JP4867407B2 - Alcoholic hydroxyl-terminated imide oligomer - Google Patents
Alcoholic hydroxyl-terminated imide oligomer Download PDFInfo
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- JP4867407B2 JP4867407B2 JP2006064699A JP2006064699A JP4867407B2 JP 4867407 B2 JP4867407 B2 JP 4867407B2 JP 2006064699 A JP2006064699 A JP 2006064699A JP 2006064699 A JP2006064699 A JP 2006064699A JP 4867407 B2 JP4867407 B2 JP 4867407B2
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- alcoholic hydroxyl
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- imide oligomer
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- 230000001476 alcoholic effect Effects 0.000 title claims description 90
- 150000003949 imides Chemical class 0.000 title claims description 73
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 59
- -1 alicyclic diamine compound Chemical class 0.000 claims description 51
- 150000001875 compounds Chemical class 0.000 claims description 27
- 125000003277 amino group Chemical group 0.000 claims description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- NBAUUNCGSMAPFM-UHFFFAOYSA-N 3-(3,4-dicarboxyphenyl)phthalic acid Chemical compound 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 description 16
- 239000000126 substance Substances 0.000 claims description 16
- 239000003960 organic solvent Substances 0.000 claims description 12
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 125000001931 aliphatic group Chemical group 0.000 claims description 7
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 3
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 6
- 125000005462 imide group Chemical group 0.000 claims 1
- 239000002904 solvent Substances 0.000 description 17
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 16
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- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 14
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- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 8
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- 238000004519 manufacturing process Methods 0.000 description 7
- 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 6
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- 125000002723 alicyclic group Chemical group 0.000 description 6
- 238000000034 method Methods 0.000 description 6
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- 229910052757 nitrogen Inorganic materials 0.000 description 5
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- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
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- 125000004018 acid anhydride group Chemical group 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
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- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
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- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 150000005690 diesters Chemical class 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 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 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000006358 imidation reaction Methods 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
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- 229920000647 polyepoxide Polymers 0.000 description 2
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- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-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
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- MXZROAOUCUVNHX-UHFFFAOYSA-N 2-Aminopropanol Chemical compound CCC(N)O MXZROAOUCUVNHX-UHFFFAOYSA-N 0.000 description 1
- JCBPETKZIGVZRE-UHFFFAOYSA-N 2-aminobutan-1-ol Chemical compound CCC(N)CO JCBPETKZIGVZRE-UHFFFAOYSA-N 0.000 description 1
- 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 1
- BYPFICORERPGJY-UHFFFAOYSA-N 3,4-diisocyanatobicyclo[2.2.1]hept-2-ene Chemical compound C1CC2(N=C=O)C(N=C=O)=CC1C2 BYPFICORERPGJY-UHFFFAOYSA-N 0.000 description 1
- XMUDRLWXESKMEF-UHFFFAOYSA-N COCCOCCOC.C(COCCOCCO)O Chemical compound COCCOCCOC.C(COCCOCCO)O XMUDRLWXESKMEF-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- ZWXPDGCFMMFNRW-UHFFFAOYSA-N N-methylcaprolactam Chemical compound CN1CCCCCC1=O ZWXPDGCFMMFNRW-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 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 1
- 239000002253 acid Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- QTQUJRIHTSIVOF-UHFFFAOYSA-N amino(phenyl)methanol Chemical compound NC(O)C1=CC=CC=C1 QTQUJRIHTSIVOF-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
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- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical compound NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-N 0.000 description 1
- GEQHKFFSPGPGLN-UHFFFAOYSA-N cyclohexane-1,3-diamine Chemical compound NC1CCCC(N)C1 GEQHKFFSPGPGLN-UHFFFAOYSA-N 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 1
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- 125000003700 epoxy group Chemical group 0.000 description 1
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- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
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- CRTPBQPFRKSOBC-UHFFFAOYSA-N methoxymethane;1-methoxy-2-[2-(2-methoxyethoxy)ethoxy]ethane Chemical compound COC.COCCOCCOCCOC CRTPBQPFRKSOBC-UHFFFAOYSA-N 0.000 description 1
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
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- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 1
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- Indole Compounds (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Description
この発明は、２，３，３’，４’−ビフェニルテトラカルボン酸成分と脂環式ジアミン成分の組合せからなり両末端にアルコール性水酸基を有する新規なアルコール性水酸基末端イミドオリゴマーに関する。このアルコール性水酸基末端イミドオリゴマーは、耐熱性が高いにもかかわらず、有機溶媒への可溶性が極めて高い。しかも両末端には種々の反応に利用できるアルコール性水酸基があるので、例えば高級脂肪族ジオール化合物とともに有機溶媒中でジイソシアネート化合物と反応させて、アルコール性水酸基末端イミドオリゴマーに由来する耐熱性セグメントと高級脂肪族ジオール化合物に由来する柔軟性ゼグメントとからなる、耐熱性と柔軟性とを併せ持ったポリウレタンを容易に調製することができる。このようなポリウレタンは種々の組成物の成分として好適である。 The present invention relates to a novel alcoholic hydroxyl-terminated imide oligomer comprising a combination of a 2,3,3 ', 4'-biphenyltetracarboxylic acid component and an alicyclic diamine component and having an alcoholic hydroxyl group at both ends. This alcoholic hydroxyl group-terminated imide oligomer has extremely high solubility in an organic solvent despite its high heat resistance. Moreover, since there are alcoholic hydroxyl groups that can be used for various reactions at both ends, for example, a reaction with a diisocyanate compound in an organic solvent together with a higher aliphatic diol compound, a heat resistant segment derived from an alcoholic hydroxyl group-terminated imide oligomer and a higher A polyurethane having both heat resistance and flexibility, comprising a flexible segment derived from an aliphatic diol compound, can be easily prepared. Such polyurethanes are suitable as components of various compositions.
芳香族イミドオリゴマーは、耐熱性、耐薬品性、電気特性などの優れた特長を有するが、末端に反応性基を導入して例えば高級脂肪族系樹脂と反応しようとすると、両者を溶解する溶媒がないために反応できなかった。また、他の樹脂との相溶性が低いために、組成物の成分として利用するのが容易ではなかった。 Aromatic imide oligomers have excellent features such as heat resistance, chemical resistance, and electrical properties, but if a reactive group is introduced at the end to react with, for example, a higher aliphatic resin, the solvent dissolves both. It was not possible to react because there was no. Moreover, since the compatibility with other resin is low, it was not easy to utilize as a component of a composition.
特許文献１には、ビフェニルテトラカルボン酸類と芳香族ジアミン化合物とフェノール性又はアルコール性水酸基を少なくとも１個有するモノアミン化合物とを溶媒中で反応させて得られた水酸基末端変性イミドオリゴマーが開示されている。しかし、このオリゴマーはアミド類などの特定の有機溶媒にしか溶解しなかった。
特許文献２には、特許文献１の水酸基末端変性イミドオリゴマーとエポキシ基を有する化合物とを主成分とする熱硬化性樹脂組成物が開示されている。しかし、この組成物を加熱処理して得られた硬化膜は柔軟性や屈曲性が劣るものであった。
Patent Document 1 discloses a hydroxyl-terminated modified imide oligomer obtained by reacting a biphenyltetracarboxylic acid, an aromatic diamine compound, and a monoamine compound having at least one phenolic or alcoholic hydroxyl group in a solvent. . However, this oligomer was only soluble in certain organic solvents such as amides.
Patent Document 2 discloses a thermosetting resin composition containing as a main component the hydroxyl group-terminated modified imide oligomer of Patent Document 1 and a compound having an epoxy group. However, the cured film obtained by heat-treating this composition has poor flexibility and flexibility.
この発明の目的は、耐熱性が優れ且つ有機溶媒に対する溶解性や他の樹脂に対する相溶性が改良された新規なアルコール性水酸基末端イミドオリゴマーを提供することである。 An object of the present invention is to provide a novel alcoholic hydroxyl group-terminated imide oligomer having excellent heat resistance and improved solubility in organic solvents and compatibility with other resins.
この発明は、下記化学式（１）の化学構造を有するアルコール性水酸基末端イミドオリゴマーに関する。 The present invention relates to an alcoholic hydroxyl group-terminated imide oligomer having a chemical structure represented by the following chemical formula (1).
また、この発明は、Ｙがイソホロンジアミン、ノルボルネンジアミン、ジアミノシクロヘキサン、４，４’−メチレンビス（シクロヘキシルアミン）からなる群から選ばれる脂環式ジアミン化合物からアミノ基を除いた２価の炭化水素基である前記アルコール性水酸基末端イミドオリゴマー、および、Ｙがイソホロンジアミンからアミノ基を除いた２価の炭化水素基である前記アルコール性水酸基末端イミドオリゴマー、さらに、Ｒが炭素数が１〜１０の２価の脂肪族炭化水素基である前記アルコール性水酸基末端イミドオリゴマーに関する。 The present invention also provides a divalent hydrocarbon group in which Y is an alicyclic diamine compound selected from the group consisting of isophorone diamine, norbornene diamine, diaminocyclohexane, and 4,4′-methylene bis (cyclohexylamine). The alcoholic hydroxyl-terminated imide oligomer, and the alcoholic hydroxyl-terminated imide oligomer in which Y is a divalent hydrocarbon group obtained by removing an amino group from isophoronediamine, and further R is 2 having 1 to 10 carbon atoms. It is related with the said alcoholic hydroxyl-terminated imide oligomer which is a valent aliphatic hydrocarbon group.
また、有機溶媒中で、２，３，３’，４’−ビフェニルテトラカルボン酸成分と脂環式ジアミン成分とアルコール性水酸基を有するモノアミン化合物とを重合反応及び／又はイミド化反応することを特徴とする前記アルコール性水酸基末端イミドオリゴマーの製造方法に関する。 In addition, a polymerization reaction and / or imidation reaction of a 2,3,3 ′, 4′-biphenyltetracarboxylic acid component, an alicyclic diamine component, and a monoamine compound having an alcoholic hydroxyl group is performed in an organic solvent. To the method for producing the alcoholic hydroxyl-terminated imide oligomer.
この発明によって、耐熱性が優れ且つ有機溶媒に対する溶解性や他の樹脂に対する相溶性が優れた新規なアルコール性水酸基末端イミドオリゴマーを提供することができる。このイミドオリゴマーは、イソホロンやシクロヘキサノンなどの溶媒に対しても充分な溶解性を持っている。このため、例えばこのイミドオリゴマーと高級脂肪族ジオール化合物とジイソシアネート化合物とを前記溶媒中に溶解して反応させて、アルコール性水酸基末端イミドオリゴマーに由来する耐熱性セグメントと高級脂肪族ジオール化合物に由来する柔軟性ゼグメントとからなる、耐熱性と柔軟性とを併せ持ったポリウレタンを容易に調製することができる。 According to the present invention, it is possible to provide a novel alcoholic hydroxyl group-terminated imide oligomer having excellent heat resistance, solubility in organic solvents, and compatibility with other resins. This imide oligomer has sufficient solubility in solvents such as isophorone and cyclohexanone. For this reason, for example, this imide oligomer, a higher aliphatic diol compound and a diisocyanate compound are dissolved and reacted in the solvent, resulting in a heat resistant segment derived from an alcoholic hydroxyl-terminated imide oligomer and a higher aliphatic diol compound. A polyurethane composed of a flexible segment and having both heat resistance and flexibility can be easily prepared.
この発明のアルコール性水酸基末端イミドオリゴマーは前記化学式（１）の化学構造を有する。式中、Ｘは前記化学式（２）の化学構造を有する４価の基であり、Ｒは炭素数が１〜２０の２価の炭化水素基であり、Ｙは炭素数が５〜３０の脂環式ジアミン化合物からアミノ基を除いた２価の炭化水素基であり、ｍは１〜５０の整数である。 The alcoholic hydroxyl-terminated imide oligomer of the present invention has the chemical structure represented by the chemical formula (1). In the formula, X is a tetravalent group having the chemical structure of the chemical formula (2), R is a divalent hydrocarbon group having 1 to 20 carbon atoms, and Y is a fat having 5 to 30 carbon atoms. It is a divalent hydrocarbon group obtained by removing an amino group from a cyclic diamine compound, and m is an integer of 1 to 50.
この発明のアルコール性水酸基末端イミドオリゴマーの好ましい態様は以下のとおりである。
（１）Ｙがイソホロンジアミン、ノルボルネンジアミン、ジアミノシクロヘキサン、４，４’−メチレンビス（シクロヘキシルアミン）からなる群から選ばれる脂環式ジアミン化合物からアミノ基を除いた２価の炭化水素基である前記アルコール性水酸基末端イミドオリゴマー。
（２）Ｙがイソホロンジアミンからアミノ基を除いた２価の炭化水素基である前記アルコール性水酸基末端イミドオリゴマー。
（３）Ｒが炭素数が１〜１０より好ましくは炭素数が１〜５の２価の炭化水素基である前記アルコール性水酸基末端イミドオリゴマー。
（４）ｍが１〜２０より好ましくは１〜１０特に１〜５の前記アルコール性水酸基末端イミドオリゴマー。
（５）ｍが異なる複数種のオリゴマーからなる前記アルコール性水酸基末端イミドオリゴマーの混合物。
Preferred embodiments of the alcoholic hydroxyl-terminated imide oligomer of the present invention are as follows.
(1) Y is a divalent hydrocarbon group obtained by removing an amino group from an alicyclic diamine compound selected from the group consisting of isophoronediamine, norbornenediamine, diaminocyclohexane, and 4,4′-methylenebis (cyclohexylamine). Alcoholic hydroxyl-terminated imide oligomer.
(2) The alcoholic hydroxyl group-terminated imide oligomer, wherein Y is a divalent hydrocarbon group obtained by removing an amino group from isophoronediamine.
(3) The alcoholic hydroxyl group-terminated imide oligomer, wherein R is a divalent hydrocarbon group having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms.
(4) The alcoholic hydroxyl group-terminated imide oligomer wherein m is 1 to 20, more preferably 1 to 10, particularly 1 to 5.
(5) A mixture of the alcoholic hydroxyl-terminated imide oligomers comprising a plurality of oligomers having different m.
この発明のアルコール性水酸基末端イミドオリゴマーについて詳細に説明する。
このアルコール性水酸基末端イミドオリゴマーは、溶媒中で２，３，３’，４’−ビフェニルテトラカルボン酸成分、脂環式ジアミン化合物、及びアルコール性水酸基を有するモノアミン化合物を所定の配合割合で反応させることによって好適に得ることができる。
The alcoholic hydroxyl group-terminated imide oligomer of the present invention will be described in detail.
This alcoholic hydroxyl-terminated imide oligomer reacts a 2,3,3 ′, 4′-biphenyltetracarboxylic acid component, an alicyclic diamine compound, and a monoamine compound having an alcoholic hydroxyl group in a solvent at a predetermined blending ratio. It can obtain suitably.
２，３，３’，４’−ビフェニルテトラカルボン酸成分としては、２，３，３’，４’−テトラカルボン酸、その酸二無水物、及びその低級アルコールエステル（特に炭素数１〜５の脂肪族アルコールのエステル）などの誘導体を挙げることができる。 Examples of the 2,3,3 ′, 4′-biphenyltetracarboxylic acid component include 2,3,3 ′, 4′-tetracarboxylic acid, its dianhydride, and its lower alcohol ester (particularly having 1 to 5 carbon atoms). Derivatives such as esters of aliphatic alcohols).
脂環式ジアミン化合物としては、分子内に１個又は複数個の脂環（好ましくは、１個又２個の脂環）を有し該脂環に２個のアミノ基又はアミノ基を有する炭化水素基が結合したジアミノ化合物である。該脂環にアルキル基などのアミノ基以外の炭化水素基が結合しても構わない。具体的にはイソホロンジアミン、ノルボルネンジアミン、１，２−ジアミノシクロヘキサン、１，３−ジアミノシクロヘキサン、１，４−ジアミノシクロヘキサン、４，４’−メチレンビス（シクロヘキシルアミン）などを挙げることができ、好ましくはイソホロンジアミンである。
なお、この発明では、脂環式ジアミン成分として、脂環式ジアミン化合物に代替して、当該化合物のアミノ基をイソシアネート基に置換した脂環式ジイソシアネート化合物を用いても構わない。具体的にはイソホロンジイソシアネート、ノルボルネンジイソシアネート、１，２−ジイソシアネートシクロヘキサン、１，３−ジイソシアネートシクロヘキサン、１，４−ジイソシアネートシクロヘキサン、４，４’−メチレンビス（シクロヘキシルイソシアネート）などを挙げることができる。
As the alicyclic diamine compound, one or a plurality of alicyclic rings (preferably one or two alicyclic rings) in the molecule and two amino groups or amino groups in the alicyclic ring. It is a diamino compound to which a hydrogen group is bonded. A hydrocarbon group other than an amino group such as an alkyl group may be bonded to the alicyclic ring. Specific examples include isophorone diamine, norbornene diamine, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 4,4′-methylenebis (cyclohexylamine), and preferably Isophorone diamine.
In the present invention, as the alicyclic diamine component, instead of the alicyclic diamine compound, an alicyclic diisocyanate compound in which the amino group of the compound is substituted with an isocyanate group may be used. Specific examples include isophorone diisocyanate, norbornene diisocyanate, 1,2-diisocyanate cyclohexane, 1,3-diisocyanate cyclohexane, 1,4-diisocyanate cyclohexane, 4,4′-methylene bis (cyclohexyl isocyanate), and the like.
アルコール性水酸基を有するモノアミン化合物としては、分子中にアルコール性水酸基とアミノ基とを各１個有する炭化水素化合物であれば特に限定するものではない。アミノエタノール、アミノプロパノール、アミノブタノールなどのアルコール性水酸基を有する脂肪族モノアミン化合物、好ましくは炭素数が１〜１０、より好ましくは炭素数が１〜５のアルコール性水酸基を有する脂肪族モノアミン化合物、アミノシクロヘキサノールなどのアルコール性水酸基を有する脂環式モノアミン化合物、好ましくは炭素数が３〜２０のアルコール性水酸基を有する脂環式モノアミン化合物、アミノベンジルアルコール、アミノフェニチルアルコールなどのアルコール性水酸基を有する芳香族モノアミン化合物、好ましくは炭素数が７〜２０のアルコール性水酸基を有する芳香族モノアミン化合物を好適に挙げることができる。 The monoamine compound having an alcoholic hydroxyl group is not particularly limited as long as it is a hydrocarbon compound having one alcoholic hydroxyl group and one amino group in the molecule. Aliphatic monoamine compounds having an alcoholic hydroxyl group such as aminoethanol, aminopropanol, aminobutanol, preferably an aliphatic monoamine compound having an alcoholic hydroxyl group having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, amino An alicyclic monoamine compound having an alcoholic hydroxyl group such as cyclohexanol, preferably an alicyclic monoamine compound having an alcoholic hydroxyl group having 3 to 20 carbon atoms, an alcoholic hydroxyl group such as aminobenzyl alcohol or aminophenethyl alcohol Preferred examples include aromatic monoamine compounds, preferably aromatic monoamine compounds having an alcoholic hydroxyl group having 7 to 20 carbon atoms.
この発明のアルコール性水酸基末端イミドオリゴマーは、両側にイミド環を持った非対称のビフェニル構造と脂肪族環とが結合した構造であるために、耐熱性が高いにもかかわらず、溶媒に対する溶解性が著しく向上したと考えられる。このアルコール性水酸基末端イミドオリゴマーは前記構造によって溶媒に対する高い溶解性のみならず他の樹脂に対する高い相溶性も有している。 The alcoholic hydroxyl-terminated imide oligomer of the present invention has a structure in which an asymmetric biphenyl structure having an imide ring on both sides and an aliphatic ring are bonded to each other. It is thought that it improved remarkably. This alcoholic hydroxyl-terminated imide oligomer has not only high solubility in a solvent but also high compatibility with other resins due to the above structure.
２，３，３’，４’−ビフェニルテトラカルボン酸成分以外の芳香族テトラカルボン酸成分を脂環式ジアミン化合物と組合せても、溶解性を高めるのは容易ではない。脂環式ジアミン化合物の代わりに芳香族ジアミン化合物を用いたのでは、２，３，３’，４’−ビフェニルテトラカルボン酸成分と組合せても、溶解性を高めるのは容易ではない。さらに、脂環式ジアミン化合物の代わりに脂肪族ジアミン化合物を用いても、必ずしも溶解性は高くならないし、耐熱性は低下する。
また、この発明のイミドオリゴマーの末端は種々の反応に利用できるアルコール性水酸基であるが、末端をフェノール性水酸基にすると高い溶解性を得るのが難しくなる。
Even if an aromatic tetracarboxylic acid component other than the 2,3,3 ′, 4′-biphenyltetracarboxylic acid component is combined with the alicyclic diamine compound, it is not easy to increase the solubility. If an aromatic diamine compound is used instead of the alicyclic diamine compound, it is not easy to increase the solubility even when combined with the 2,3,3 ′, 4′-biphenyltetracarboxylic acid component. Furthermore, even if an aliphatic diamine compound is used instead of the alicyclic diamine compound, the solubility does not necessarily increase and the heat resistance decreases.
Moreover, although the terminal of the imide oligomer of this invention is an alcoholic hydroxyl group that can be used for various reactions, it is difficult to obtain high solubility if the terminal is a phenolic hydroxyl group.
以上のとおり、この発明のアルコール性水酸基末端イミドオリゴマーは、２，３，３’，４’−ビフェニルテトラカルボン酸成分と脂環式ジアミン化合物とアルコール性水酸基を有するモノアミン化合物を組合せたことによって特に優れた耐熱性と溶解性とを達成したことを特徴とする。 As described above, the alcoholic hydroxyl-terminated imide oligomer of the present invention is particularly obtained by combining a 2,3,3 ′, 4′-biphenyltetracarboxylic acid component, an alicyclic diamine compound, and a monoamine compound having an alcoholic hydroxyl group. It is characterized by achieving excellent heat resistance and solubility.
以下に、この発明のアルコール性水酸基末端イリドオリゴマーの製造方法について説明する。
この発明のアルコール性水酸基末端イミドオリゴマーは、２，３，３’，４’−ビフェニルテトラカルボン酸成分と、脂環式ジアミン化合物と、アルコール性水酸基を有するモノアミン化合物からなるアミン成分とを、テトラカルボン酸成分の酸無水物基（または隣接した２個のカルボキル基）と、脂環式ジアミン化合物及びアルコール性水酸基を有するモノアミン化合物からなるアミン成分の合計のアミノ基とが略当量（通常は当量比（酸無水物基／アミノ基）が０．９５から１．０５）となるようにして、有機溶媒中で重合反応及び／又はイミド化反応させて得ることができる。限定されるものではないが、より具体的には次のような製造方法が採用できる。
Below, the manufacturing method of the alcoholic hydroxyl-terminal ylide oligomer of this invention is demonstrated.
The alcoholic hydroxyl-terminated imide oligomer of the present invention comprises a 2,3,3 ′, 4′-biphenyltetracarboxylic acid component, an alicyclic diamine compound, and an amine component composed of a monoamine compound having an alcoholic hydroxyl group. The acid anhydride group (or two adjacent carboxyl groups) of the carboxylic acid component and the total amino group of the amine component consisting of the monoamine compound having an alicyclic diamine compound and an alcoholic hydroxyl group are approximately equivalent (usually equivalent) It can be obtained by carrying out a polymerization reaction and / or an imidization reaction in an organic solvent so that the ratio (acid anhydride group / amino group) is 0.95 to 1.05). Although not limited, more specifically, the following manufacturing method can be employed.
（ａ）２，３，３’，４’−ビフェニルテトラカルボン酸成分と、脂環式ジアミン化合物及びアルコール性水酸基を有するモノアミン化合物からなるアミン成分とを、酸無水基（または隣接した２個のカルボン酸基）とアミノ基とが略当量となるような割合で使用して、有機溶媒中１００℃以下程度の低温で反応させてアミド−酸結合を有するイミド前駆体オリゴマーを生成し、次いで、そのイミド前駆体を０℃〜１４０℃程度の低温でイミド化剤を添加するか或いは１４０℃〜２５０℃程度の高温で加熱して縮合・イミド化させる方法。
（ｂ）２，３，３’，４’−ビフェニルテトラカルボン酸成分と、脂環式ジアミン化合物及びアルコール性水酸基を有するモノアミン化合物からなるアミン成分とを、酸無水基（または隣接した２個のカルボン酸基）とアミノ基とが略当量となるような割合で使用して、有機溶媒中１４０℃〜２５０℃程度の高温で加熱して縮合・イミド化させる方法。
(A) a 2,3,3 ′, 4′-biphenyltetracarboxylic acid component and an amine component composed of an alicyclic diamine compound and a monoamine compound having an alcoholic hydroxyl group are converted into an acid anhydride group (or two adjacent groups). Carboxylic acid group) and amino group are used at a ratio such that they are approximately equivalent, and are reacted in an organic solvent at a low temperature of about 100 ° C. or less to produce an imide precursor oligomer having an amide-acid bond, A method of condensing and imidizing the imide precursor by adding an imidizing agent at a low temperature of about 0 ° C. to 140 ° C. or heating at a high temperature of about 140 ° C. to 250 ° C.
(B) A 2,3,3 ′, 4′-biphenyltetracarboxylic acid component and an amine component composed of an alicyclic diamine compound and a monoamine compound having an alcoholic hydroxyl group are combined with an acid anhydride group (or two adjacent groups). A method in which a carboxylic acid group) and an amino group are used in a ratio such that they are approximately equivalent and heated in an organic solvent at a high temperature of about 140 ° C. to 250 ° C. for condensation and imidization.
これらの製造方法の中で、２，３，３’，４’−ビフェニルテトラカルボン酸成分として２，３，３’，４’−ビフェニルテトラカルボン酸の低級脂肪族アルコール（特に炭素数が１〜５の脂肪族アルコール）のジエステル（隣接した２個のカルボキシル基がエステルとカルボン酸になっている）を用いた前記（ｂ）の方法が、反応中においても溶解性を保持し易く且つ反応を制御し易いので特に好適である。２，３，３’，４’−ビフェニルテトラカルボン酸二無水物を用いた前記（ｂ）の方法や、ポリイミド前駆体を経由する前記（ａ）の方法では反応中に反応物が析出する場合がある。
２，３，３’，４’−ビフェニルテトラカルボン酸の低級脂肪族アルコールのジエステルは、２，３，３’，４’−ビフェニルテトラカルボン酸二無水物と低級アルコールとを好ましくは加熱して反応させることによって容易に得ることができるので、原料としては２，３，３’，４’−ビフェニルテトラカルボン酸二無水物を用い、最初の工程で低級アルコールと反応させジエステルを生成させ、次の工程でジアミン成分を加えて前記（ｂ）の反応を行うことが好都合である。
なお、イミド化反応で水やアルコールが脱離する場合には、トルエンやキシレンを加えて共沸によって脱離した水やアルコールを除去しながら反応させてもよい。
Among these production methods, 2,3,3 ′, 4′-biphenyltetracarboxylic acid component is a 2,3,3 ′, 4′-biphenyltetracarboxylic acid lower aliphatic alcohol (particularly having 1 to 3 carbon atoms). 5 (aliphatic alcohol) diester (the two adjacent carboxyl groups are an ester and a carboxylic acid), the method of (b) is easy to maintain solubility during the reaction It is particularly suitable because it is easy to control. In the case of the method (b) using 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride or the method (a) via a polyimide precursor, the reactant precipitates during the reaction. There is.
The diester of lower aliphatic alcohol of 2,3,3 ′, 4′-biphenyltetracarboxylic acid is preferably obtained by heating 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride and lower alcohol. Since it can be easily obtained by reaction, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride is used as a raw material, and is reacted with a lower alcohol in the first step to form a diester. It is convenient to carry out the reaction (b) by adding a diamine component in the step (b).
In addition, when water and alcohol desorb | save by imidation reaction, you may make it react, adding toluene and xylene and removing water and alcohol desorbed by azeotropy.
また、脂環式ジアミン化合物に代替して、脂環式ジアミン成分として当該ジアミン化合物のアミノ基をイソシアネート基に置換した脂環式ジイソシアネート化合物を用いることもできる。この場合には、予め過剰量の２，３，３’，４’−ビフェニルテトラカルボン酸成分と脂環式ジイソシアネート化合物とをイミド化反応させて、末端に２，３，３’，４’−ビフェニルテトラカルボン酸成分を有するオリゴマーを生成し、次いで前記生成物とアルコール性水酸基を有するモノアミン化合物とを反応させることが好都合である。 Moreover, it can replace with an alicyclic diamine compound and can also use the alicyclic diisocyanate compound which substituted the amino group of the said diamine compound to the isocyanate group as an alicyclic diamine component. In this case, an excess amount of 2,3,3 ′, 4′-biphenyltetracarboxylic acid component and an alicyclic diisocyanate compound are imidized in advance to form 2,3,3 ′, 4′-terminal at the terminal. It is convenient to produce an oligomer having a biphenyltetracarboxylic acid component and then react the product with a monoamine compound having an alcoholic hydroxyl group.
アルコール性水酸基末端イミドオリゴマーを製造する際に使用される溶媒としては、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、Ｎ−メチルカプロラクタムなどのアミド類溶媒、ジメチルスルホキシド、ヘキサメチルフォスホルムアミド、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、キシレノールなどのフェノール類溶媒、ジエチレングリコールジメチルエーテル（ジグライム）、トリエチレングリコールジメチルエーテル（トリグライム）、テトラグライムなどのジグライム類溶媒、γ−ブチロラクトンなどのラクトン類溶媒、イソホロン、シクロヘキサノン、３，３，５−トリメチルシクロヘキサノンなどのケトン類溶媒、ピリジン、エチレングリコール、ジオキサン、テトラメチル尿素などのその他の溶媒を挙げることができる。これらの有機溶媒は単独で用いても複数種を混合して用いても構わない。 Examples of the solvent used in producing the alcoholic hydroxyl-terminated imide oligomer include amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, and N-methylcaprolactam. Solvents, solvents containing sulfur atoms such as dimethyl sulfoxide, hexamethylphosphamide, dimethyl sulfone, tetramethylene sulfone, dimethyltetramethylene sulfone, phenol solvents such as cresol, phenol, xylenol, diethylene glycol dimethyl ether (diglyme), triethylene glycol Diglyme solvents such as dimethyl ether (triglyme) and tetraglyme, lactone solvents such as γ-butyrolactone, isophorone, cyclohexanone, 3,3,5-trime Ketones solvents such as Le cyclohexanone, pyridine, ethylene glycol, dioxane, and other solvents such as tetramethylurea. These organic solvents may be used alone or in combination of two or more.
前記製造方法で調製したアルコール性水酸基末端イミドオリゴマーは、通常は前記化学式（１）中のｍが異なる複数種のオリゴマーからなるアルコール性水酸基末端イミドオリゴマーの混合物になっている。ｍが異なる複数種のアルコール性水酸基末端イミドオリゴマーからなる混合物を、それぞれのイミドオリゴマーに分離して用いても構わないが、分離しないで混合物のままで用いるのが好適である。
なお、アルコール性水酸基末端イミドオリゴマーのｍ（混合物の場合はｍの平均値）は、脂環式ジアミン化合物とアルコール性水酸基を有するモノアミン化合物との仕込み比（モル比）によって容易に制御することができる。
この発明のアルコール性水酸基末端イミドオリゴマーは、前記化学式（１）中のｍが１〜５０であり、好ましくはｍが１〜２０であり、より好ましくは１〜１０であり、特に１〜５であることが好適である。ｍが５０を越えると溶解に時間がかかるなどの問題が生じる。また、反応基の密度が低くなると他の化合物と反応させる時の使い勝手が悪くなる。
前記製造方法で調製したアルコール性水酸基末端イミドオリゴマーは、その反応混合液を、そのまま又は適宜濃縮あるいは希釈して、アルコール性水酸基末端イミドオリゴマー溶液として使用することもできるし、あるいは、その反応液を水等の非溶解性溶媒に注ぎ込んで、アルコール性水酸基末端イミドオリゴマーを粉末生成物として単離して使用することもできる。単離した粉末生成物は必要時に有機極性溶媒に溶解して使用することもできる。
The alcoholic hydroxyl-terminated imide oligomer prepared by the above production method is usually a mixture of alcoholic hydroxyl-terminated imide oligomers composed of plural types of oligomers having different m in the chemical formula (1). A mixture composed of a plurality of types of alcoholic hydroxyl-terminated imide oligomers having different m may be used separately for each imide oligomer, but it is preferable to use the mixture as it is without separation.
In addition, m (average value of m in the case of a mixture) of the alcoholic hydroxyl-terminated imide oligomer can be easily controlled by the charging ratio (molar ratio) of the alicyclic diamine compound and the monoamine compound having an alcoholic hydroxyl group. it can.
In the alcoholic hydroxyl group-terminated imide oligomer of the present invention, m in the chemical formula (1) is 1 to 50, preferably m is 1 to 20, more preferably 1 to 10, particularly 1 to 5. Preferably it is. When m exceeds 50, there arises a problem that dissolution takes time. Further, when the density of the reactive group is lowered, usability when reacting with another compound is deteriorated.
The alcoholic hydroxyl-terminated imide oligomer prepared by the above production method can be used as an alcoholic hydroxyl-terminated imide oligomer solution as it is or by concentrating or diluting the reaction mixture as it is, or alternatively, The alcoholic hydroxyl-terminated imide oligomer can be isolated and used as a powder product by pouring into a non-soluble solvent such as water. The isolated powder product can be used by dissolving in an organic polar solvent when necessary.
以下、実施例などによって本発明を更に詳細に説明する。尚、本発明は以下の実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. In addition, this invention is not limited to a following example.
以下の各例において測定、評価は次の方法で行った。
〔１Ｈ−ＮＭＲスペクトル〕
１Ｈ−ＮＭＲスペクトルは、核磁気共鳴スペクトロメータ−（日本電子株式会社製ＡＬ−３００）を用いて、試料を重ジメチルスルホキシドまたは重クロロホルムに溶解して測定した。
〔熱分解温度〕
熱分解温度は、熱重量分析計（島津製作所製ＴＧＡ−５０）を用いて、１０℃／ｍｉｎで昇温し、５％重量減少温度を求めた。
〔イソホロンに対する溶解性〕
イソホロンに試料の水酸基末端イミドオリゴマーを濃度が２０重量％となるように添加し、１００℃で３０分間加熱後、室温（２０℃）に冷却した。目視観察によって加熱時及び冷却後も均一に溶解した場合を○、加熱時に溶解し冷却後に析出した場合を△、加熱時も溶解しない場合を×とした。
In the following examples, measurement and evaluation were performed by the following methods.
[ 1 H-NMR spectrum]
1 H-NMR spectrum was measured by dissolving a sample in heavy dimethyl sulfoxide or heavy chloroform using a nuclear magnetic resonance spectrometer (AL-300 manufactured by JEOL Ltd.).
[Pyrolysis temperature]
The thermal decomposition temperature was raised at 10 ° C./min using a thermogravimetric analyzer (TGA-50 manufactured by Shimadzu Corporation) to obtain a 5% weight loss temperature.
[Solubility in isophorone]
The sample hydroxyl-terminated imide oligomer was added to isophorone so as to have a concentration of 20% by weight, heated at 100 ° C. for 30 minutes, and then cooled to room temperature (20 ° C.). The case where it melt | dissolved uniformly also at the time of heating and cooling by visual observation was set to (circle), the case where it melt | dissolved at the time of heating, and deposited after cooling was set to (triangle | delta), and the case where it did not melt | dissolve also at the time of heating was set as x.
〔実施例１〕
窒素導入管、ディーンスタークレシバー、冷却管を備えた容量５００ミリリットルのガラス製セパラブルフラスコに、２，３，３’，４’−ビフェニルテトラカルボン酸二無水物５８．８ｇ（０．２０モル）、イソホロンジアミン１７．０ｇ（０．１０モル）、３−アミノプロパノール１５．０ｇ（０．２０モル）、及びジメチルアセトアミド２００ミリリットルを仕込み、窒素雰囲気下、１００℃で１時間撹拌した。次いで、トルエン５０ミリリットルを加え、１８０℃４時間加熱し、イミド化反応により生じた水をトルエンと共沸により除いた。反応溶液を水２リットルに注ぎ込んで、生じた沈殿を濾取し、水洗後減圧乾燥し、アルコール性水酸基末端イミドオリゴマーの粉末７８．８ｇを得た。このアルコール性水酸基末端イミドオリゴマーの１Ｈ−ＮＭＲスペクトルを図１に示す。図１のプロパノールの２位メチレンプロトン（１．６５〜１．８５ｐｐｍ）とビフェニルテトラカルボン酸イミドのフェニレンプロトン（７．６０〜８．２０ｐｐｍ）の積分強度比から、２官能性水酸基末端イミドオリゴマーは化学式（１）のｍ（平均値）が１の２官能性水酸基末端イミドオリゴマーであることが確認できた。
得られたアルコール性水酸基末端イミドオリゴマーの溶解性と熱的性質を表１に示す。
[Example 1]
Into a 500 ml glass separable flask equipped with a nitrogen inlet tube, Dean Star crucibar, and cooling tube, 58.8 g (0.20 mol) of 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride. , 17.0 g (0.10 mol) of isophoronediamine, 15.0 g (0.20 mol) of 3-aminopropanol, and 200 ml of dimethylacetamide were stirred and stirred at 100 ° C. for 1 hour in a nitrogen atmosphere. Next, 50 ml of toluene was added and heated at 180 ° C. for 4 hours, and water generated by the imidization reaction was removed azeotropically with toluene. The reaction solution was poured into 2 liters of water, and the resulting precipitate was collected by filtration, washed with water and dried under reduced pressure to obtain 78.8 g of an alcoholic hydroxyl group-terminated imide oligomer powder. The 1 H-NMR spectrum of this alcoholic hydroxyl-terminated imide oligomer is shown in FIG. From the integrated intensity ratio of the 2-position methylene proton (1.65-1.85 ppm) of propanol and the phenylene proton (7.60-8.20 ppm) of biphenyltetracarboxylic imide in FIG. 1, the bifunctional hydroxyl-terminated imide oligomer is It was confirmed that m (average value) of chemical formula (1) was a bifunctional hydroxyl-terminated imide oligomer having 1.
Table 1 shows the solubility and thermal properties of the resulting alcoholic hydroxyl-terminated imide oligomer.
〔実施例２〕
窒素導入管、ディーンスタークレシバー、冷却管を備えた容量５００ミリリットルのガラス製セパラブルフラスコに、２，３，３’，４’−ビフェニルテトラカルボン酸二無水物５８．８ｇ（０．２０モル）、エチルアルコール２０．３ｇ（０．４４モル）、γ−ブチロラクトン８３．６ｇを仕込み、窒素雰囲気下９０℃で１時間撹拌して２，３，３’，４’−ビフェニルテトラカルボン酸ジエステルを得た。この反応混合液に、さらに、イソホロンジアミン１７．０ｇ（０．１０モル）と３−アミノプロパノール１５．０ｇ（０．２０モル）を添加し、１２０℃に昇温して２時間、１８０℃に昇温して９時間攪拌してアルコール性水酸基末端イミドオリゴマー溶液を得た。
この反応溶液から溶媒を減圧下にて除去し、その残留混合物の１Ｈ−ＮＭＲスペクトルを測定した。得られた１Ｈ−ＮＭＲスペクトルを図２に示す。図１と同様なスペクトルが得られており、実施例１と同一の構造を有するアルコール性水酸基末端イミドオリゴマーであることが確認できた。
[Example 2]
Into a 500 ml glass separable flask equipped with a nitrogen inlet tube, Dean Star crucibar, and cooling tube, 58.8 g (0.20 mol) of 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride. , 20.3 g (0.44 mol) of ethyl alcohol and 83.6 g of γ-butyrolactone were added and stirred at 90 ° C. for 1 hour under a nitrogen atmosphere to obtain 2,3,3 ′, 4′-biphenyltetracarboxylic acid diester. It was. To this reaction mixture, 17.0 g (0.10 mol) of isophoronediamine and 15.0 g (0.20 mol) of 3-aminopropanol were further added, the temperature was raised to 120 ° C., and the temperature was increased to 180 ° C. for 2 hours. The mixture was heated up and stirred for 9 hours to obtain an alcoholic hydroxyl group-terminated imide oligomer solution.
The solvent was removed from the reaction solution under reduced pressure, and the 1 H-NMR spectrum of the residual mixture was measured. The obtained 1 H-NMR spectrum is shown in FIG. A spectrum similar to that in FIG. 1 was obtained, and it was confirmed that the alcoholic hydroxyl group-terminated imide oligomer had the same structure as in Example 1.
〔実施例３〜７〕
表１に示す種類と量の２，３，３’，４’−ビフェニルテトラカルボン酸成分、脂環式ジアミン成分及びアルコール性水酸基を有するモノアミン化合物を使用し、実施例１と同様にしてアルコール性水酸基末端イミドオリゴマーの粉末を得た。それらについて１Ｈ−ＮＭＲスペクトルを測定し生成を確認した。得られたアルコール性水酸基末端イミドオリゴマーの各特性を表１に示す。図３〜７に１Ｈ−ＮＭＲスペクトルを示す。
[Examples 3 to 7]
Alcoholic properties were used in the same manner as in Example 1 using the types and amounts of 2,3,3 ′, 4′-biphenyltetracarboxylic acid component, alicyclic diamine component, and monoamine compound having an alcoholic hydroxyl group shown in Table 1. A powder of a hydroxyl-terminated imide oligomer was obtained. About them, 1 H-NMR spectrum was measured to confirm the production. Table 1 shows the characteristics of the obtained alcoholic hydroxyl group-terminated imide oligomer. The 1 H-NMR spectrum is shown in FIGS.
〔比較例１〕
窒素導入管、ディーンスタークレシバー、冷却管を備えた容量５００ミリリットルのガラス製セパラブルフラスコに、２，３，３’，４’−ビフェニルテトラカルボン酸二無水物２９．４ｇ（０．１０モル）、４，４’−ジフェニルメタンジイソシアネート１２．５ｇ（０．０５モル）及びジメチルアセトアミド１００ミリリットルを仕込み、窒素雰囲気下、１８０℃で４時間撹拌した。前記反応混合物に、さらに３−アミノプロパノール７．５ｇ（０．１０モル）とトルエン３５ミリリットルを加え、１８０℃４時間加熱し、イミド化反応により生じた水をトルエンと共沸により除いた。反応溶液を水１リットルに投入して、生じた沈殿を濾取し、水洗後減圧乾燥し、アルコール性水酸基末端イミドオリゴマーを得た。得られたアルコール性水酸基末端イミドオリゴマーの溶解性と熱的性質を表１に示す。
〔比較例２〜５〕
表１に示す種類と量のテトラカルボン酸成分、ジアミン成分及び水酸基を有するモノアミン化合物を使用し、実施例１と同様にして水酸基末端イミドオリゴマーの粉末を得た。それらの各特性を表１に示す。
[Comparative Example 1]
In a 500 ml glass separable flask equipped with a nitrogen inlet tube, a Dean Star crucibar, and a condenser tube, 29.4 g (0.10 mol) of 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride 4,4′-diphenylmethane diisocyanate (12.5 g, 0.05 mol) and 100 ml of dimethylacetamide were charged and stirred at 180 ° C. for 4 hours in a nitrogen atmosphere. To the reaction mixture, 7.5 g (0.10 mol) of 3-aminopropanol and 35 ml of toluene were further added, heated at 180 ° C. for 4 hours, and water generated by the imidization reaction was removed azeotropically with toluene. The reaction solution was poured into 1 liter of water, and the resulting precipitate was collected by filtration, washed with water and dried under reduced pressure to obtain an alcoholic hydroxyl group-terminated imide oligomer. Table 1 shows the solubility and thermal properties of the resulting alcoholic hydroxyl-terminated imide oligomer.
[Comparative Examples 2 to 5]
Using the kind and amount of tetracarboxylic acid component, diamine component and monoamine compound having a hydroxyl group shown in Table 1, a hydroxyl-terminated imide oligomer powder was obtained in the same manner as in Example 1. Their respective characteristics are shown in Table 1.
〔参考例１〕
窒素導入管を備えた容量１００ミリリットルのガラス製フラスコに、水添ポリブタジエンポリオールＧＩ−２０００（日本曹達株式会社製、水酸基価：４６．２ＫＯＨｍｇ／ｇ） ７．８６ｇ（５．０ミリモル）、２，２−ビス（ヒドロキシメチル）プロピオン酸０．１６８ｇ（１．２５ミリモル）、４，４’−ジフェニルメタンジイソシアネート２．５６ｇ（１０．２ミリモル）、イソホロン１０ｇを仕込み、窒素雰囲気下、８０℃で１．５時間撹拌した。次いで、実施例１で調製したアルコール性水酸基末端イミドオリゴマー４．１７ｇ（５．０ミリモル）、イソホロン１２．１ｇを加え、８０℃で１．５時間撹拌した。得られた樹脂溶液は、ポリマ−固形分濃度４０重量％、粘度６．３Ｐａ・ｓの溶液であった。ＧＰＣから求めた数平均分子量は１１０００であった。
このようにしてアルコール性水酸基末端イミドオリゴマーに由来する耐熱性セグメントと高級脂肪族ジオール化合物に由来する柔軟性ゼグメントとからなる耐熱性と柔軟性とを併せ持ったポリウレタンを得ることが出来た。
なお、この例で用いた水添ポリブタジエンポリオールＧＩ−２０００は、イソホロン、シクロヘキサノンなどのケトン類溶媒には溶解するが、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−ピロリドンなどのアミド類溶媒には溶解しない。
[Reference Example 1]
In a glass flask having a capacity of 100 milliliters equipped with a nitrogen introduction tube, hydrogenated polybutadiene polyol GI-2000 (manufactured by Nippon Soda Co., Ltd., hydroxyl value: 46.2 KOHmg / g) 7.86 g (5.0 mmol), 2, 0.168 g (1.25 mmol) of 2-bis (hydroxymethyl) propionic acid, 2.56 g (10.2 mmol) of 4,4′-diphenylmethane diisocyanate, and 10 g of isophorone were charged, and 1. at 80 ° C. in a nitrogen atmosphere. Stir for 5 hours. Subsequently, 4.17 g (5.0 mmol) of the alcoholic hydroxyl group-terminated imide oligomer prepared in Example 1 and 12.1 g of isophorone were added and stirred at 80 ° C. for 1.5 hours. The obtained resin solution was a solution having a polymer solid content concentration of 40% by weight and a viscosity of 6.3 Pa · s. The number average molecular weight determined from GPC was 11,000.
In this way, a polyurethane having both heat resistance and flexibility composed of a heat resistant segment derived from an alcoholic hydroxyl-terminated imide oligomer and a flexible segment derived from a higher aliphatic diol compound could be obtained.
The hydrogenated polybutadiene polyol GI-2000 used in this example is soluble in ketone solvents such as isophorone and cyclohexanone, but N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2- It does not dissolve in amide solvents such as pyrrolidone.
〔参考例２〕
窒素導入管を備えた容量３００ミリリットルのガラス製フラスコに、ジオール化合物であるクラレポリオールＣ−２０１５（株式会社クラレ製、平均分子量２０００）１０.０ｇ（５．０１ミリモル）、２，２−ビス（ヒドロキシメチル）プロピオン酸０．１６８ｇ（１．２５ミリモル）、４，４’−ジフェニルメタンジイソシアネート２．５６ｇ（１０．２５ミリモル）を仕込み、窒素雰囲気下、８０℃で１．５時間撹拌した。次いで、実施例１で調製したアルコール性水酸基末端イミドオリゴマー４．１９ｇ（５．０１ミリモル）、イソホロン２５．３８ｇを加え、８０℃で１．５時間撹拌した。得られた樹脂溶液は、ポリマー固形分濃度４０重量％、粘度２４Ｐａ・ｓの溶液であった。ＧＰＣから求めた数平均分子量は６４００であった。
このようにしてアルコール性水酸基末端イミドオリゴマーに由来する耐熱性セグメントとジオール化合物に由来する柔軟性ゼグメントとからなる耐熱性と柔軟性とを併せ持ったポリウレタンを得ることが出来た。
[Reference Example 2]
In a glass flask having a capacity of 300 ml equipped with a nitrogen introduction tube, 10.0 g (5.01 mmol) of Kuraray polyol C-2015 (manufactured by Kuraray Co., Ltd., average molecular weight 2000), 2,2-bis ( Hydroxymethyl) propionic acid (0.168 g, 1.25 mmol) and 4,4′-diphenylmethane diisocyanate (2.56 g, 10.25 mmol) were charged, and the mixture was stirred at 80 ° C. for 1.5 hours in a nitrogen atmosphere. Next, 4.19 g (5.01 mmol) of the alcoholic hydroxyl-terminated imide oligomer prepared in Example 1 and 25.38 g of isophorone were added, and the mixture was stirred at 80 ° C. for 1.5 hours. The obtained resin solution was a solution having a polymer solid content concentration of 40% by weight and a viscosity of 24 Pa · s. The number average molecular weight determined from GPC was 6400.
In this way, a polyurethane having both heat resistance and flexibility composed of a heat resistant segment derived from an alcoholic hydroxyl-terminated imide oligomer and a flexible segment derived from a diol compound could be obtained.
さらに、参考例１、２で得られたポリウレタンは、エポキシ樹脂との相溶性が良好であり、エポキシ樹脂と組合せた組成物から耐熱性と柔軟性とを兼ね備えた硬化物を得ることができた。 Furthermore, the polyurethanes obtained in Reference Examples 1 and 2 had good compatibility with the epoxy resin, and a cured product having both heat resistance and flexibility could be obtained from the composition combined with the epoxy resin. .
この発明によって、耐熱性が優れ且つ有機溶媒に対する溶解性や他の樹脂に対する相溶性が優れた新規なアルコール性水酸基末端イミドオリゴマーを提供することができる。このアルコール性水酸基末端イミドオリゴマーは、各種樹脂の変性や樹脂組成分の成分として有用に使用することができる。 According to the present invention, it is possible to provide a novel alcoholic hydroxyl group-terminated imide oligomer having excellent heat resistance, solubility in organic solvents, and compatibility with other resins. This alcoholic hydroxyl-terminated imide oligomer can be usefully used as a component of various resin modifications and resin components.
Claims (5)
但し、式中、Ｘは下記化学式（２）の化学構造を有する４価の基であり、
Ｒは、炭素数が１〜１０のアルコール性水酸基を有する脂肪族モノアミン化合物からアミノ基及びアルコール性水酸基を除いた２価の炭化水素基、又は
炭素数が７〜２０のアルコール性水酸基を有する芳香族モノアミン化合物からアミノ基及びアルコール性水酸基を除いた２価の炭化水素基であり、
Ｙは炭素数が５〜３０の脂環式ジアミン化合物からアミノ基を除いた２価の炭化水素基であり、ｍは１〜５０の整数である。
However, in the formula, X is a tetravalent group having the chemical structure of the following chemical formula (2),
R is a divalent hydrocarbon group obtained by removing an amino group and an alcoholic hydroxyl group from an aliphatic monoamine compound having an alcoholic hydroxyl group having 1 to 10 carbon atoms, or
A divalent hydrocarbon group obtained by removing an amino group and an alcoholic hydroxyl group from an aromatic monoamine compound having an alcoholic hydroxyl group having 7 to 20 carbon atoms,
Y is a divalent hydrocarbon group obtained by removing an amino group from an alicyclic diamine compound having 5 to 30 carbon atoms, and m is an integer of 1 to 50.
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