JP5026727B2 - Method for producing high purity cyanate ester - Google Patents
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- JP5026727B2 JP5026727B2 JP2006101491A JP2006101491A JP5026727B2 JP 5026727 B2 JP5026727 B2 JP 5026727B2 JP 2006101491 A JP2006101491 A JP 2006101491A JP 2006101491 A JP2006101491 A JP 2006101491A JP 5026727 B2 JP5026727 B2 JP 5026727B2
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- naphthols
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- 239000004643 cyanate ester Substances 0.000 title claims description 38
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- -1 cyanogen halide Chemical class 0.000 claims description 39
- 150000003512 tertiary amines Chemical class 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 150000004780 naphthols Chemical class 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 23
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 21
- 239000003960 organic solvent Substances 0.000 claims description 19
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims description 10
- 230000002378 acidificating effect Effects 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 3
- 230000002051 biphasic effect Effects 0.000 claims description 3
- 239000003929 acidic solution Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 description 28
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 27
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 27
- 239000000243 solution Substances 0.000 description 16
- 239000012071 phase Substances 0.000 description 15
- 239000006227 byproduct Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000012044 organic layer Substances 0.000 description 8
- QPJDMGCKMHUXFD-UHFFFAOYSA-N cyanogen chloride Chemical compound ClC#N QPJDMGCKMHUXFD-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000004811 liquid chromatography Methods 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 150000001913 cyanates Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical class NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- BDQNKCYCTYYMAA-UHFFFAOYSA-N O=C=Nc1cccc2c1cccc2 Chemical compound O=C=Nc1cccc2c1cccc2 BDQNKCYCTYYMAA-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- ATDGTVJJHBUTRL-UHFFFAOYSA-N cyanogen bromide Chemical compound BrC#N ATDGTVJJHBUTRL-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000003918 potentiometric titration Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 2
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 1
- LJPCNSSTRWGCMZ-UHFFFAOYSA-N 3-methyloxolane Chemical compound CC1CCOC1 LJPCNSSTRWGCMZ-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- MGHPNCMVUAKAIE-UHFFFAOYSA-N diphenylmethanamine Chemical compound C=1C=CC=CC=1C(N)C1=CC=CC=C1 MGHPNCMVUAKAIE-UHFFFAOYSA-N 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- MXHTZQSKTCCMFG-UHFFFAOYSA-N n,n-dibenzyl-1-phenylmethanamine Chemical compound C=1C=CC=CC=1CN(CC=1C=CC=CC=1)CC1=CC=CC=C1 MXHTZQSKTCCMFG-UHFFFAOYSA-N 0.000 description 1
- FRQONEWDWWHIPM-UHFFFAOYSA-N n,n-dicyclohexylcyclohexanamine Chemical compound C1CCCCC1N(C1CCCCC1)C1CCCCC1 FRQONEWDWWHIPM-UHFFFAOYSA-N 0.000 description 1
- ORSUTASIQKBEFU-UHFFFAOYSA-N n,n-diethylbutan-1-amine Chemical compound CCCCN(CC)CC ORSUTASIQKBEFU-UHFFFAOYSA-N 0.000 description 1
- LSXCWVFVNJOMIX-UHFFFAOYSA-N n,n-diethylcyclohexanamine;pyridine Chemical compound C1=CC=NC=C1.CCN(CC)C1CCCCC1 LSXCWVFVNJOMIX-UHFFFAOYSA-N 0.000 description 1
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 description 1
- OOHAUGDGCWURIT-UHFFFAOYSA-N n,n-dipentylpentan-1-amine Chemical compound CCCCCN(CCCCC)CCCCC OOHAUGDGCWURIT-UHFFFAOYSA-N 0.000 description 1
- MTHFROHDIWGWFD-UHFFFAOYSA-N n-butyl-n-methylbutan-1-amine Chemical compound CCCCN(C)CCCC MTHFROHDIWGWFD-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229940031826 phenolate Drugs 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Description
本発明は、シアン酸エステルの工業的に有利な製造方法に関する。 The present invention relates to an industrially advantageous process for producing cyanate esters.
シアン酸エステルは、プリント基板用、電子部品の封止用、複合材料用、成形材料用及び接着材料用等として有用である。
従来、このシアン酸エステルの製造方法として、（１）ハロゲン化シアンとフェノール類を３級アミン存在下で反応させる方法、（２）アルコール系またはフェノール系のアルカリ金属塩とハロゲン化シアンとを反応させる方法が知られている。
The cyanate ester is useful for printed circuit boards, sealing electronic components, composite materials, molding materials, adhesive materials, and the like.
Conventionally, as a method for producing this cyanate ester, (1) a method in which cyanogen halide and phenols are reacted in the presence of a tertiary amine, and (2) a reaction between an alcoholic or phenolic alkali metal salt and cyanogen halide. The method of making it known is known.
しかしながら、（１）の方法は、揮発性の低い液状のジアルキルシアノアミドが副生し、生成するプレポリマーに不純物として残存し、熱硬化時に揮発してボイドを生じさせるという欠点を有する。また、（２）の方法では、アルコール系又はフェノール系化合物として水酸基の隣接位に嵩高い置換基を有するものを用いなければ、生成したシアネートがフェノキサイドと反応してイミドカーボネートを副生してしまうという問題があった。製品としてのシアン酸エステルの中に、ジアルキルシアノアミドやイミドカーボネート類等の副生物や未反応物等の不純物が存在すると、貯蔵安定性等を害し、ひいてはさらなるシアン酸エステルの制御された重合が困難となる。 However, the method (1) has a drawback that a liquid dialkylcyanoamide having low volatility is produced as a by-product and remains as an impurity in the resulting prepolymer and volatilizes during heat curing to generate voids. In the method (2), unless an alcoholic or phenolic compound having a bulky substituent at the adjacent position of the hydroxyl group is used, the produced cyanate reacts with phenoxide to produce imide carbonate as a by-product. There was a problem that. If there are impurities such as by-products such as dialkyl cyanoamides and imide carbonates and unreacted substances in the cyanate ester as a product, storage stability will be impaired, and further controlled polymerization of cyanate ester will occur. It becomes difficult.
これらの方法の改良法として、特許文献１には、水と有機溶媒との混合溶媒中、触媒量の３級アミンを用いて、置換基を有しないフェノール類のシアン酸エステルを製造する方法が提案されている。また、特許文献２、３には、反応溶媒として水を用い、アルカリ金属塩の存在下、フェノラートとハロゲン化シアンとを反応させることにより、副生物の生成が抑制され、高純度のシアン酸エステルを得る方法が提案されている。 As an improved method of these methods, Patent Document 1 discloses a method for producing a phenolic cyanate ester having no substituent using a catalytic amount of a tertiary amine in a mixed solvent of water and an organic solvent. Proposed. In Patent Documents 2 and 3, by using water as a reaction solvent and reacting phenolate with cyanogen halide in the presence of an alkali metal salt, the production of by-products is suppressed, and a high-purity cyanate ester is used. The method of obtaining is proposed.
しかしながら、特許文献１に記載の方法でもなお、イミドカーボネート類が副生することが特許文献２によって明らかにされている。また、特許文献２や３に記載された方法でも、目的物の収率等においてなお満足のいくものではなく、より効率よく高純度の目的物が得られる方法の開発が望まれていた。 However, Patent Document 2 reveals that imide carbonates are still produced as a by-product even in the method described in Patent Document 1. In addition, even the methods described in Patent Documents 2 and 3 are still not satisfactory in the yield of the target product, and the development of a method capable of obtaining a high-purity target product more efficiently has been desired.
本発明に関連して、特許文献４には、本発明の製造方法により得られるシアン酸エステルが開示されている。また、この文献には、３−メチルテトラヒドロフランなどの有機溶媒中、３級アミンなどの塩基性化合物の存在下、対応するフェノール化合物とハロゲン化シアンとを反応させることにより、目的とするシアン酸エステルが製造できる旨も記載されている。
本発明は、このような従来技術の実情に鑑みてなされたものであり、ジアルキルシアノアミドやイミドカーボネート類等の副生を抑制し、より高純度のシアン酸エステルを高収率で得ることができる、シアン酸エステルの製造方法を提供することを課題とする。 The present invention has been made in view of such a situation of the prior art, and can suppress by-products such as dialkyl cyanoamides and imide carbonates to obtain a higher purity cyanate ester in a high yield. An object of the present invention is to provide a process for producing a cyanate ester.
本発明者等は、後述する式（ＩＩ）で表されるシアン酸エステルを効率よく製造する方法について鋭意研究した結果、水と有機溶媒との二相系溶媒中、３級アミンを塩基として用い、ｐＨを酸性に制御しながらナフトール類とハロゲン化シアンとを反応させると、ナフトール類の損失を防止でき、かつ、ジアルキルシアノアミド及びイミドカーボネート類等の副生を抑制でき、有機層中に安定に純度の高いシアン酸エステルを生成、抽出することができることを見出し、本発明を完成するに至った。 As a result of intensive studies on a method for efficiently producing a cyanate ester represented by the formula (II) described later, the present inventors have used a tertiary amine as a base in a two-phase solvent of water and an organic solvent. , By reacting naphthols with cyanogen halide while controlling the pH to be acidic, the loss of naphthols can be prevented, and by-products such as dialkylcyanoamides and imide carbonates can be suppressed, and the organic layer is stable. It was found that a highly pure cyanate ester can be produced and extracted, and the present invention has been completed.
かくして本発明によれば、下記（１）〜（４）のシアン酸エステルの製造方法が提供される。
（１）式（Ｉ）
Thus, according to the present invention, the following methods (1) to (4) for producing cyanate esters are provided.
(1) Formula (I)
（式中、ｎは１〜５０の整数を表す。）で表されるナフトール類、ハロゲン化シアン、及び３級アミンを、水と有機溶媒の二相系溶媒中、酸性条件下で反応させることを特徴とする、式（ＩＩ） (In the formula, n represents an integer of 1 to 50) The naphthols, cyanogen halide, and tertiary amine represented by the above are reacted in a two-phase solvent of water and an organic solvent under acidic conditions. Characterized by the formula (II)
(式中、ｎは前記と同じ意味を表す。)で表されるシアン酸エステルの製造方法。
（２）ハロゲン化シアンの前記二相系溶媒の酸性溶液に、前記ナフトール類、及び該ナフトール類の水酸基に対し１．０〜２．０当量の３級アミンを添加して、所定時間反応させた後、この反応系にさらに０．１〜１．０当量の３級アミンを添加して反応させることを特徴とする（１）に記載のシアン酸エステルの製造方法。
(Wherein n represents the same meaning as described above).
(2) Add 1.0 to 2.0 equivalents of a tertiary amine to the naphthols and the hydroxyl group of the naphthols in an acidic solution of the cyanide halide in the two-phase solvent, and react for a predetermined time. Thereafter, 0.1 to 1.0 equivalent of a tertiary amine is further added to the reaction system for reaction, and the process for producing a cyanate ester according to (1).
（３）ｐＨ６以下の酸性条件下で反応させることを特徴とする（１）又は（２）に記載のシアン酸エステルの製造方法。
（４）前記式（Ｉ）で表されるナフトール類の水酸基に対し、０．１〜３当量の酸を用いて反応系を酸性にすることを特徴とする（１）〜（３）いずれかに記載のシアン酸エステルの製造方法。
(3) The process for producing a cyanate ester according to (1) or (2), wherein the reaction is carried out under acidic conditions of pH 6 or less.
(4) Any of (1) to (3), wherein the reaction system is acidified using 0.1 to 3 equivalents of acid with respect to the hydroxyl group of the naphthols represented by the formula (I). The manufacturing method of cyanate ester as described in any one of.
本発明の製造方法によれば、ナフトール類の損失を防止でき、かつ、ジアルキルシアノアミド及びイミドカーボネート類等の副生を抑制して、安全かつ簡便に高純度のシアン酸エステルを高収率で得ることができる。 According to the production method of the present invention, loss of naphthols can be prevented, and by-products such as dialkylcyanoamides and imide carbonates can be suppressed, and high-purity cyanate esters can be produced safely and easily in high yield. Obtainable.
以下、本発明を詳細に説明する。
本発明は、前記式（Ｉ）で表されるナフトール類（以下、「ナフトール類（Ｉ）」という。）、ハロゲン化シアン及び３級アミンを、水と有機溶媒の二相系溶媒中、酸性条件下で反応させることを特徴とする、前記式（ＩＩ）で表されるシアン酸エステル（以下、「シアン酸エステル（ＩＩ）」という。）の製造方法である。
Hereinafter, the present invention will be described in detail.
In the present invention, naphthols represented by the above formula (I) (hereinafter referred to as “naphthols (I)”), cyanogen halide and tertiary amine are acidified in a two-phase solvent of water and an organic solvent. It is a process for producing a cyanate ester represented by the above formula (II) (hereinafter referred to as “cyanate ester (II)”), characterized by reacting under conditions.
本発明においては、前記式（Ｉ）で表されるナフトール類（Ｉ）を用いる。式（Ｉ）中、ｎは１〜５０の整数を表し、１〜１０が好ましい。 In the present invention, the naphthols (I) represented by the formula (I) are used. In formula (I), n represents an integer of 1 to 50, preferably 1 to 10.
前記ナフトール類（Ｉ）の多くは公知物質であり、公知の方法（例えば、特許３１２２８３４号、特許２８６６７４７号に記載の方法）により製造することができる。また、市販されているものをそのままナフトール類（Ｉ）として用いることもできる。 Most of the naphthols (I) are known substances and can be produced by known methods (for example, methods described in Japanese Patent Nos. 322834 and 2866747). Moreover, what is marketed can also be used as naphthols (I) as it is.
本発明に用いるハロゲン化シアンとしては、塩化シアン及び臭化シアンが挙げられる。
ハロゲン化シアンとしては、シアン化ナトリウム等の金属シアニドとハロゲンとを反応させる方法等の公知の製造方法により得られたハロゲン化シアンを用いてもよいし、市販品を用いてもよい。また、金属シアニドとハロゲンとを反応させて得られたハロゲン化シアンを含有する反応液をそのまま用いることもできる。
Examples of the cyanogen halide used in the present invention include cyanogen chloride and cyanogen bromide.
As the cyanide halide, a cyanide halide obtained by a known production method such as a method of reacting a metal cyanide such as sodium cyanide with a halogen may be used, or a commercially available product may be used. Further, a reaction solution containing cyanogen halide obtained by reacting metal cyanide and halogen can be used as it is.
ハロゲン化シアンの使用量は、ナフトール類（Ｉ）の水酸基に対して、通常０．５〜５当量、好ましくは０．８〜３当量、より好ましくは１．０〜１．５当量である。 The usage-amount of cyanogen halide is 0.5-5 equivalent normally with respect to the hydroxyl group of naphthol (I), Preferably it is 0.8-3 equivalent, More preferably, it is 1.0-1.5 equivalent.
本発明に用いる３級アミンとしては、特に制約なく、具体的には、トリメチルアミン、トリエチルアミン、トリ−ｎ−ブチルアミン、トリアミルアミン、ジイソプロピルエチルアミン、ジエチル−ｎ−ブチルアミン、メチルジ−ｎ−ブチルアミン、メチルエチル−ｎ−ブチルアミン、ドデシルジメチルアミン、トリベンジルアミン、トリエタノールアミン等の脂肪族第３級アミン；Ｎ，Ｎ−ジメチルアニリン、Ｎ，Ｎ−ジエチルアニリン、ジフェニルメチルアミン、ピリジン等の芳香族環状アミン；ジエチルシクロヘキシルアミン、トリシクロヘキシルアミン、１，４−ジアザビシクロ[２．２．２]オクタン、１，８−ジアザビシクロ[５．４．０]−７−ウンデセン、１，５−ジアザビシクロ[４．３．０]−５−ノネン等の脂肪族環状アミン；等が挙げられる。これらの中でも、収率よく目的物が得られることなどから、脂肪族第３級アミンが好ましく、トリメチルアミン、トリエチルアミン、トリ−ｎ−ブチルアミン、ジイソプロピルエチルアミンがより好ましく、トリエチルアミンが特に好ましい。 The tertiary amine used in the present invention is not particularly limited, and specifically, trimethylamine, triethylamine, tri-n-butylamine, triamylamine, diisopropylethylamine, diethyl-n-butylamine, methyldi-n-butylamine, methylethyl -Aliphatic tertiary amines such as n-butylamine, dodecyldimethylamine, tribenzylamine, and triethanolamine; aromatic cyclic amines such as N, N-dimethylaniline, N, N-diethylaniline, diphenylmethylamine, and pyridine Diethylcyclohexylamine, tricyclohexylamine, 1,4-diazabicyclo [2.2.2] octane, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3. An aliphatic cyclic amine such as 0] -5-nonene; And the like. Among these, an aliphatic tertiary amine is preferable because the target product can be obtained in a high yield. Trimethylamine, triethylamine, tri-n-butylamine, and diisopropylethylamine are more preferable, and triethylamine is particularly preferable.
３級アミンの使用量は、ナフトール類（Ｉ）の水酸基に対して、通常１．０〜１０当量であり、好ましくは１．０〜３．５当量、より好ましくは２．０〜３．０当量である。このような範囲で３級アミンを用いることにより、収率よく目的とするシアン酸エステルを得ることができる。 The amount of the tertiary amine used is usually 1.0 to 10 equivalents, preferably 1.0 to 3.5 equivalents, more preferably 2.0 to 3.0 equivalents relative to the hydroxyl group of the naphthols (I). Is equivalent. By using a tertiary amine in such a range, the target cyanate ester can be obtained with good yield.
また、後述するように、原料を残存させずに反応を完結させることができ、目的物を収率よく得ることができることから、３級アミンは分割して用いるのが好ましい。 Further, as will be described later, since the reaction can be completed without leaving the raw material, and the target product can be obtained with good yield, the tertiary amine is preferably used in divided portions.
本発明においては、反応溶媒として、水と有機溶媒との二相系溶媒を用いる。二相系溶媒を用いることで、塩基として３級アミンを用いても、低揮発性で液状のジアルキルシアノアミドの副生を抑制することができる。 In the present invention, a two-phase solvent of water and an organic solvent is used as the reaction solvent. By using a two-phase solvent, even if a tertiary amine is used as a base, by-product formation of a low-volatile and liquid dialkylcyanoamide can be suppressed.
また、本発明の製造方法によれば、いかなるときも攪拌を停止することにより反応の進行を停止させることができる。そのため、有害物質の発生等、万が一のトラブルにも迅速な対応が可能である。また、各種用途に対して障害となる塩素イオン等を水相に除去することができるため、高品質な製品を製造することができる。したがって、本発明の製造方法は工業的規模での実施に適している。 Further, according to the production method of the present invention, the progress of the reaction can be stopped by stopping stirring at any time. For this reason, it is possible to respond promptly to troubles such as the generation of harmful substances. Moreover, since chlorine ions etc. which become obstacles to various uses can be removed to the aqueous phase, a high-quality product can be produced. Therefore, the production method of the present invention is suitable for implementation on an industrial scale.
前記二相系溶媒に用いる水としては、特に制約されず、水道水であっても、蒸留水であっても、脱イオン水であってもよい。効率よく目的とするシアン酸エステルを得る上では、不純物の少ない蒸留水や脱イオン水の使用が好ましい。 The water used for the two-phase solvent is not particularly limited, and may be tap water, distilled water, or deionized water. In order to efficiently obtain the target cyanate ester, it is preferable to use distilled water or deionized water with few impurities.
前記二相系溶媒に用いる有機溶媒としては、水と非混和性で、反応に不活性なものであれば特に制約はない。具体的には、塩化メチレン、クロロホルム、四塩化炭素、クロロベンゼン、ブロモベンゼン等のハロゲン化炭化水素系溶媒；ｎ−ヘキサン、シクロヘキサン、イソオクタン、シクロヘキサノン、シクロぺンタノン、２−ブタノン等の脂肪族系溶媒；ベンゼン、トルエン、キシレン、エチルベンゼン等の芳香族系溶媒；メチルエチルケトン、メチルイソブチルケトン等のケトン系溶媒；ベンゾニトリル等のニトリル系溶媒；ニトロベンゼン等のニトロ系溶媒；ジエチルエーテル、ジイソプロピルエーテル、テトラヒドロフラン等のエーテル系溶媒；酢酸エチル、安息香酸エチル等のエステル系溶媒；等が挙げられる。 The organic solvent used for the two-phase solvent is not particularly limited as long as it is immiscible with water and inert to the reaction. Specifically, halogenated hydrocarbon solvents such as methylene chloride, chloroform, carbon tetrachloride, chlorobenzene and bromobenzene; aliphatic solvents such as n-hexane, cyclohexane, isooctane, cyclohexanone, cyclopentanone and 2-butanone Aromatic solvents such as benzene, toluene, xylene and ethylbenzene; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; nitrile solvents such as benzonitrile; nitro solvents such as nitrobenzene; diethyl ether, diisopropyl ether, tetrahydrofuran, etc. Ether solvents; ester solvents such as ethyl acetate and ethyl benzoate; and the like.
用いる二相系溶媒において、水と有機溶媒との使用割合は、水と有機溶媒との重量比で、通常、水：有機溶媒＝１：１００〜１００：１、好ましくは１：１０〜１０：１、より好ましくは１：５〜５：１の範囲である。 In the two-phase solvent used, the ratio of water to organic solvent used is the weight ratio of water to organic solvent, usually water: organic solvent = 1: 100 to 100: 1, preferably 1:10 to 10: 1, more preferably in the range of 1: 5 to 5: 1.
また、二相系溶媒の使用量は、特に制限されないが、ナフトール類（Ｉ）１重量部に対して、通常０．１〜１００重量部、好ましくは１〜５０重量部である。 Moreover, the usage-amount of a two-phase type solvent is although it does not restrict | limit in particular, It is 0.1-100 weight part normally with respect to 1 weight part of naphthols (I), Preferably it is 1-50 weight part.
本発明の製造方法においては、酸性条件下で反応を行う。
酸性条件としては、ｐＨ６以下であるのが好ましく、イミドカーボネート等の副生物の生成抑制のために、ｐＨ１以下であるのがより好ましい。
In the production method of the present invention, the reaction is carried out under acidic conditions.
The acidic condition is preferably pH 6 or less, and more preferably pH 1 or less in order to suppress the formation of by-products such as imide carbonate.
反応系を酸性条件とするには、反応系に酸を添加すればよい。酸の添加量は、酸性条件で反応を行うことができる量であれば、特に限定されないが、収率よく目的とするシアン酸エステルを得る上では、ナフトール類（Ｉ）の水酸基に対して、０．１〜３当量の酸を添加することによるのが好ましい。 In order to make the reaction system acidic, an acid may be added to the reaction system. The amount of acid added is not particularly limited as long as the reaction can be carried out under acidic conditions. However, in order to obtain the desired cyanate ester in a high yield, the amount of acid added to the hydroxyl group of naphthols (I) Preference is given to adding 0.1 to 3 equivalents of acid.
用いる酸としては、塩酸、硝酸、硫酸、燐酸等の無機酸；酢酸、乳酸、プロピオン酸などの有機酸；が挙げられる。中でも、無機酸の使用が好ましく、塩酸の使用が特に好ましい。 Examples of the acid to be used include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid; organic acids such as acetic acid, lactic acid and propionic acid. Among these, use of an inorganic acid is preferable, and use of hydrochloric acid is particularly preferable.
ナフトール類（Ｉ）とハロゲン化シアンとの反応は、ハロゲン化シアン、ナフトール類（Ｉ）及び３級アミンを、前記二相系溶媒中、酸性条件下で撹拌することによって行うことができる。 The reaction of naphthols (I) and cyanogen halide can be carried out by stirring cyanogen halide, naphthols (I) and tertiary amine in the above two-phase solvent under acidic conditions.
具体的には、（ｉ）前記二相系溶媒に、ハロゲン化シアン、ナフトール類（Ｉ）及び３級アミンの所定量を添加して、全容を撹拌する方法、(ii)ハロゲン化シアン及びナフトール類（Ｉ）の二相系溶媒の溶液中に、３級アミンを添加して、全容を撹拌する方法、(iii)ハロゲン化シアン及び３級アミンの二相系溶媒の溶液中に、ナフトール類（Ｉ）（又はナフトール類（Ｉ）の溶液）を添加して、全容を撹拌する方法、(iv)３級アミン及びナフトール類（Ｉ）の二相系溶媒の溶液中に、ハロゲン化シアンの水溶液を添加して、全容を撹拌する方法、（ｖ）ハロゲン化シアンの二相系溶媒溶液中に、ナフトール類（Ｉ）及び３級アミンを添加して、全容を撹拌する方法等が挙げられる。 Specifically, (i) a method of adding a predetermined amount of cyanogen halide, naphthols (I) and tertiary amine to the two-phase solvent and stirring the whole volume, (ii) cyanogen halide and naphthol A method in which a tertiary amine is added to a solution of a biphasic solvent of the class (I) and the whole volume is stirred; (iii) a naphthol compound in a biphasic solvent of a cyanogen halide and a tertiary amine. (I) (or a solution of naphthols (I)) and the whole volume is stirred; (iv) a solution of a tertiary amine and a naphthol (I) in a two-phase solvent solution of cyanogen halide Examples include a method of stirring the entire volume by adding an aqueous solution, and a method of stirring the entire volume by adding (v) a naphthol (I) and a tertiary amine to a two-phase solvent solution of cyanogen halide. .
これらの中でも、収率よく目的とするシアン酸エステルを得る上では、（ｖ）の方法が好ましい。（ｖ）の方法の場合、副反応を抑制する上では、ナフトール類（Ｉ）及び３級アミンを適当な有機溶媒で希釈した溶液を添加するのが好ましい。ナフトール類（Ｉ）及び３級アミンを溶解させる有機溶媒としては、用いる二相系溶媒の有機溶媒と同じものであっても異なるものであっても構わない。 Among these, the method (v) is preferable for obtaining the target cyanate ester in a high yield. In the case of the method (v), it is preferable to add a solution obtained by diluting the naphthols (I) and the tertiary amine with an appropriate organic solvent in order to suppress side reactions. The organic solvent for dissolving the naphthols (I) and the tertiary amine may be the same as or different from the organic solvent of the two-phase solvent used.
なお、前述のように、３級アミンは所定量を分割して添加するのが好ましい。
３級アミンを分割して添加する方法としては、反応系にナフトール類（Ｉ）及び３級アミンの一部を有機溶媒で溶解させたものを滴下して所定時間反応させた後、さらに、残りの３級アミン（又は３級アミンの有機溶媒溶液）を滴下して反応を完結させる方法が挙げられる。
As described above, the tertiary amine is preferably added in a predetermined amount.
As a method of adding the tertiary amine in a divided manner, the naphthol (I) and a part of the tertiary amine dissolved in an organic solvent are dropped into the reaction system and reacted for a predetermined time, and then the remaining amount The tertiary amine (or the organic solvent solution of tertiary amine) is dripped and the reaction is completed.
より具体的には、反応系に、ナフトール類（Ｉ）及びナフトール類（Ｉ）の水酸基に対して１．０〜２．０当量の３級アミンを添加し、所定時間反応させた後、さらに０．１〜１．０当量の３級アミンを添加して反応させる方法が好ましい。このような方法により目的物を収率よく得ることができる。 More specifically, naphthols (I) and a tertiary amine equivalent to 1.0 to 2.0 equivalents of a hydroxyl group of naphthols (I) are added to the reaction system and reacted for a predetermined time. A method in which 0.1 to 1.0 equivalent of a tertiary amine is added and reacted is preferred. By such a method, the target product can be obtained with good yield.
反応温度は、ハロゲン化シアンとして塩化シアンを用いる場合は、通常−２０〜＋２０℃の範囲である。より安全に反応を行う上では、−１０〜０℃の範囲が好ましい。ハロゲン化シアンとして臭化シアンを用いる場合は、−５〜＋５０℃の範囲が好ましい。
反応時間は反応規模にもよるが、通常、数分から数時間である。
The reaction temperature is usually in the range of -20 to + 20 ° C when cyanogen chloride is used as the cyanogen halide. In order to perform the reaction more safely, a range of −10 to 0 ° C. is preferable. When cyanogen bromide is used as the cyanogen halide, a range of −5 to + 50 ° C. is preferable.
Although the reaction time depends on the reaction scale, it is usually from several minutes to several hours.
反応終了後は、通常の後処理操作、及び所望により分離・精製操作を行うことにより、目的とするシアン酸エステル（ＩＩ）を単離することができる。 After completion of the reaction, the desired cyanate ester (II) can be isolated by carrying out ordinary post-treatment operations and, if desired, separation / purification operations.
具体的には、反応液からシアン酸エステル（ＩＩ）を含む有機溶媒層を分取し、水洗後、濃縮または溶媒置換すればよい。濃縮する場合には、減圧下８０℃以下の温度に加熱して有機溶媒を留去するのが好ましい。温度を高くしすぎると重合が始まるおそれがあるため好ましくない。 Specifically, an organic solvent layer containing cyanate ester (II) is separated from the reaction solution, washed with water, and then concentrated or solvent-substituted. In the case of concentration, it is preferable to distill off the organic solvent by heating to a temperature of 80 ° C. or lower under reduced pressure. An excessively high temperature is not preferable because polymerization may start.
得られるシアン酸エステル（ＩＩ）の純度は、液体クロマトグラフィー又はＩＲスペクトル法等で分析することができる。 The purity of the obtained cyanate ester (II) can be analyzed by liquid chromatography, IR spectroscopy or the like.
本発明によれば、副生物の生成を抑え、高純度のシアン酸エステル（ＩＩ）を高収率で得ることができる。
得られるシアン酸エステル（ＩＩ）は、プリント基板用、電子部品の封止用、複合材料用、成形材料用及び接着材料用等として有用である。
According to the present invention, production of by-products can be suppressed, and high-purity cyanate ester (II) can be obtained in high yield.
The obtained cyanate ester (II) is useful for printed circuit boards, for sealing electronic components, for composite materials, for molding materials, and for adhesive materials.
以下、実施例により本発明をさらに詳細に説明する。但し、本発明はこれらの実施例により何ら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. However, the present invention is not limited to these examples.
（実施例１）
温度計、攪拌器、滴下漏斗及び還流冷却器を取りつけた反応器を予め０〜５℃に冷却しておき、その中に塩化シアン７．４７ｇ（０．１２２ｍｏｌ）、３５％塩酸９．７５ｇ（０．０９３５ｍｏｌ）、水７６ｍｌ、塩化メチレン４４ｍｌを仕込んだ。
Example 1
A reactor equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser was previously cooled to 0 to 5 ° C., and 7.47 g (0.122 mol) of cyanogen chloride and 9.75 g of 35% hydrochloric acid ( 0.0935 mol), 76 ml of water, and 44 ml of methylene chloride were charged.
反応器内の温度を−５〜＋５℃、ｐＨ１以下を保ちながら、そこへ、１−ナフトールアラルキル（新日鐵化学社製、以下にて同じ。）２０ｇ（０．０９３５ｍｏｌ）、及びトリエチルアミン１８．８８ｇ（０．１８７ｍｏｌ）を塩化メチレン９２ｍｌに溶解した溶液を１時間かけて滴下し、滴下終了後、同温度で１５分間撹拌した。反応液を分液し、有機層を分取した。得られた有機層を水１００ｍｌで２回洗浄した後、減圧下で濃縮し、最終的に８０℃で１時間濃縮乾固させて、目的とするシアン酸エステル２３．２ｇを得た。 While maintaining the temperature in the reactor at −5 to + 5 ° C. and pH 1 or less, 20 g (0.0935 mol) of 1-naphthol aralkyl (manufactured by Nippon Steel Chemical Co., Ltd., the same applies below) and triethylamine 18. A solution in which 88 g (0.187 mol) was dissolved in 92 ml of methylene chloride was added dropwise over 1 hour. After completion of the addition, the solution was stirred at the same temperature for 15 minutes. The reaction solution was separated, and the organic layer was separated. The obtained organic layer was washed twice with 100 ml of water, concentrated under reduced pressure, and finally concentrated to dryness at 80 ° C. for 1 hour to obtain 23.2 g of the intended cyanate ester.
得られたシアン酸エステルを液体クロマトグラフィー及びＩＲスペクトルにより分析したところ、原料が約１０％残存した。副反応により生じるジエチルシアノアミドの含有率は０．１重量％以下であった。また、硝酸銀を用いた電位差滴定で検出された塩素イオンは１０ｐｐｍ以下であった。 When the obtained cyanate ester was analyzed by liquid chromatography and IR spectrum, about 10% of the raw material remained. The content of diethylcyanoamide generated by the side reaction was 0.1% by weight or less. Moreover, the chlorine ion detected by potentiometric titration using silver nitrate was 10 ppm or less.
（実施例２）
温度計、攪拌器、滴下漏斗及び還流冷却器を取りつけた反応器を予め０〜５℃に冷却しておき、そこへ塩化シアン７．４７ｇ（０．１２２ｍｏｌ）、３５％塩酸９．７５ｇ（０．０９３５ｍｏｌ）、水７６ｍｌ、及び塩化メチレン４４ｍｌを仕込んだ。
(Example 2)
A reactor equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser was previously cooled to 0 to 5 ° C., to which 7.47 g (0.122 mol) of cyanogen chloride and 9.75 g (0% of 35% hydrochloric acid) 0935 mol), 76 ml of water, and 44 ml of methylene chloride.
この反応器内の温度を−５〜＋５℃、ｐＨを１以下を保ちながら、撹拌下、１−ナフトールアラルキル２０ｇ（０．０９３５ｍｏｌ）、及びトリエチルアミン１４．１６ｇ（０．１４ｍｏｌ）を塩化メチレン９２ｍｌに溶解した溶液を１時間かけて滴下し、滴下終了後、更にトリエチルアミン４．７２ｇ（０．０４７ｍｏｌ）を１５分間かけて滴下した。 While maintaining the temperature in the reactor at -5 to + 5 ° C. and maintaining the pH at 1 or less, 20 g (0.0935 mol) of 1-naphthol aralkyl and 14.16 g (0.14 mol) of triethylamine were added to 92 ml of methylene chloride. The dissolved solution was added dropwise over 1 hour, and after completion of the addition, 4.72 g (0.047 mol) of triethylamine was further added dropwise over 15 minutes.
滴下終了後、同温度で１５分間撹拌後、反応液を分液し、有機層を分取した。得られた有機層を水１００ｍｌで２回洗浄した後、減圧下で濃縮し、最終的に８０℃で１時間濃縮乾固させて、目的とするシアン酸エステル２３．５ｇを得た。 After completion of dropping, the reaction solution was separated after stirring at the same temperature for 15 minutes, and the organic layer was separated. The obtained organic layer was washed twice with 100 ml of water, then concentrated under reduced pressure, and finally concentrated to dryness at 80 ° C. for 1 hour to obtain 23.5 g of the intended cyanate ester.
得られたシアン酸エステルを、液体クロマトグラフィー及びＩＲスペクトルにより分析したところ、原料ピークは検出されなかった。副反応により生じるジエチルシアノアミドの含有率は０．１重量％以下であった。また、硝酸銀を用いた電位差滴定で検出された塩素イオンは１０ｐｐｍ以下であった。 When the obtained cyanate ester was analyzed by liquid chromatography and IR spectrum, no starting material peak was detected. The content of diethylcyanoamide generated by the side reaction was 0.1% by weight or less. Moreover, the chlorine ion detected by potentiometric titration using silver nitrate was 10 ppm or less.
（比較例１）
温度計、攪拌器、滴下漏斗及び還流冷却器を取りつけた反応器を予め０〜５℃に冷却しておき、その中に塩化シアン７．４７ｇ（０．１２２ｍｏｌ）、塩化メチレン４４ｍｌを仕込んだ。
反応器内の温度を−６〜−２℃とし、そこへ、塩化メチレン９２ｍｌで溶解した１−ナフトールアラルキル２０ｇ（０．０９３５ｍｏｌ）と、トリエチルアミン１０．３９ｇ（０．１０３ｍｏｌ）溶液をこの反応器内に１時間かけて滴下し、滴下終了後、同温度で１５分間撹拌した。
(Comparative Example 1)
A reactor equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser was previously cooled to 0 to 5 ° C., and 7.47 g (0.122 mol) of cyanogen chloride and 44 ml of methylene chloride were charged therein.
The temperature in the reactor was set to −6 to −2 ° C., and 20 g (0.0935 mol) of 1-naphthol aralkyl dissolved in 92 ml of methylene chloride and 10.39 g (0.103 mol) of triethylamine were added to the reactor. Was added dropwise over 1 hour, and after completion of the dropwise addition, the mixture was stirred at the same temperature for 15 minutes.
反応溶液に水１００ｍｌを加えて分液した後、有機層を水１００ｍｌで２回洗浄した。有機層を減圧下で濃縮し、最終的に８０℃で１時間濃縮乾固し、目的とするシアン酸エステル２３．５ｇを得た。
得られたシアン酸エステルを、液体クロマトグラフィーにて分析したところ、副反応により生じるジエチルシアノアミドが、３．３重量％不純物として含まれていた。
After adding 100 ml of water to the reaction solution for liquid separation, the organic layer was washed twice with 100 ml of water. The organic layer was concentrated under reduced pressure and finally concentrated to dryness at 80 ° C. for 1 hour to obtain 23.5 g of the intended cyanate ester.
The obtained cyanate ester was analyzed by liquid chromatography. As a result, diethylcyanoamide produced by the side reaction was contained as 3.3 wt% impurities.
（比較例２）
温度計、攪拌器、滴下漏斗及び還流冷却器を取りつけた反応器を予め０〜５℃に冷却しておき、その中に塩化シアン７．４７ｇ（０．１２２ｍｏｌ）、水８２ｍｌ、塩化メチレン４４ｍｌを仕込んだ。
(Comparative Example 2)
A reactor equipped with a thermometer, stirrer, dropping funnel and reflux condenser was previously cooled to 0 to 5 ° C., and 7.47 g (0.122 mol) of cyanogen chloride, 82 ml of water and 44 ml of methylene chloride were contained therein. Prepared.
反応器内の温度を−５〜＋５℃とし、そこへ、１−ナフトールアラルキル２０ｇ（０．０９３５ｍｏｌ）、及びトリエチルアミン１４．１６ｇ（０．１４ｍｏｌ）を塩化メチレン９２ｍｌに溶解した溶液を１時間かけて滴下し、滴下終了後、更にトリエチルアミン４．７２ｇ（０．０４７ｍｏｌ）を１５分間かけて滴下した。滴下終了後、同温度で１５分間撹拌したところ、有機溶媒不溶性の重合物が生成した。有機層を液体クロマトグラフィーにて分析したが、目的物も原料も検出されなかった。
The temperature in the reactor was set to −5 to + 5 ° C., and a solution of 20 g (0.0935 mol) of 1-naphthol aralkyl and 14.16 g (0.14 mol) of triethylamine in 92 ml of methylene chloride was added over 1 hour. After dropping, 4.72 g (0.047 mol) of triethylamine was further added dropwise over 15 minutes. After completion of the dropwise addition, the mixture was stirred at the same temperature for 15 minutes, whereby an organic solvent insoluble polymer was formed. The organic layer was analyzed by liquid chromatography, but neither the target product nor the raw material was detected.
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| WO2014203866A1 (en) | 2013-06-18 | 2014-12-24 | 三菱瓦斯化学株式会社 | Resin composition, prepreg, resin sheet and metal foil-clad laminate |
| WO2015060418A1 (en) | 2013-10-25 | 2015-04-30 | 三菱瓦斯化学株式会社 | Cyanic acid ester compound, curable resin composition containing said compound, and cured product thereof |
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