JP2011102259A - Aromatic diamine compound and manufacturing method for the same, and synthetic resin - Google Patents
Aromatic diamine compound and manufacturing method for the same, and synthetic resin Download PDFInfo
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- JP2011102259A JP2011102259A JP2009257550A JP2009257550A JP2011102259A JP 2011102259 A JP2011102259 A JP 2011102259A JP 2009257550 A JP2009257550 A JP 2009257550A JP 2009257550 A JP2009257550 A JP 2009257550A JP 2011102259 A JP2011102259 A JP 2011102259A
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- -1 Aromatic diamine compound Chemical class 0.000 title claims abstract description 79
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- 229920003002 synthetic resin Polymers 0.000 title claims description 21
- 239000000057 synthetic resin Substances 0.000 title claims description 21
- 239000002994 raw material Substances 0.000 claims abstract description 25
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- 229920001721 polyimide Polymers 0.000 claims description 18
- NIELKVFLOQJZIC-UHFFFAOYSA-N triazine;dihydrochloride Chemical compound Cl.Cl.C1=CN=NN=C1 NIELKVFLOQJZIC-UHFFFAOYSA-N 0.000 claims description 18
- 239000004642 Polyimide Substances 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 9
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 7
- 150000004985 diamines Chemical class 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 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 claims description 4
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims description 4
- ZMCUDHNSHCRDBT-UHFFFAOYSA-M caesium bicarbonate Chemical compound [Cs+].OC([O-])=O ZMCUDHNSHCRDBT-UHFFFAOYSA-M 0.000 claims description 3
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 3
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 235000011181 potassium carbonates Nutrition 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 229940086066 potassium hydrogencarbonate Drugs 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 abstract description 8
- 229920006015 heat resistant resin Polymers 0.000 abstract 1
- 229920005989 resin Polymers 0.000 abstract 1
- 239000011347 resin Substances 0.000 abstract 1
- 238000005481 NMR spectroscopy Methods 0.000 description 10
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical class C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- WKTCUHXVNOMCLP-UHFFFAOYSA-N Nc1ccc(Nc2nc(Nc3ccc(N)cc3)nc(Nc3ccc(cc3)C#C)n2)cc1 Chemical compound Nc1ccc(Nc2nc(Nc3ccc(N)cc3)nc(Nc3ccc(cc3)C#C)n2)cc1 WKTCUHXVNOMCLP-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 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
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- CSCPPACGZOOCGX-WFGJKAKNSA-N acetone d6 Chemical compound [2H]C([2H])([2H])C(=O)C([2H])([2H])[2H] CSCPPACGZOOCGX-WFGJKAKNSA-N 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000011903 deuterated solvents Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 229920005575 poly(amic acid) Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- NNTUXHWLOQDIQJ-UHFFFAOYSA-N 3-[3-(3-aminophenoxy)-5-(2-phenylethynyl)phenoxy]aniline Chemical compound NC=1C=C(OC2=CC(=CC(=C2)C#CC2=CC=CC=C2)OC2=CC(=CC=C2)N)C=CC1 NNTUXHWLOQDIQJ-UHFFFAOYSA-N 0.000 description 1
- JXYITCJMBRETQX-UHFFFAOYSA-N 4-ethynylaniline Chemical compound NC1=CC=C(C#C)C=C1 JXYITCJMBRETQX-UHFFFAOYSA-N 0.000 description 1
- ZHBXLZQQVCDGPA-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)sulfonyl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(S(=O)(=O)C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 ZHBXLZQQVCDGPA-UHFFFAOYSA-N 0.000 description 1
- JBXDPFLNXCZBSD-UHFFFAOYSA-N CC1(C=CCC(C)=CC2C1C2)N Chemical compound CC1(C=CCC(C)=CC2C1C2)N JBXDPFLNXCZBSD-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- KZTYYGOKRVBIMI-UHFFFAOYSA-N S-phenyl benzenesulfonothioate Natural products C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000006358 imidation reaction Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000343 polyazomethine Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- FDRPZJWMPZUHBN-UHFFFAOYSA-N triazin-2-ium;chloride Chemical compound Cl.C1=CN=NN=C1 FDRPZJWMPZUHBN-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Abstract
Description
本発明は、新規な芳香族ジアミン化合物及びその製造方法並びに該芳香族ジアミン化合物を原料とした合成樹脂に関する。より詳しくは、エチニルフェニルアミノ置換トリアジン骨格を有する芳香族ジアミン化合物とその製造方法並びに該芳香族ジアミン化合物を原料とした合成樹脂に関する。 The present invention relates to a novel aromatic diamine compound, a method for producing the same, and a synthetic resin using the aromatic diamine compound as a raw material. More specifically, the present invention relates to an aromatic diamine compound having an ethynylphenylamino-substituted triazine skeleton, a method for producing the same, and a synthetic resin using the aromatic diamine compound as a raw material.
従来の全芳香族ポリイミド、ポリアミド，ポリアゾメチンなどは優れた耐熱性を有すると共に、優れた機械的特性を有し、広く工業材料として使用されてきたが、これらの多くは有機溶媒に不溶であり、その成形性に多くの問題があった。
このような合成樹脂の中でアリール基を置換したポリイミドやポリアミドは有機溶媒に可溶であることが知られている（例えば，非特許文献１、非特許文献２）。
従って、かさ高いエチニルフェニルアミノ置換トリアジン骨格を有する芳香族ジアミン化合物を用いることにより、有機溶媒に可溶な（すなわち成形性に優れる）耐熱性合成樹脂を得ることが期待されている。
しかし、かかる期待や多くの試みにも関わらずトリアジン骨格を有する芳香族ジアミン化合物の合成に成功した例は未だ報告されておらず、トリアジン骨格を有する芳香族ジアミン化合物は、その製造方法も解明されていないため存在していない。
その結果、トリアジン骨格を有する芳香族ジアミン化合物から得られる合成樹脂が、優れた耐熱性、機械的特性及び成形性を実際に有しているかどうかも知られていない。
Conventional fully aromatic polyimides, polyamides, polyazomethines, etc. have excellent heat resistance and excellent mechanical properties, and have been widely used as industrial materials, but many of these are insoluble in organic solvents. There were many problems with its moldability.
Among such synthetic resins, it is known that polyimides and polyamides substituted with aryl groups are soluble in organic solvents (for example, Non-Patent Document 1 and Non-Patent Document 2).
Therefore, it is expected to obtain a heat-resistant synthetic resin that is soluble in an organic solvent (that is, excellent in moldability) by using an aromatic diamine compound having a bulky ethynylphenylamino-substituted triazine skeleton.
However, in spite of such expectations and many attempts, no examples of successful synthesis of aromatic diamine compounds having a triazine skeleton have been reported yet, and the production method of aromatic diamine compounds having a triazine skeleton has been elucidated. Does not exist.
As a result, it is not known whether a synthetic resin obtained from an aromatic diamine compound having a triazine skeleton actually has excellent heat resistance, mechanical properties, and moldability.
一方、特許文献１には、加熱による架橋が可能なペンダントフェニルエチニル基を有するポリイミドなどの高分子化合物の製造に用いられる芳香族ジアミン化合物であって、柔軟性に優れた骨格を有し、ポリイミドの熱成形性に寄与する芳香族ジアミン化合物が記載されている。該公報の段落番号（００２６）の式（５）には、１ ， ３ − ビス（ ３ − アミノフェノキシ） − ５ − （ フェニルエチニル） ベンゼンが記載されている。
しかし、この特許文献１記載技術では、基本骨格はトリアジン骨格ではなく、フェニルエチニル基が直接ベンゼン環に導入された骨格であり、該ポリイミドは熱成形性に優れているものの、溶解性に優れていないという問題があった。
On the other hand, Patent Document 1 discloses an aromatic diamine compound used for production of a polymer compound such as a polyimide having a pendant phenylethynyl group that can be crosslinked by heating, and has a skeleton excellent in flexibility. An aromatic diamine compound that contributes to the thermoformability of is described. Formula (5) in paragraph (0026) of this publication describes 1,3-bis (3-aminophenoxy) -5- (phenylethynyl) benzene.
However, in the technique described in Patent Document 1, the basic skeleton is not a triazine skeleton, but a skeleton in which a phenylethynyl group is directly introduced into a benzene ring. Although the polyimide has excellent thermoformability, it has excellent solubility. There was no problem.
本発明は、かかる問題を解決するべく、耐熱性および機械的特性に優れ、しかも有機溶媒に溶解できる成形性に優れた耐熱性合成樹脂の原料となる新規な芳香族ジアミン化合物及びその製造方法並びに該芳香族ジアミン化合物を原料とした合成樹脂を提供することを目的とする。 In order to solve such problems, the present invention provides a novel aromatic diamine compound that is a raw material for a heat-resistant synthetic resin that is excellent in heat resistance and mechanical properties and that is excellent in moldability that can be dissolved in an organic solvent, and a method for producing the same. It aims at providing the synthetic resin which used this aromatic diamine compound as a raw material.
請求項１に係る発明は、次式（化１）で表される芳香族ジアミン化合物に関する。 The invention according to claim 1 relates to an aromatic diamine compound represented by the following formula (Formula 1).
請求項２に係る発明は、次式（化２）で表される、請求項１に記載の芳香族ジアミン化合物に関する。
The invention according to
請求項３に係る発明は、次式（化３）で表されるトリアジンジクロリドを原料として、次式（化４）で表される芳香族ジアミン化合物を誘導することを特徴とする芳香族ジアミン化合物の製造方法に関する。 The invention according to claim 3 is characterized in that an aromatic diamine compound represented by the following formula (Chemical Formula 4) is derived from a triazine dichloride represented by the following formula (Chemical Formula 3) as a raw material. It relates to the manufacturing method.
請求項４に係る発明は、次式（化５）で表されるトリアジンジクロリドを原料として、次式（化６）で表される芳香族ジアミン化合物を誘導することを特徴とする、請求項３に記載の芳香族ジアミン化合物の製造方法に関する。 The invention according to claim 4 is characterized in that an aromatic diamine compound represented by the following formula (Chemical Formula 6) is derived from triazine dichloride represented by the following formula (Chemical Formula 5) as a raw material. It relates to the manufacturing method of the aromatic diamine compound as described in above.
請求項５に係る発明は、前記トリアジンジクロリドとジアミン化合物を塩基存在下に反応させて下記（化７）で表される芳香族ジアミン化合物を誘導する芳香族ジアミン化合物の製造方法。 The invention according to claim 5 is a method for producing an aromatic diamine compound in which the triazine dichloride and a diamine compound are reacted in the presence of a base to derive an aromatic diamine compound represented by the following (Chemical Formula 7).
請求項６に係る発明は、前記塩基として、炭酸カリウム、炭酸ナトリウム、炭酸セシウム、炭酸水素カリウム、炭酸水素ナトリウム及び炭酸水素セシウムから選ばれる１種以上を用いることを特徴とする請求項５に記載の芳香族ジアミン化合物の製造方法に関する。
The invention according to
請求項７に係る発明は、反応時の溶媒として、テトラヒドロフラン（ＴＨＦ）、ジオキサン、アセトン、メチルエチルケトン、シクロヘキサノン、Ｎ,Ｎ−ジメチルホルムアミド（ＤＭＦ）、Ｎ,Ｎ−ジメチルアセトアミド（ＤＭＡｃ）、Ｎ−メチルピロリドン（ＮＭＰ）、１，３-ジメチル-２-イミダゾリジノン（ＤＭＩ）を使用することを特徴とする請求項５又は６に記載の芳香族ジアミン化合物の製造方法に関する。
In the invention according to claim 7, as a solvent during the reaction, tetrahydrofuran (THF), dioxane, acetone, methyl ethyl ketone, cyclohexanone, N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N-methyl The method for producing an aromatic diamine compound according to
請求項８に係る発明は、反応温度が２０〜２００℃であることを特徴とする請求項５乃至７のいずれかに記載の芳香族ジアミン化合物の製造方法に関する。 The invention according to claim 8 relates to the method for producing an aromatic diamine compound according to any one of claims 5 to 7, wherein the reaction temperature is 20 to 200 ° C.
請求項９に係る発明は、前記トリアジンジクロリドは、塩化シアヌルとエチニルフェニルアミン化合物を塩基存在下に反応させて製造することを特徴とする請求項４乃至８のいずれかに記載の芳香族ジアミン化合物の製造方法に関する。 The invention according to claim 9 is the aromatic diamine compound according to any one of claims 4 to 8, wherein the triazine dichloride is produced by reacting cyanuric chloride and an ethynylphenylamine compound in the presence of a base. It relates to the manufacturing method.
請求項１０に係る発明は、請求項１又は２に記載の芳香族ジアミン化合物を用いて合成した芳香族ポリイミド合成樹脂に関する。
The invention according to claim 10 relates to an aromatic polyimide synthetic resin synthesized using the aromatic diamine compound according to
請求項１１に係る発明は、請求項１又は２に記載の芳香族ジアミン化合物と、ペルフルオロノネニル基含有ジアミン（ＦＮＤＡ）とを用いて合成した含フッ素芳香族ポリイミド合成樹脂に関する。
The invention according to claim 11 relates to a fluorine-containing aromatic polyimide synthetic resin synthesized using the aromatic diamine compound according to
請求項１２に係る発明は、さらにビフェニルテトラカルボン酸二無水物を用いて合成した請求項１０又は１１に記載の芳香族ポリイミド合成樹脂に関する。 The invention according to claim 12 relates to the aromatic polyimide synthetic resin according to claim 10 or 11, further synthesized using biphenyltetracarboxylic dianhydride.
請求項１及び２に係る発明によれば、耐熱性および機械的特性に優れ、しかも有機溶媒に溶解できる成形性に優れた耐熱性合成樹脂の原料となる新規な芳香族ジアミン化合物を提供することができる。
請求項３乃至５に係る発明によれば、トリアジンジクロリドを原料として、耐熱性および機械的特性に優れ、しかも有機溶媒に溶解できる成形性に優れた耐熱性合成樹脂の原料となる新規な芳香族ジアミン化合物を製造することができる。
請求項６乃至８に係る発明によれば、本発明の芳香族ジアミン化合物を収率よく製造することができる。
請求項９に係る発明によれば原料となるトリアジンクロリドを容易に製造することができるので本発明の芳香族ジアミン化合物を大量に製造することができる。
請求項１０乃至１１に係る発明によれば易加工性と耐溶剤性を有するコーティング合成樹脂を提供することができる。
According to the inventions according to
According to the inventions according to claims 3 to 5, a novel aromatic compound that is a raw material for a heat-resistant synthetic resin that is excellent in heat resistance and mechanical properties and can be dissolved in an organic solvent using triazine dichloride as a raw material. A diamine compound can be produced.
According to the
Since the triazine chloride used as a raw material can be manufactured easily according to the invention concerning Claim 9, the aromatic diamine compound of this invention can be manufactured in large quantities.
According to the invention which concerns on Claims 10 thru | or 11, the coating synthetic resin which has easy workability and solvent resistance can be provided.
本発明者は、トリアジン骨格を有する芳香族ジアミン化合物を得る方法について鋭意研究を行った。かかる化合物を合成するための条件は、多大に上り、その条件を洗い直したところ、使用する原料に左右されることが判明した。ただ、同じ材料であっても、合成がなされる場合となされない場合とがあり、一定の原料の選択は、必要条件ではあるが、その他にも合成を左右する条件が存在することが分かった。多大な合成条件を鋭意研究し、その条件を解明し、本発明をなすに到った。
以下、本発明を具体的に説明する。
This inventor earnestly researched about the method of obtaining the aromatic diamine compound which has a triazine frame | skeleton. The conditions for synthesizing such compounds have increased greatly, and after re-washing the conditions, it has been found that the conditions depend on the raw materials used. However, even if the same material is used, it may or may not be synthesized, and selection of a certain raw material is a necessary condition, but there are other conditions that affect synthesis. . We have intensively studied a lot of synthesis conditions, elucidated the conditions, and arrived at the present invention.
Hereinafter, the present invention will be specifically described.
本発明は、以下の一般式（Ｉ）で表される芳香族ジアミン化合物である。 The present invention is an aromatic diamine compound represented by the following general formula (I).
好ましくは、式（ＩＩ）で表される芳香族ジアミン化合物（２，４‐ビス（ｐ‐アミノアニリノ）‐６‐（ｐ‐エチニルアニリノ）‐１，３，５‐トリアジン）である。
An aromatic diamine compound represented by the formula (II) (2,4-bis (p-aminoanilino) -6- (p-ethynylanilino) -1,3,5-triazine) is preferable.
本発明の一般式（Ｉ）で表される芳香族ジアミン化合物は以下の一般式（ＩＩＩ）によって表されるトリアジンジクロリドを原料として製造することができる。 The aromatic diamine compound represented by the general formula (I) of the present invention can be produced using triazine dichloride represented by the following general formula (III) as a raw material.
好ましい化合物である上記式（ＩＩ）で表される芳香族ジアミン化合物は、以下の式（ＩＶ）で表されるトリアジンジクロリドを原料として製造することができる。 The aromatic diamine compound represented by the above formula (II), which is a preferred compound, can be produced using triazine dichloride represented by the following formula (IV) as a raw material.
この上記一般式（ＩＶ）によって表されるトリアジンジクロリドは、塩化シアヌルとエチニルフェニルアミン化合物を塩基存在下で反応させることにより、容易に製造することができる。 The triazine dichloride represented by the general formula (IV) can be easily produced by reacting cyanuric chloride with an ethynylphenylamine compound in the presence of a base.
上記一般式（Ｉ）および式（ＩＩ）によって表される芳香族ジアミン化合物の製造は、それぞれ上記一般式（ＩＩＩ）および式（ＩＶ）で表されるトリアジンジクロリドを原料として、一段階の工程で行われる。
以下、代表的な例によって説明する。
Production of the aromatic diamine compound represented by the general formula (I) and the formula (II) is a one-step process using the triazine dichloride represented by the general formula (III) and the formula (IV) as raw materials, respectively. Done.
Hereinafter, a typical example will be described.
上記一般式（Ｉ）および式（ＩＩ）で表される芳香族ジアミン化合物は、それぞれ上記一般式（ＩＩＩ）および式（ＩＶ）で表されるトリアジンジクロリドと過剰のジアミン化合物を塩基存在下に反応させることによって得られる。 The aromatic diamine compounds represented by the above general formulas (I) and (II) react with the triazine dichloride represented by the above general formulas (III) and (IV), respectively, in the presence of a base. To obtain.
ジアミン化合物の量は，トリアジンジクロリドの量の１０〜２０倍molとすることが好ましい。１０倍molより少なければトリアジンジクロリドとジアミン化合物の重合が起こってしまい，２０倍molより多ければ目的とする芳香族ジアミン化合物の製造効率が低くなるので，いずれの場合も収率が悪くなり好ましくないからである。 The amount of the diamine compound is preferably 10 to 20 times mol of the amount of triazine dichloride. If it is less than 10 times mol, polymerization of triazine dichloride and a diamine compound occurs, and if it is more than 20 times mol, the production efficiency of the desired aromatic diamine compound is lowered. Because.
反応溶媒中には塩基を存在させることで、副生する塩化水素を中和することができる。
この反応に用いる塩基としては、炭酸カリウム、炭酸ナトリウム、炭酸セシウム、炭酸水素カリウム、炭酸水素ナトリウム、炭酸水素セシウムなどが好ましい。
The presence of a base in the reaction solvent can neutralize by-produced hydrogen chloride.
As the base used in this reaction, potassium carbonate, sodium carbonate, cesium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, cesium hydrogen carbonate and the like are preferable.
反応溶媒としては、テトラヒドロフラン（ＴＨＦ）、ジオキサンなどのエーテル系溶媒、アセトン、メチルエチルケトン、シクロヘキサノンなどのケトン系溶媒、Ｎ,Ｎ−ジメチルホルムアミド（ＤＭＦ）、Ｎ,Ｎ−ジメチルアセトアミド（ＤＭＡｃ）、Ｎ−メチルピロリドン（ＮＭＰ）、１，３-ジメチル-２-イミダゾリジノン（ＤＭＩ）などの非プロトン性極性溶媒が好ましい。 Examples of the reaction solvent include ether solvents such as tetrahydrofuran (THF) and dioxane, ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone, N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N- Aprotic polar solvents such as methylpyrrolidone (NMP) and 1,3-dimethyl-2-imidazolidinone (DMI) are preferred.
反応温度は２０〜２００℃が好ましい。２０℃より低い温度もしくは２００℃よりも高い温度であれば、芳香族ジアミン化合物を製造することができないからである。尚、経済的には３０℃〜１５０℃の温度範囲がより好ましい。 The reaction temperature is preferably 20 to 200 ° C. This is because an aromatic diamine compound cannot be produced if the temperature is lower than 20 ° C or higher than 200 ° C. In terms of economy, a temperature range of 30 ° C to 150 ° C is more preferable.
反応時間は用いた試薬の種類や量、溶媒の種類、反応温度などによって異なるが、一般に数十分から数日間反応させるのが好ましい。 While the reaction time varies depending on the type and amount of the reagent used, the type of solvent, the reaction temperature, etc., it is generally preferable to carry out the reaction for several tens of minutes to several days.
このようにして得られる上記一般式（Ｉ）および式（ＩＩ）の芳香族ジアミン化合物はそのまま種々の高分子化合物の原料となる。 The aromatic diamine compounds of the above general formulas (I) and (II) thus obtained are used as raw materials for various polymer compounds as they are.
以下、本発明を実施例によって具体的に説明するが、本発明は下記実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to the following Example.
〈試験方法〉
以下の実施例において、得られる化合物の組成・構造の同定等は、次の手法により行った。
（Ａ）ＦＴ‐ＩＲ（フーリエ変換赤外分光法）（ＫＢｒ，ｃｍ−１）：ＪＡＳＣＯ ＦＴ-ＩＲ４２００を用いて、ＫＢr錠剤法により測定した。
（Ｂ）１Ｈ ＮＭＲ（核磁気共鳴分光法）（４００ＭＨｚ，ｐｐｍ）：Ｂｕｒｕｋｅｒ ＡＣ４００を用いて、テトラメチルシラン（ＴＭＳ）を含む重水素化溶媒中で測定した。
（Ｃ）１３Ｃ ＮＭＲ（核磁気共鳴分光法）（１００Ｈｚ，ｐｐｍ）：Ｂｕｒｕｋｅｒ ＡＣ４００を用いて、テトラメチルシラン（ＴＭＳ）を含む重水素化溶媒中で測定した。
（Ｄ）元素分析：ＰｅｒｋｉｎＥｌｍｅｒ２４００を用いて、炭素、水素および窒素元素の定量分析を行った。
<Test method>
In the following examples, the composition and structure of the obtained compound were identified by the following method.
(A) FT-IR (Fourier transform infrared spectroscopy) (KBr, cm −1 ): Measured by the KBr tablet method using JASCO FT-IR4200.
(B) 1 H NMR (nuclear magnetic resonance spectroscopy) (400 MHz, ppm): Measured in a deuterated solvent containing tetramethylsilane (TMS) using a Buruker AC400.
(C) 13 C NMR (nuclear magnetic resonance spectroscopy) (100 Hz, ppm): Measured in a deuterated solvent containing tetramethylsilane (TMS) using a Burker AC400.
(D) Elemental analysis: Using a PerkinElmer 2400, quantitative analysis of carbon, hydrogen and nitrogen elements was performed.
（実施例１）
（トリアジンジクロリドの製造）
以下の操作により、芳香族ジアミン化合物の原料となるトリアジンジクロリドの製造を行った。
Example 1
(Production of triazine dichloride)
Triazine dichloride as a raw material for the aromatic diamine compound was produced by the following operation.
〈操作〉
マグネット攪拌子、塩化カルシウム管、滴下ロートおよび温度計を備えた５００ｍＬの三口フラスコに、１８．４４ｇ（０．１０ｍｏｌ）の塩化シアヌルと１００ｍＬのテトラヒドロフラン（ＴＨＦ）を入れ、攪拌しながら溶解させた後に、氷浴で０〜５℃に冷却した。１１．７２ｇ（０．１０ｍｏｌ）のｐ‐エチニルアニリンを６０ｍＬのＴＨＦに溶かした溶液を温度上昇に注意しながらゆっくりと滴下し、０〜５℃で２時間撹拌した。
<operation>
After putting 18.44 g (0.10 mol) of cyanuric chloride and 100 mL of tetrahydrofuran (THF) into a 500 mL three-necked flask equipped with a magnetic stirrer, calcium chloride tube, dropping funnel and thermometer, and dissolving them with stirring. Cooled in an ice bath to 0-5 ° C. A solution prepared by dissolving 11.72 g (0.10 mol) of p-ethynylaniline in 60 mL of THF was slowly added dropwise while paying attention to the temperature rise, and the mixture was stirred at 0 to 5 ° C. for 2 hours.
次に、５．３０ｇ（０．０５ｍｏｌ）の炭酸ナトリウムを３０ｍＬの蒸留水に溶かした水溶液を、温度上昇に注意しながらゆっくりと滴下し、０〜５℃で２時間撹拌した。その後、反応混合物を飽和食塩水で洗浄し、有機層を回収した。有機層を無水硫酸ナトリウムで一晩乾燥した。無水硫酸ナトリウムをろ別した後、ろ液からＴＨＦを留去することにより、６‐（ｐ‐エチニルアニリノ）‐１，３，５‐トリアジン‐２，４‐ジクロリドの粗生成物を得た。これをヘキサン／トルエンの混合溶媒により再結晶した後、１４０℃／０．１Ｔｏｒｒで昇華精製し、さらに再結晶を行い、８０℃で９時間減圧乾燥した。 Next, an aqueous solution prepared by dissolving 5.30 g (0.05 mol) of sodium carbonate in 30 mL of distilled water was slowly added dropwise while being careful of temperature rise, and stirred at 0 to 5 ° C. for 2 hours. Thereafter, the reaction mixture was washed with saturated brine, and the organic layer was recovered. The organic layer was dried over anhydrous sodium sulfate overnight. After filtering off anhydrous sodium sulfate, THF was distilled off from the filtrate to obtain a crude product of 6- (p-ethynylanilino) -1,3,5-triazine-2,4-dichloride. . This was recrystallized with a mixed solvent of hexane / toluene, purified by sublimation at 140 ° C./0.1 Torr, further recrystallized, and dried under reduced pressure at 80 ° C. for 9 hours.
上記の操作により得られた結晶について特性を調査した。その結果を以下に示す。
〈結果〉
（１）形状：無色針状結晶
（２）収率：５４％（１４．３ｇ）
（３）融点：１９９〜２００℃
（４）ＦＴ‐ＩＲ（ＫＢｒ，ｃｍ−１）：３２８７（Ｎ-Ｈ），２１０４（Ｃ≡Ｃ），１６１５（Ｃ＝Ｃ），１５４１（Ｃ＝Ｎ）
（５）１Ｈ ＮＭＲ（４００ＭＨｚ，ａｃｅｔｏｎｅ‐ｄ6，ｐｐｍ）：３．６５（ｓ，１Ｈ，Ｃ≡ＣＨ），７．５４（ｄ，２Ｈ，ｐｈｅｎｙｌｅｎｅ），７．７９（ｄ，２Ｈ，ｐｈｅｎｙｌｅｎｅ），１０．０２（ｓ，１Ｈ，ＮＨ）
（６）１３Ｃ ＮＭＲ（１００Ｈｚ，ａｃｅｔｏｎｅ‐ｄ6，ｐｐｍ）：７９．２，８３．８（Ｃ≡Ｃ），１１９．４，１２１．９，１３３．４，１３８．４（ｐｈｅｎｙｌｅｎｅ），１６５．２，１６９．５，１７０．５（ｔｒｉａｚｉｎｅ）
（７）元素分析（Ｃ１１Ｈ６Ｃｌ2Ｎ4 分子量２６５．１０）
計算値：Ｃ：４９．８４％，Ｈ：２．２８％，Ｎ：２１．１３％
実験値：Ｃ：４９．９７％，Ｈ：２．５４％，Ｎ：２１．２２％
The characteristics of the crystals obtained by the above operation were investigated. The results are shown below.
<result>
(1) Shape: colorless needle crystal (2) Yield: 54% (14.3 g)
(3) Melting point: 199-200 ° C
(4) FT-IR (KBr, cm −1 ): 3287 (N—H), 2104 (C≡C), 1615 (C = C), 1541 (C = N)
(5) 1 H NMR (400 MHz, acetone-d 6 , ppm): 3.65 (s, 1H, C≡CH), 7.54 (d, 2H, phenylene), 7.79 (d, 2H, phenylene) ), 10.02 (s, 1H, NH)
(6) 13 C NMR (100 Hz, acetone-d 6 , ppm): 79.2, 83.8 (C≡C), 119.4, 121.9, 133.4, 138.4 (phenylene), 165 .2,169.5,170.5 (triazine)
(7) Elemental analysis (C 11 H 6 Cl 2 N 4 molecular weight 265.10)
Calculated values: C: 49.84%, H: 2.28%, N: 21.13%
Experimental value: C: 49.97%, H: 2.54%, N: 21.22%
（芳香族ジアミン化合物の製造）
上記の操作により得られた結晶を原料として以下の操作により芳香族ジアミン化合物を製造した。本例における芳香族ジアミン化合物は、前記式（ＩＩ）で表される２，４‐ビス（ｐ‐アミノアニリノ）‐６‐（ｐ‐エチニルアニリノ）‐１，３，５‐トリアジンである。
(Production of aromatic diamine compounds)
An aromatic diamine compound was produced by the following operation using the crystal obtained by the above operation as a raw material. The aromatic diamine compound in this example is 2,4-bis (p-aminoanilino) -6- (p-ethynylanilino) -1,3,5-triazine represented by the formula (II).
〈操作〉
マグネット攪拌子、冷却管、滴下ロートおよび窒素導入管を備えた５００ｍＬの三口フラスコに、１００ｍＬの１，４‐ジオキサン、５．３０ｇ（０．０５０ｍｏｌ）の炭酸ナトリウムおよび５４．０７ｇ（０．５０ｍｏｌ）のｐ‐フェニレンジアミンを加え、還流温度で攪拌し溶解させた。そこに、１３．２６ｇ（０．０５０ｍｏｌ）の６‐（ｐ‐エチニルアニリノ）‐１，３，５‐トリアジン‐２，４‐ジクロリドを２５０ｍＬの１，４‐ジオキサンに溶かした溶液をゆっくりと滴下した。その後、還流温度のまま一晩攪拌した。反応混合物を１．５Ｌの熱水に投入し、生成物を析出させた。
<operation>
To a 500 mL three-necked flask equipped with a magnetic stir bar, condenser, dropping funnel and nitrogen inlet tube, add 100 mL of 1,4-dioxane, 5.30 g (0.050 mol) of sodium carbonate and 54.07 g (0.50 mol). Of p-phenylenediamine was added and stirred at reflux temperature to dissolve. Then slowly add a solution of 13.26 g (0.050 mol) of 6- (p-ethynylanilino) -1,3,5-triazine-2,4-dichloride in 250 mL of 1,4-dioxane. It was dripped. Thereafter, the mixture was stirred overnight at the reflux temperature. The reaction mixture was poured into 1.5 L of hot water to precipitate the product.
これを熱水で４回、蒸留水で１回洗浄した。ろ過により回収した析出物をアセトン中で３０分間加熱還流させ、不溶分をろ別した。ろ液からアセトンを留去することにより、褐色の粗生成物を得た。これを活性炭を用いて１，４‐ジオキサン／ヘキサンの混合溶媒により２回再結晶を行い、１００℃で９時間減圧乾燥した。 This was washed 4 times with hot water and once with distilled water. The precipitate collected by filtration was heated to reflux in acetone for 30 minutes, and the insoluble matter was filtered off. Acetone was distilled off from the filtrate to obtain a brown crude product. This was recrystallized twice using a mixed solvent of 1,4-dioxane / hexane using activated carbon, and dried under reduced pressure at 100 ° C. for 9 hours.
〈結果〉
（１）形状：淡黄色粉末結晶
（２）収率：６３％（１２．９ｇ）
（３）融点：２４２〜２４４℃（硬化反応）
（４）ＦＴ‐ＩＲ（ＫＢｒ，ｃｍ−１）：３３６５（Ｎ‐Ｈ），２１０１（Ｃ≡Ｃ），１６１０（Ｃ＝Ｃ），１５７０（Ｃ＝Ｎ），１５０１（Ｃ＝Ｃ）
（５）１Ｈ ＮＭＲ（４００ＭＨｚ，ＤＭＳО‐ｄ6，ｐｐｍ）：４．００（ｓ，１Ｈ，Ｃ≡ＣＨ），４．８１（ｓ，４Ｈ，ＮＨ２），６．５５（ｄ，４Ｈ，ｐｈｅｎｙｌｅｎｅ），７．３３-７．３５（ｍ，６Ｈ，ｐｈｅｎｙｌｅｎｅ），７．８６（ｄ，２Ｈ，ｐｈｅｎｙｌｅｎｅ），８．７１（ｓ，２Ｈ，ＮＨ），９．１９（ｓ，１Ｈ，ＮＨ）（図１参照）
（６）１３Ｃ ＮＭＲ（１００Ｈｚ，ＤＭＳО‐ｄ6，ｐｐｍ）：７９．３，８４．１（Ｃ≡Ｃ），１１３．９，１１９．４，１２２．９，１２８．８，１３１．９，１４１．３，１４４．３（ｐｈｅｎｙｌｅｎｅ），１６３．９，１６４．２（ｔｒｉａｚｉｎｅ）（図２参照）
（７）元素分析（Ｃ２３Ｈ２０Ｎ８ 分子量４０８．４６）
計算値：Ｃ：６７．６３％、Ｈ：４．９４％、Ｎ：２７．４３％
実験値：Ｃ：６７．４６％、Ｈ：４．９７％、Ｎ：２７．４５％
<result>
(1) Shape: pale yellow powder crystal (2) Yield: 63% (12.9 g)
(3) Melting point: 242-244 ° C. (curing reaction)
(4) FT-IR (KBr, cm -1 ): 3365 (NH), 2101 (C≡C), 1610 (C = C), 1570 (C = N), 1501 (C = C)
(5) 1 H NMR (400 MHz, DMSO-d 6 , ppm): 4.00 (s, 1H, C≡CH), 4.81 (s, 4H, NH 2 ), 6.55 (d, 4H, phenylene), 7.33-7.35 (m, 6H, phenylene), 7.86 (d, 2H, phenylene), 8.71 (s, 2H, NH), 9.19 (s, 1H, NH) (See Figure 1)
(6) 13 C NMR (100 Hz, DMSO-d 6 , ppm): 79.3, 84.1 (C≡C), 113.9, 119.4, 122.9, 128.8, 131.9, 141.3, 144.3 (phenylene), 163.9, 164.2 (triazine) (see FIG. 2)
(7)
Calculated values: C: 67.63%, H: 4.94%, N: 27.43%
Experimental values: C: 67.46%, H: 4.97%, N: 27.45%
（実施例２）
（合成樹脂の製造）
本例では、本発明に係る芳香族ジアミン化合物を用いて含フッ素芳香族ポリイミドを合成した。ペルフルオロノネニル基含有ジアミン（ＦＮＤＡ）とエチニル基含有ジアミン（ＥＤＡ）を種々のモル比（総モル量２．５ｍｍｏｌ）でＮＭＰ（１０ｍＬ）に溶解させた。この溶液にビフェニルテトラカルボン酸二無水物（ＢＰＤＡ）（２．５ｍｍｏｌ）を加え、６時間反応させ、ポリアミド酸溶液を得た。この溶液をガラス板にキャストし、段階的に３００〜３５０℃まで加熱してポリイミドフィルムを作製した。
尚、反応式は図３に示した。
(Example 2)
(Manufacture of synthetic resin)
In this example, a fluorine-containing aromatic polyimide was synthesized using the aromatic diamine compound according to the present invention. Perfluorononenyl group-containing diamine (FNDA) and ethynyl group-containing diamine (EDA) were dissolved in NMP (10 mL) at various molar ratios (total molar amount 2.5 mmol). Biphenyltetracarboxylic dianhydride (BPDA) (2.5 mmol) was added to this solution and reacted for 6 hours to obtain a polyamic acid solution. This solution was cast on a glass plate and heated stepwise to 300 to 350 ° C. to produce a polyimide film.
The reaction formula is shown in FIG.
上記した通り、ペルフルオロノネニル基含有ジアミン（ＦＮＤＡ）とエチニル基含有ジアミン（ＥＤＡ）のジアミンモノマーと、テトラカルボン酸二無水物（ＢＰＤＡ）の重付加により、対数粘度が０．６〜１．３ｄＬ／ｇの高分子量のポリアミド酸を合成した。 As described above, the logarithmic viscosity is 0.6 to 1.3 dL by polyaddition of a diamine monomer of a perfluorononenyl group-containing diamine (FNDA) and an ethynyl group-containing diamine (EDA) and tetracarboxylic dianhydride (BPDA). / G high molecular weight polyamic acid was synthesized.
これを化学イミド化することによりＮＭＰやＤＭＩなどの溶媒に可溶なポリイミド共重合体を得ることができた。また、３００℃で熱イミド化することによりポリイミド共重合体フィルムを作製することができた。熱イミド化したポリイミドについてはＥＤＡ含量５０ｍｏｌ％以上で不溶化となり、３５０℃で熱イミド化したポリイミドについてはＥＤＡ含量が２０ｍｏｌ％以上で不溶化となった。熱イミド過程でエチニル基の熱架橋反応が起こったためである。 By chemically imidizing this, a polyimide copolymer soluble in a solvent such as NMP or DMI could be obtained. Moreover, the polyimide copolymer film was able to be produced by carrying out the thermal imidation at 300 degreeC. The thermally imidized polyimide was insolubilized at an EDA content of 50 mol% or more, and the polyimide imidized at 350 ° C. was insolubilized at an EDA content of 20 mol% or more. This is because the thermal crosslinking reaction of the ethynyl group occurred during the thermal imide process.
ＥＤＡ含量が増加するにつれて、ガラス転移温度は２８７℃から３４１℃に増加し、熱膨張係数は４３から２０ｐｐｍ／℃に減少した。また、動的粘弾性測定では、ＥＤＡ含量が増加するにつれてガラス転移温度以上での貯蔵弾性率は高くなった。 As the EDA content increased, the glass transition temperature increased from 287 ° C. to 341 ° C. and the coefficient of thermal expansion decreased from 43 to 20 ppm / ° C. In the dynamic viscoelasticity measurement, the storage elastic modulus above the glass transition temperature increased as the EDA content increased.
フィルムの引張特性に関しては、ＥＤＡ含量が増加するにつれて引張強度が９５から１２１ＭＰａに増加し、破断伸びは７から２％に低下し、引張弾性率は５から８ＧＰａに増加した。さらに、フィルム表面の水の接触角は、ＥＤＡ含量が５０mol％まで９０°以上と高い撥水性を示し、フィルム最表面にフッ素原子団が偏析していた。 Regarding the tensile properties of the film, as the EDA content increased, the tensile strength increased from 95 to 121 MPa, the elongation at break decreased from 7 to 2%, and the tensile modulus increased from 5 to 8 GPa. Furthermore, the water contact angle on the film surface showed a high water repellency of 90 ° or more until the EDA content was 50 mol%, and fluorine atom groups were segregated on the outermost surface of the film.
以上の結果から、本発明の含フッ素芳香族ポリイミドは、易加工性と耐溶剤性を有するフッ素系コーティング合成樹脂としての応用も可能であることが分かった。
上記の結果を表１に示す。
From the above results, it was found that the fluorine-containing aromatic polyimide of the present invention can be applied as a fluorine-based coating synthetic resin having easy processability and solvent resistance.
The results are shown in Table 1.
なお、上記重合における原料としてビフェニルテトラカルボン酸二無水物（ＢＰＤＡ）を例示したが、それ以外に、ピロメリト酸二無水物（ＰＭＤＡ）、ベンゾフェノンテトラカルボン酸二無水物（ＢＴＤＡ）、ジフェニルスルホンテトラカルボン酸二無水物（ＤＳＤＡ）、オキシジフタル酸二無水物（ＯＤＰＡ）、ヘキサフルオロイソプロピリデンジフタル酸二無水物（６ＦＤＡ）等についても同様の結果が得られた。 In addition, although biphenyl tetracarboxylic dianhydride (BPDA) was illustrated as a raw material in the said superposition | polymerization, pyromellitic dianhydride (PMDA), benzophenone tetracarboxylic dianhydride (BTDA), diphenyl sulfone tetracarboxylic other than that was illustrated. Similar results were obtained for acid dianhydride (DSDA), oxydiphthalic dianhydride (ODPA), hexafluoroisopropylidenediphthalic dianhydride (6FDA), and the like.
本発明により耐熱性及び機械的特性に優れ、しかも有機溶媒に溶解できるため、成形性にも優れた耐熱性、耐溶剤性合成樹脂の原料となる新規な芳香族ジアミン化合物及びその製造方法並びに該芳香族ジアミン化合物を原料とした合成樹脂が提供される。 According to the present invention, it is excellent in heat resistance and mechanical properties, and can be dissolved in an organic solvent. Therefore, it is excellent in moldability. A novel aromatic diamine compound as a raw material for a solvent-resistant synthetic resin, a method for producing the same, and the method A synthetic resin using an aromatic diamine compound as a raw material is provided.
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Cited By (5)
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| JP2011257731A (en) * | 2010-05-10 | 2011-12-22 | Jnc Corp | Diamine, liquid crystal aligning agent and liquid crystal display element |
| WO2013024820A1 (en) * | 2011-08-12 | 2013-02-21 | 宇部興産株式会社 | Polyimide precursor, polyimide, polyimide film, and method for manufacturing triazine compound used for manufacturing same |
| JP2014005228A (en) * | 2012-06-22 | 2014-01-16 | Iwate Univ | Aromatic diamine compound and method of producing the same, and aromatic polyimide synthetic resin |
| CN107200845A (en) * | 2017-06-14 | 2017-09-26 | 中国科学院上海有机化学研究所 | A kind of high glass-transition temperature and low thermal expansion coefficient polyimide and its preparation method and application |
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| JP2007297319A (en) * | 2006-04-28 | 2007-11-15 | Wakayama Seika Kogyo Kk | 1,3-bis(aminophenoxy)-5-(phenylethynyl)benzene derivative and method for producing the same |
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| JP2011257731A (en) * | 2010-05-10 | 2011-12-22 | Jnc Corp | Diamine, liquid crystal aligning agent and liquid crystal display element |
| WO2013024820A1 (en) * | 2011-08-12 | 2013-02-21 | 宇部興産株式会社 | Polyimide precursor, polyimide, polyimide film, and method for manufacturing triazine compound used for manufacturing same |
| KR20140051405A (en) * | 2011-08-12 | 2014-04-30 | 우베 고산 가부시키가이샤 | Polyimide precursor, polyimide, polyimide film, and method for manufacturing triazine compound used for manufacturing same |
| CN103874723A (en) * | 2011-08-12 | 2014-06-18 | 宇部兴产株式会社 | Polyimide precursor, polyimide, polyimide film, and method for manufacturing triazine compound used for manufacturing same |
| JPWO2013024820A1 (en) * | 2011-08-12 | 2015-03-05 | 宇部興産株式会社 | Polyimide precursor, polyimide, polyimide film, and method for producing triazine compound used for production thereof |
| US9511565B2 (en) | 2011-08-12 | 2016-12-06 | Ube Industries, Ltd. | Polyimide precursor, polyimide, polyimide film, and method for manufacturing triazine compound used for manufacturing same |
| KR101945073B1 (en) | 2011-08-12 | 2019-02-01 | 우베 고산 가부시키가이샤 | Polyimide precursor, polyimide, polyimide film, and method for manufacturing triazine compound used for manufacturing same |
| JP2014005228A (en) * | 2012-06-22 | 2014-01-16 | Iwate Univ | Aromatic diamine compound and method of producing the same, and aromatic polyimide synthetic resin |
| CN107200845A (en) * | 2017-06-14 | 2017-09-26 | 中国科学院上海有机化学研究所 | A kind of high glass-transition temperature and low thermal expansion coefficient polyimide and its preparation method and application |
| JP2019156921A (en) * | 2018-03-09 | 2019-09-19 | 国立大学法人岩手大学 | Polyimide, polyimide film, polyimide metal laminate, and polyamide acid |
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