) α,ω-dimethylpolysiloxane system A terminal-modified imide oligomer having an unsaturated terminal group at the oligomer end and an imide bond inside the oligomer obtained by reacting a diamine compound, (c) unsaturated dicarboxylic acids and/or unsaturated monoamine in an organic solvent. Yes, the imide oligomer has a logarithmic viscosity (concentration: 0.5 g/100 ml solvent, solvent: N-methyl-2-pyrrolidone, measurement temperature: 30°C) of 1.0 or less, and a melting point of 100°C or less. An elastic molded article obtained by thermally crosslinking a terminal-modified imide oligomer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1058488A JPH01188528A (en) | 1988-01-22 | 1988-01-22 | Terminal-modified imide oligomer and elastic molded article produced therefrom |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1058488A JPH01188528A (en) | 1988-01-22 | 1988-01-22 | Terminal-modified imide oligomer and elastic molded article produced therefrom |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01188528A true JPH01188528A (en) | 1989-07-27 |
Family
ID=11754296
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1058488A Pending JPH01188528A (en) | 1988-01-22 | 1988-01-22 | Terminal-modified imide oligomer and elastic molded article produced therefrom |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01188528A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5128444A (en) * | 1989-04-18 | 1992-07-07 | Ube Industries, Ltd. | Thermosetting resin composition and thermosetting dry film |
| JPH05331445A (en) * | 1992-06-04 | 1993-12-14 | Sumitomo Bakelite Co Ltd | Production of film adhesive |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5624344A (en) * | 1979-08-06 | 1981-03-07 | Hitachi Ltd | Photosensitive heat-resistant polymer composition |
| JPS61179233A (en) * | 1985-02-02 | 1986-08-11 | Agency Of Ind Science & Technol | Polyimide prepreg |
| JPS61203132A (en) * | 1985-02-01 | 1986-09-09 | ゼネラル・エレクトリツク・カンパニイ | Crystal silicone-imide copolymer |
| JPS61247733A (en) * | 1985-04-25 | 1986-11-05 | Hitachi Chem Co Ltd | Production of acetylene-terminated polyamic acid, acetylene-terminated polyimide and addition-polymerized polyimide |
-
1988
- 1988-01-22 JP JP1058488A patent/JPH01188528A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5624344A (en) * | 1979-08-06 | 1981-03-07 | Hitachi Ltd | Photosensitive heat-resistant polymer composition |
| JPS61203132A (en) * | 1985-02-01 | 1986-09-09 | ゼネラル・エレクトリツク・カンパニイ | Crystal silicone-imide copolymer |
| JPS61179233A (en) * | 1985-02-02 | 1986-08-11 | Agency Of Ind Science & Technol | Polyimide prepreg |
| JPS61247733A (en) * | 1985-04-25 | 1986-11-05 | Hitachi Chem Co Ltd | Production of acetylene-terminated polyamic acid, acetylene-terminated polyimide and addition-polymerized polyimide |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5128444A (en) * | 1989-04-18 | 1992-07-07 | Ube Industries, Ltd. | Thermosetting resin composition and thermosetting dry film |
| JPH05331445A (en) * | 1992-06-04 | 1993-12-14 | Sumitomo Bakelite Co Ltd | Production of film adhesive |
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