JP5256635B2 - Novel alicyclic compound, method for producing novel alicyclic compound, and polymer composition - Google Patents
Novel alicyclic compound, method for producing novel alicyclic compound, and polymer composition Download PDFInfo
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- JP5256635B2 JP5256635B2 JP2007088562A JP2007088562A JP5256635B2 JP 5256635 B2 JP5256635 B2 JP 5256635B2 JP 2007088562 A JP2007088562 A JP 2007088562A JP 2007088562 A JP2007088562 A JP 2007088562A JP 5256635 B2 JP5256635 B2 JP 5256635B2
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- Prior art keywords
- alicyclic
- general formula
- acrylate
- meth
- formula
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims description 30
- 229920000642 polymer Polymers 0.000 title claims description 29
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 150000001334 alicyclic compounds Chemical class 0.000 title description 9
- -1 alicyclic imide Chemical class 0.000 claims description 82
- 125000002723 alicyclic group Chemical group 0.000 claims description 52
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 41
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 25
- 238000006116 polymerization reaction Methods 0.000 claims description 19
- 239000000178 monomer Substances 0.000 claims description 17
- 229920002554 vinyl polymer Polymers 0.000 claims description 15
- 150000003949 imides Chemical class 0.000 claims description 14
- YHQGMYUVUMAZJR-UHFFFAOYSA-N α-terpinene Chemical compound CC(C)C1=CC=C(C)CC1 YHQGMYUVUMAZJR-UHFFFAOYSA-N 0.000 claims description 14
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 13
- 229930003658 monoterpene Natural products 0.000 claims description 13
- 235000002577 monoterpenes Nutrition 0.000 claims description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
- UAHWPYUMFXYFJY-UHFFFAOYSA-N beta-myrcene Chemical compound CC(C)=CCCC(=C)C=C UAHWPYUMFXYFJY-UHFFFAOYSA-N 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 238000005984 hydrogenation reaction Methods 0.000 claims description 8
- WSTYNZDAOAEEKG-UHFFFAOYSA-N Mayol Natural products CC1=C(O)C(=O)C=C2C(CCC3(C4CC(C(CC4(CCC33C)C)=O)C)C)(C)C3=CC=C21 WSTYNZDAOAEEKG-UHFFFAOYSA-N 0.000 claims description 7
- 125000000524 functional group Chemical group 0.000 claims description 7
- VYBREYKSZAROCT-UHFFFAOYSA-N alpha-myrcene Natural products CC(=C)CCCC(=C)C=C VYBREYKSZAROCT-UHFFFAOYSA-N 0.000 claims description 6
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 claims description 6
- OGLDWXZKYODSOB-UHFFFAOYSA-N α-phellandrene Chemical compound CC(C)C1CC=C(C)C=C1 OGLDWXZKYODSOB-UHFFFAOYSA-N 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- 238000012719 thermal polymerization Methods 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 4
- OGLDWXZKYODSOB-SNVBAGLBSA-N alpha-phellandrene Natural products CC(C)[C@H]1CC=C(C)C=C1 OGLDWXZKYODSOB-SNVBAGLBSA-N 0.000 claims description 3
- 239000003505 polymerization initiator Substances 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 67
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 48
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 25
- 239000002904 solvent Substances 0.000 description 23
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 20
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 18
- 150000008064 anhydrides Chemical class 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- 239000000047 product Substances 0.000 description 15
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 12
- 230000005587 bubbling Effects 0.000 description 12
- 229910001873 dinitrogen Inorganic materials 0.000 description 11
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 238000004817 gas chromatography Methods 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 150000003613 toluenes Chemical class 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 150000008065 acid anhydrides Chemical class 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000005886 esterification reaction Methods 0.000 description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- 229920002799 BoPET Polymers 0.000 description 5
- 238000005698 Diels-Alder reaction Methods 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 5
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000007112 amidation reaction Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000020169 heat generation Effects 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229930003651 acyclic monoterpene Natural products 0.000 description 3
- 150000007514 bases Chemical class 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000006358 imidation reaction Methods 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- GRWFGVWFFZKLTI-IUCAKERBSA-N (-)-α-pinene Chemical compound CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
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- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
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- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
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- 125000000217 alkyl group Chemical group 0.000 description 2
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- 230000009435 amidation Effects 0.000 description 2
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- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
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- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 2
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- TXXHDPDFNKHHGW-UHFFFAOYSA-N muconic acid Chemical compound OC(=O)C=CC=CC(O)=O TXXHDPDFNKHHGW-UHFFFAOYSA-N 0.000 description 2
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- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- FRCAGVUKJQCWBD-UHFFFAOYSA-L iodine green Chemical compound [Cl-].[Cl-].C1=CC(N(C)C)=CC=C1C(\C=1C=CC(=CC=1)[N+](C)(C)C)=C/1C=C(C)C(=[N+](C)C)C=C\1 FRCAGVUKJQCWBD-UHFFFAOYSA-L 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
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- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
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- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
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- 150000004706 metal oxides Chemical class 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
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- 239000012046 mixed solvent Substances 0.000 description 1
- FONOEURACRGRDD-UHFFFAOYSA-N n-ethenylformamide;prop-2-enamide Chemical compound C=CNC=O.NC(=O)C=C FONOEURACRGRDD-UHFFFAOYSA-N 0.000 description 1
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- 239000001301 oxygen Substances 0.000 description 1
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- 239000003973 paint Substances 0.000 description 1
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- 230000035699 permeability Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000002990 phenothiazines Chemical class 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
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- 229920001296 polysiloxane Polymers 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- GRWFGVWFFZKLTI-UHFFFAOYSA-N rac-alpha-Pinene Natural products CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 description 1
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- 238000010898 silica gel chromatography Methods 0.000 description 1
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- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
- SCWPFSIZUZUCCE-UHFFFAOYSA-N β-terpinene Chemical compound CC(C)C1=CCC(=C)CC1 SCWPFSIZUZUCCE-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Indole Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は、新規脂環イミド（メタ）アクリレート、新規脂環イミド（メタ）アクリレートの製造方法および重合体組成物に関する。より詳細には、天然原料（モノテルペン化合物）を用いた新規脂環イミド（メタ）アクリレート、新規脂環イミド（メタ）アクリレートの製造方法、および該脂環イミド（メタ）アクリレートを含有する重合用組成物ならびに該重合用組成物を重合してなる重合体組成物に関する。 The present invention relates to a novel alicyclic imide (meth) acrylate , a method for producing a novel alicyclic imide (meth) acrylate , and a polymer composition. More specifically, a novel alicyclic imide (meth) acrylate using a natural raw material (monoterpene compound), a method for producing a new alicyclic imide (meth) acrylate , and a polymerization containing the alicyclic imide (meth) acrylate to compositions and polymer composition obtained by polymerizing the polymerizable composition.
脂環構造を有する重合性モノマーは、特に電子材料や光学材料の分野で賞用されており、これら材料の各種性能（耐熱性や強度、透明性、耐湿性等）を一層向上させるべく、種々の分子構造が検討されている。例えば特許文献１に係る特定の脂環イミドアクリレートは、耐熱性等に優れた重合体組成物を与えるとされている。しかし、従来の脂環系重合性モノマーは、脂環構造が石油系原料に由来するものであり、原油価格の変動に伴う製品コストの高騰や、環境負荷、資源枯渇といった問題があった。
本発明は、天然物由来の原料を用いた新規な脂環式化合物を提供することを主な目的とする。 The main object of the present invention is to provide a novel alicyclic compound using a natural product-derived raw material.
本発明者は、天然原料由来の脂環式化合物について鋭意検討を重ねた結果、所定のモノテルペン化合物に由来する脂環骨格を有する脂環式化合物が新規であり、当該化合物を合成する方法を見出し、本発明を完成するに到った。 As a result of intensive investigations on alicyclic compounds derived from natural raw materials, the present inventor has found that an alicyclic compound having an alicyclic skeleton derived from a predetermined monoterpene compound is novel and a method for synthesizing the compound. The headline and the present invention have been completed.
即ち本発明は、下記一般式（３−１）、（３−２）、（３−３）、（３−４）および（３−５）から選ばれる１種の脂環イミド（メタ）アクリレート； That is, the present invention provides one alicyclic imide (meth) acrylate selected from the following general formulas (3-1), (3-2), (3-3), (3-4) and (3-5). ;
下記工程（Ｉ）と工程（ＩＩ）を経由することを特徴とする、下記一般式（３−１）、（３−２）、（３−３）、（３−４）および（３−５）から選ばれる１種脂環イミドアクリレートの製造方法； The following general formulas (3-1), (3-2), (3-3), (3-4) and (3-5) are characterized by passing through the following steps (I) and (II). method for producing one alicyclic imide acrylate selected from);
（各式中、Ｒ(In each formula, R １1 は下記一般式（２）で示す官能基を表す。なお、破線部はその炭素−炭素結合が不飽和結合であってもよいことを表す。）Represents a functional group represented by the following general formula (2). The broken line portion indicates that the carbon-carbon bond may be an unsaturated bond. )
[工程（I）]
下記一般式（４−１）で示される脂環式ジカルボン酸または下記一般式（４−２）で示される脂環式ジカルボン酸無水物に、下記一般式（５）で示されるモノアミン化合物を反応させて、下記一般式（６）で示される脂環式マレイミド化合物を製造する工程。
[Process (I)]
The monoamine compound represented by the following general formula (5) is reacted with the alicyclic dicarboxylic acid represented by the following general formula (4-1) or the alicyclic dicarboxylic acid anhydride represented by the following general formula (4-2). A step of producing an alicyclic maleimide compound represented by the following general formula (6).
（式（４−１）および（４−２）中、Ｒ２はα-テルピネン、α−フェランドレン、ミルセンおよびはアロオメシンから選ばれるモノテルペン化合物に由来する脂環骨格を表す。） (Formula (4-1) and (4-2) in, R 2 is alpha-terpinene, alpha-phellandrene, myrcene and represents an alicyclic skeleton derived from a monoterpene compound Ru is selected from Aroomeshin.)
（式（５）中、Ｒ３、Ｒ４、ｎは前記同様である。また、Ｒ６は水酸基またはハロゲン原子を表す。） (In Formula (5), R 3 , R 4 , and n are the same as described above. R 6 represents a hydroxyl group or a halogen atom.)
（式（６）中、Ｒ２、Ｒ３、Ｒ４、ｎ、Ｒ６は前記同様である。） (In formula (6), R 2 , R 3 , R 4 , n, and R 6 are the same as above.)
[工程（II）]
一般式（６）で表される該脂環式マレイミド化合物に、下記一般式（７）で示すビニル化合物を反応させる工程。
[Process (II)]
A step of reacting the alicyclic maleimide compound represented by the general formula (6) with a vinyl compound represented by the following general formula (7).
（式（７）中、ｍおよびＲ５は前記同様である） (In formula (7), m and R 5 are the same as above)
および、当該重合性モノマー、ならびに必要に応じて当該重合性モノマーと共重合させるためのその他の重合性モノマー、ならびに必要に応じて光重合開始剤を含有する重合用組成物；当該重合用組成物を重合してなる重合体組成物、に関する。 And a polymerizable composition containing the polymerizable monomer and, if necessary, another polymerizable monomer for copolymerization with the polymerizable monomer, and, if necessary, a photopolymerization initiator; The present invention relates to a polymer composition obtained by polymerizing
本発明の脂環式化合物は、天然原料である、α-テルピネン、α−フェランドレン、ミルセンおよびアロオメシンから選ばれる環式または非環式のモノテルペン化合物）を用いたものであるため、従来の石油系原料を用いた脂環式化合物と比べて、環境負荷等の問題が小さい。また、このものは、アルキル基が結合した嵩高いビシクロ骨格、または、長鎖アルキル基が結合したシクロ骨格を有しており、従来の脂環式化合物とは異なる有利な効果（例えば、その重合体の、高耐熱性、低吸水性、低透湿性など）が期待される。 Since the alicyclic compound of the present invention uses a natural raw material , a cyclic or acyclic monoterpene compound selected from α-terpinene, α-ferrandrene, myrcene, and aloomesin ), Compared with alicyclic compounds using petroleum-based raw materials, problems such as environmental impact are small. In addition, this compound has a bulky bicyclo skeleton to which an alkyl group is bonded or a cyclo skeleton to which a long chain alkyl group is bonded, and has an advantageous effect different from that of a conventional alicyclic compound (for example, its heavy weight). High heat resistance, low water absorption, low moisture permeability, etc.) are expected.
また、本発明の脂環式化合物を重合してなる重合体組成物は、各種の工学材料、例えば光学材料〔光ディスク記録媒体用オーバーコート剤、ハードコート剤、溝材、レンズ等〕や、電子材料〔層間絶縁膜、レジスト、ダイボンド剤、ダイオード・水晶振動子等の接着剤、ダイオード等の素子、モールド部材、ダイボンドフィルム、ソルダーレジスト等〕としても有用であることが期待される。また、該重合体組成物は、塗料用バインダー、印刷インキ用バインダー、接着剤、粘着剤、歯科材料、製紙用薬品等の他、各種成形品としても有用であると期待され、例えばレンズ〔フレネルレンズ、レンチキュラーレンズ、プリズムシート等〕においても有用であることが期待される。 In addition, the polymer composition obtained by polymerizing the alicyclic compound of the present invention includes various engineering materials such as optical materials (overcoat agents for optical disk recording media, hard coat agents, groove materials, lenses, etc.), electronic It is also expected to be useful as a material (interlayer insulating film, resist, die bond agent, adhesive such as a diode / crystal resonator, element such as a diode, mold member, die bond film, solder resist, etc.). The polymer composition is also expected to be useful as various molded products in addition to paint binders, printing ink binders, adhesives, pressure-sensitive adhesives, dental materials, papermaking chemicals, and the like. For example, lenses [Fresnel Lens, lenticular lens, prism sheet, and the like].
本発明に係る脂環イミドアクリレートは、下記一般式（３−１）、（３−２）、（３−３）、（３−４）および（３−５）から選ばれる１種の、分子内に脂環構造と重合性二重結合を有する重合性モノマーである。 The alicyclic imide acrylate according to the present invention is a molecule selected from the following general formulas (3-1), (3-2), (3-3), (3-4) and (3-5). It is a polymerizable monomer having an alicyclic structure and a polymerizable double bond.
前記一般式（３−１）、（３−２）、（３−３）、（３−４）および（３−５）から選ばれる１種の脂環イミド（メタ）アクリレートに関し、一般式（３−１）の脂環骨格はα−テルピネンに、一般式（３−２）のそれはα−フェランドレンに、一般式（３−３）のそれはミルセンに、一般式（３−４）のそれはアロオメシンに由来する。 Regarding one alicyclic imide (meth) acrylate selected from the general formulas (3-1), (3-2), (3-3), (3-4) and (3-5) , the general formula ( The alicyclic skeleton of 3-1) is α-terpinene, that of general formula (3-2) is α-ferrandrene, that of general formula (3-3) is myrcene, and that of general formula (3-4) is Derived from aloomesin.
（各式中、Ｒ１は前記一般式（２）で示す官能基を表す。なお、破線部はその炭素−炭素結合が不飽和結合であってもよいことを表す。） (In each formula, R 1 represents the functional group represented by the general formula (2). The broken line portion represents that the carbon-carbon bond may be an unsaturated bond.)
前記一般式（１）で示す脂環イミドアクリレートの製造方法は特に限定されないが、例えば、下記工程（I）と工程（II）を経由することにより製造することができる。 Although the manufacturing method of alicyclic imide acrylate shown by the said General formula (1) is not specifically limited, For example, it can manufacture by passing through the following process (I) and process (II).
[工程（I）]
下記一般式（４−１）で示される脂環式ジカルボン酸または下記一般式（４−２）で示される脂環式ジカルボン酸無水物（以下、両者を脂環式ジカルボン酸（無水物）と略すことがある）に、下記一般式（５）で示されるモノアミン化合物を反応させて、下記一般式（６）で示される脂環式マレイミド化合物を製造する工程。
[Process (I)]
The alicyclic dicarboxylic acid represented by the following general formula (4-1) or the alicyclic dicarboxylic acid anhydride represented by the following general formula (4-2) (hereinafter referred to as alicyclic dicarboxylic acid (anhydride)) A step of producing a cycloaliphatic maleimide compound represented by the following general formula (6) by reacting a monoamine compound represented by the following general formula (5) with the monoamine compound represented by the following general formula (5).
（式（４−１）および（４−２）中、Ｒ２はモノテルペン化合物に由来する脂環骨格を表す。） (In formulas (4-1) and (4-2), R 2 represents an alicyclic skeleton derived from a monoterpene compound.)
（式（５）中、Ｒ３およびＲ４はそれぞれ水素原子またはメチル基を、ｎは１〜６の整数を、Ｒ６は水酸基またはハロゲン原子を表す。） (In Formula (5), R 3 and R 4 each represent a hydrogen atom or a methyl group, n represents an integer of 1 to 6, and R 6 represents a hydroxyl group or a halogen atom.)
（式（６）中、Ｒ２、Ｒ３、Ｒ４、ｎ、Ｒ６は前記同様である。） (In formula (6), R 2 , R 3 , R 4 , n, and R 6 are the same as above.)
[工程（II）]
前記一般式（６）で表される脂環式マレイミド化合物に、下記一般式（７）で示すビニル化合物を反応させる工程。
[Process (II)]
A step of reacting the alicyclic maleimide compound represented by the general formula (6) with a vinyl compound represented by the following general formula (7).
（式（７）中、ｍは０を、Ｒ５は水素原子またはメチル基を表す。） (In formula (7), m represents 0 and R 5 represents a hydrogen atom or a methyl group.)
[工程（I）について]
前記一般式（４−１）または（４−２）で示す脂環式ジカルボン酸（無水物）は、例えば、各種公知のモノテルペン化合物と、マレイン酸（無水物）（マレイン酸またはマレイン酸無水物をいう）とを、各種公知の方法でディールス・アルダー反応させることにより得ることができる。他にも、一般式（４−１）の脂環式ジカルボン酸は、該モノテルペン化合物とマレイン酸ジアルキルエステルとのディールス・アルダー反応物を、更に各種公知の方法で加水分解することによっても得ることができる。また、一般式（４−２）で示す脂環式ジカルボン酸無水物は、該脂環式ジカルボン酸を各種公知の方法で脱水縮合することにより得ることもできる。なお、該脂環式ジカルボン酸（無水物）としては、後述のアミド化ないしイミド化反応が容易に進行しやすくなることから、脂環式ジカルボン酸無水物が好ましい。
[About step (I)]
The alicyclic dicarboxylic acid (anhydride) represented by the general formula (4-1) or (4-2) includes, for example, various known monoterpene compounds and maleic acid (anhydride) (maleic acid or maleic anhydride). Can be obtained by Diels-Alder reaction by various known methods. In addition, the alicyclic dicarboxylic acid of the general formula (4-1) can also be obtained by hydrolyzing the Diels-Alder reaction product of the monoterpene compound and the dialkyl maleate with various known methods. be able to. Moreover, the alicyclic dicarboxylic acid anhydride represented by the general formula (4-2) can also be obtained by dehydrating and condensing the alicyclic dicarboxylic acid by various known methods. The alicyclic dicarboxylic acid (anhydride) is preferably an alicyclic dicarboxylic acid anhydride because an amidation or imidation reaction described later easily proceeds.
該モノテルペン化合物は、分子内に共役二重結合を有するモノテルペン化合物であって、α-テルピネン（下記一般式（８−１））、α−フェランドレン（下記一般式（８−２））等の環式モノテルペン化合物や、ミルセン（下記一般式（８−３））、アロオメシン（下記一般式（８−４））等の非環式モノテルペン化合物を用いる。
ここに、α-テルピネンを用いた脂環イミドアクリレートは前記一般式（３−１）に、α−フェランドレンを用いた脂環イミドアクリレートは前記一般式（３−２）に、ミルセンを用いた脂環イミドアクリレートは前記一般式（３−３）に、アロオメシンを用いた脂環イミドアクリレートは前記一般式（３−４）または（３−５）（両者は異性体の関係にある）に対応する。
なお、該モノテルペン化合物はいずれも、高純度の市販品（通常８５％以上）がそのまま利用できる。また、本発明で用いるモノテルペン化合物には、他の環式または非環式のモノテルペン化合物（例えばβ−フェランドレン、β-テルピネン、γ-テルピネン、α−ピネン、オシメン等）が残分として含まれていてもよい。
The monoterpene compound is a monoterpene compound having a conjugated double bond in the molecule, alpha-terpinene (the following general formula (8-1)), alpha-phellandrene (the following general formula (8-2)) and cyclic monoterpene compounds such as myrcene (the following general formula (8-3)), Ru with acyclic monoterpene compounds such Aroomeshin (the following general formula (8-4)).
Here, alicyclic imide acrylate using α-terpinene was used in the general formula (3-1), and alicyclic imide acrylate using α-ferrandrene was used in the general formula (3-2). The alicyclic imide acrylate corresponds to the general formula (3-3), and the alicyclic imide acrylate using aloomesin corresponds to the general formula (3-4) or (3-5) (both are in an isomer relationship). To do.
In addition, as for this monoterpene compound, the high purity commercial item (usually 85% or more) can be utilized as it is. The monoterpene compound used in the present invention includes other cyclic or acyclic monoterpene compounds (for example, β-ferrandrene, β-terpinene, γ-terpinene, α-pinene, osymene, etc.) as a residue. It may be included.
ディールス・アルダー反応は特に限定されず、各種公知の方法を利用できる。具体的には、例えば、前記モノテルペン化合物１モルと、これに対し通常０．８〜１．２モル程度となるマレイン酸（無水物）とを、通常室温〜２００℃程度の温度で、通常３〜１２時間程度反応させればよい。なお、脂環式ジカルボン酸（無水物）の着色を考慮して、反応容器は密閉構造とし、更に窒素等の不活性ガスでパージするのが好ましい。また、反応の際には、各種公知の溶媒〔ベンゼン、トルエン、キシレン、ｎ−ペンタン、ｎ−ヘキサン、ｎ−ペンタン、シクロペンタン、酢酸メチル、酢酸エチル、酢酸イソブチル等〕から選ばれる１種を単独で、または組み合わせて用いることができる。こうして得られた脂環式ジカルボン酸（無水物）は、各種の精製手段〔減圧蒸留、水蒸気蒸留、溶媒抽出、再結晶、シリカゲルカラムクロマトグラフィー等〕で精製することもできる。 The Diels-Alder reaction is not particularly limited, and various known methods can be used. Specifically, for example, 1 mol of the monoterpene compound and maleic acid (anhydride), which is usually about 0.8 to 1.2 mol, are usually used at a temperature of about room temperature to about 200 ° C. What is necessary is just to make it react for about 3-12 hours. In consideration of the coloring of the alicyclic dicarboxylic acid (anhydride), it is preferable that the reaction vessel has a sealed structure and further purged with an inert gas such as nitrogen. In the reaction, one kind selected from various known solvents [benzene, toluene, xylene, n-pentane, n-hexane, n-pentane, cyclopentane, methyl acetate, ethyl acetate, isobutyl acetate, etc.] They can be used alone or in combination. The alicyclic dicarboxylic acid (anhydride) thus obtained can be purified by various purification means [vacuum distillation, steam distillation, solvent extraction, recrystallization, silica gel column chromatography, etc.].
また、得られた脂環式ジカルボン酸（無水物）が、分子中の脂環骨格（Ｒ２）に炭素−炭素不飽和結合を含む場合には、該脂環式ジカルボン酸（無水物）を水素化反応に供して、当該炭素−炭素不飽和結合を飽和結合にすることもできる。水素化反応は特に制限されず、各種公知の方法を利用できる。具体的には、例えば、前記脂環式ジカルボン酸（無水物）を、各種公知の金属触媒〔安定化ニッケルやパラジウム、パラジウムカーボン、白金等〕と、必要に応じてＴＨＦ等の溶媒との存在下で、通常９．８ＭＰａ以下（好ましくは０．９８〜９．８ＭＰａ）の水素圧、室温〜３００℃程度の温度、３〜２４時間程度の条件で水素化反応させればよい。 Further, when the obtained alicyclic dicarboxylic acid (anhydride) contains a carbon-carbon unsaturated bond in the alicyclic skeleton (R 2 ) in the molecule, the alicyclic dicarboxylic acid (anhydride) The carbon-carbon unsaturated bond can be converted to a saturated bond by subjecting it to a hydrogenation reaction. The hydrogenation reaction is not particularly limited, and various known methods can be used. Specifically, for example, the alicyclic dicarboxylic acid (anhydride) is present in various known metal catalysts (stabilized nickel, palladium, palladium carbon, platinum, etc.) and optionally a solvent such as THF. The hydrogenation reaction may be carried out under conditions of a hydrogen pressure of usually 9.8 MPa or less (preferably 0.98 to 9.8 MPa), a temperature of room temperature to about 300 ° C., and a time of about 3 to 24 hours.
前記一般式（５）で示すモノアミン化合物としては、前記一般式（５）中のＲ６の種類に応じて、各種公知のものを用いることができる。具体的には、例えば、Ｒ６が水酸基の場合には、各種公知のモノアミノアルコール類〔エタノールアミン、プロパノールアミン、ブタノールアミン等〕を例示できる。また、Ｒ６がハロゲン原子（フッ素、塩素、臭素等）の場合には、各種公知のハロゲン化アルキルアミン類〔２−クロロエチルアミン、２−ブロモエチルアミン、１−アミノ−２−プロピルクロライド等〕を例示できる。これらの中でも、入手容易で安価な点より、前記モノアミノアルコール類、特にエタノールアミンが好ましい。 As the monoamine compound represented by the general formula (5), various known compounds can be used depending on the type of R 6 in the general formula (5). Specifically, for example, when R 6 is a hydroxyl group, various known monoamino alcohols [ethanolamine, propanolamine, butanolamine and the like] can be exemplified. When R 6 is a halogen atom (fluorine, chlorine, bromine, etc.), various known halogenated alkylamines [2-chloroethylamine, 2-bromoethylamine, 1-amino-2-propyl chloride, etc.] It can be illustrated. Among these, the monoamino alcohols, particularly ethanolamine is preferable from the viewpoint of availability and inexpensiveness.
前記脂環式ジカルボン酸（無水物）と前記モノアミン化合物との反応は、各種公知のアミド化・イミド化反応による。具体的には、例えば、前記脂環式ジカルボン酸（無水物）１モルと、これに対し通常０．５〜３モル程度となる前記モノアミン化合物とを、通常は水と共沸する溶媒（トルエン等）の存在下、通常１０℃〜７０℃程度の温度で、通常１〜１２時間程度アミド化反応を行い、更に、通常８０℃〜１８０℃程度の温度で、通常３〜２０時間程度イミド化反応（脱水閉環反応）させればよい。 The reaction between the alicyclic dicarboxylic acid (anhydride) and the monoamine compound is based on various known amidation and imidation reactions. Specifically, for example, 1 mol of the alicyclic dicarboxylic acid (anhydride) and the monoamine compound, which is usually about 0.5 to 3 mol, are usually a solvent (toluene) azeotroped with water. Etc.) in the presence of an amidation reaction, usually at a temperature of about 10 ° C. to 70 ° C., usually for about 1 to 12 hours, and further at a temperature of about 80 ° C. to 180 ° C., usually for about 3 to 20 hours. What is necessary is just to make it react (dehydration ring closure reaction).
なお、アミド化反応時には、反応を促進する目的で、各種公知の酸又は塩基触媒を用いてもよい。具体的には、例えば、各種公知の有機スルホン酸〔アルキルスルホン酸、ｐ−トルエンスルホン酸、ベンゼンスルホン酸等〕、無機酸〔硫酸、亜リン酸等〕、塩基性化合物〔ピリジン、トリメチルアミン、トリエチルアミン等〕等を、前記脂環式ジカルボン酸（無水物）１モルに対して通常０．０００５〜０．０５モル程度用いることができる。 In the amidation reaction, various known acid or base catalysts may be used for the purpose of promoting the reaction. Specifically, for example, various known organic sulfonic acids [alkylsulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, etc.], inorganic acids [sulfuric acid, phosphorous acid, etc.], basic compounds [pyridine, trimethylamine, triethylamine, etc.] Etc.] can usually be used in an amount of about 0.0005 to 0.05 mol with respect to 1 mol of the alicyclic dicarboxylic acid (anhydride).
また、イミド化反応時には、５０℃〜１００℃程度の低温域で反応を行う目的で、各種公知の触媒を用いてもよい。具体的には、例えば、ジシクロヘキシルカルボジイミドや無水酢酸などの脱水剤と、ピリジン、トリエチルアミン、酢酸ナトリウムなどの塩基性化合物の組み合わせたものを利用できる。なお、当該塩基性化合物の使用量は、脱水剤１モルに対し、通常１〜５モル程度である。 In the imidation reaction, various known catalysts may be used for the purpose of performing the reaction in a low temperature range of about 50 ° C to 100 ° C. Specifically, for example, a combination of a dehydrating agent such as dicyclohexylcarbodiimide or acetic anhydride and a basic compound such as pyridine, triethylamine or sodium acetate can be used. In addition, the usage-amount of the said basic compound is about 1-5 mol normally with respect to 1 mol of dehydrating agents.
また、両反応時には、必要に応じて各種の重合禁止措置をとることができる。具体的には、例えば、重合禁止剤（フェノール類、ジチオカルバミン酸塩類、フェノチアジン類等）を、前記脂環式ジカルボン酸（無水物）１モルに対して通常０．０００１〜０．０１モル％程度用いたり、反応系を空気や酸素でバブリングしたりすることができる。 In both reactions, various polymerization prohibition measures can be taken as necessary. Specifically, for example, a polymerization inhibitor (phenols, dithiocarbamates, phenothiazines, etc.) is usually about 0.0001 to 0.01 mol% with respect to 1 mol of the alicyclic dicarboxylic acid (anhydride). It can be used or the reaction system can be bubbled with air or oxygen.
こうして得られた、前記一般式（６）で示す脂環式マレイミド化合物は、前記精製手段で精製してもよい。また、該脂環式マレイミド化合物が、分子中の脂環骨格に炭素−炭素不飽和結合を含む場合には、この段階においても前記同様に水素化反応を適用してもよい。 The alicyclic maleimide compound represented by the general formula (6) thus obtained may be purified by the purification means. Further, when the alicyclic maleimide compound contains a carbon-carbon unsaturated bond in the alicyclic skeleton in the molecule, a hydrogenation reaction may be applied at this stage as described above.
[工程（II）について]
該脂環式マレイミド化合物に、前記一般式（７）で示すビニル化合物を反応させる方法は、前記一般式（６）中のＲ６の種類により異なる。例えば、Ｒ６が水酸基である場合には、当該脂環式マレイミド化合物と前記ビニル化合物とをエステル化反応させればよい。また、Ｒ６がハロゲン原子である場合には、当該脂環式マレイミド化合物と前記ビニル化合物とを各種公知の方法で置換反応させればよい。
[About Process (II)]
The method of reacting the alicyclic maleimide compound with the vinyl compound represented by the general formula (7) differs depending on the type of R 6 in the general formula (6). For example, when R 6 is a hydroxyl group, the alicyclic maleimide compound and the vinyl compound may be esterified. When R 6 is a halogen atom, the alicyclic maleimide compound and the vinyl compound may be subjected to a substitution reaction by various known methods.
該ビニル化合物の具体例としては、例えばアクリル酸やメタクリル酸が挙げられる。 Specific examples of the vinyl compound, for example, acrylic acid or methacrylic acid.
前記エステル化反応は特に限定されず、各種公知の方法を利用できる。具体的には、例えば、前記脂環式マレイミド化合物１モルと、これに対し通常０．５〜２０モル程度となる前記ビニル化合物とを、通常２０℃〜１５０℃程度の温度で、通常２〜２０時間程度反応させればよい。なお、反応時には、水と共沸する芳香族系溶媒（好ましくはトルエン）を用い、水を反応系から除去しながら反応を行うのが好ましい。また、必要に応じて各種公知のエステル化触媒、例えば酸触媒〔ｐ−トルエンスルホン酸、硫酸等〕、金属酸化物・水酸化物〔水酸化リチウム、酸化カルシウム、酸化マグネシウム等〕を、前記マレイミド化合物１モルに対し、通常０．００１〜０．２モル程度用いることができる。また、必要に応じて前記重合禁止措置を適用することもできる。重合禁止剤の使用量は、該脂環式マレイミド化合物１モルに対して通常０．０００１〜０．０１モル％程度である。 The esterification reaction is not particularly limited, and various known methods can be used. Specifically, for example, 1 mol of the alicyclic maleimide compound and the vinyl compound which is usually about 0.5 to 20 mol are usually 2 to 20 ° C. What is necessary is just to make it react for about 20 hours. In the reaction, it is preferable to use an aromatic solvent (preferably toluene) azeotroped with water and perform the reaction while removing water from the reaction system. If necessary, various known esterification catalysts such as acid catalysts (p-toluenesulfonic acid, sulfuric acid, etc.), metal oxides / hydroxides (lithium hydroxide, calcium oxide, magnesium oxide, etc.) Usually, about 0.001 to 0.2 mol can be used with respect to 1 mol of the compound. Moreover, the said superposition | polymerization prohibition measure can also be applied as needed. The usage-amount of a polymerization inhibitor is about 0.0001-0.01 mol% normally with respect to 1 mol of this alicyclic maleimide compound.
前記置換反応は特に限定されず、各種公知の方法を利用できる。具体的には、例えば前記脂環式マレイミド化合物１モルと、これに対し通常０．８〜２モル程度の前記ビニル化合物と、該ビニル化合物と同モル程度の塩基性触媒（例えば水酸化ナトリウム水溶液）と、必要に応じて各種溶媒とからなる溶液に、１モル程度の前記脂環式マレイミド化合物（通常、トルエンとメタノールとからなる混合溶媒で溶解したもの）を通常３０分〜２時間かけて滴下し、通常２０℃〜１５０℃程度、通常２〜２０時間程度置換反応させればよい。 The substitution reaction is not particularly limited, and various known methods can be used. Specifically, for example, 1 mol of the alicyclic maleimide compound, usually about 0.8 to 2 mol of the vinyl compound, and a basic catalyst of the same mol as the vinyl compound (for example, sodium hydroxide aqueous solution) And about 1 mol of the alicyclic maleimide compound (usually dissolved in a mixed solvent consisting of toluene and methanol) in a solution consisting of various solvents as necessary over a period of usually 30 minutes to 2 hours. The reaction may be carried out by dropping, and the substitution reaction is usually about 20 ° C to 150 ° C, usually about 2 to 20 hours.
なお、前記脂環式マレイミド化合物が、前記一般式（６）のＲ２中に炭素−炭素不飽和結合を有する場合には、前記重合禁止措置を適用することができる。重合禁止剤の使用量は、該脂環式マレイミド化合物１モルに対して通常０．０００１〜０．０１モル％程度である。 Note that the alicyclic maleimide compound, carbon in R 2 in the general formula (6) - when carbon unsaturated bond, can be applied to the polymerization inhibiting action. The usage-amount of a polymerization inhibitor is about 0.0001-0.01 mol% normally with respect to 1 mol of this alicyclic maleimide compound.
こうして得られた、前記一般式（３−１）、（３−２）、（３−３）、（３−４）および（３−５）から選ばれる１種の脂環イミド（メタ）アクリレートは、通常はそのままでも高純度であるが、前記精製手段で精製することにより、純度をより高めることができる。また、該脂環イミド（メタ）アクリレートが、分子中の脂環骨格に炭素−炭素不飽和結合を含む場合には、前記同様水素化反応を適用してもよい。水素化した脂環イミド（メタ）アクリレートを用いた重合体は耐熱性が良く、また軟化点が高いなどの特徴を有する。 One alicyclic imide (meth) acrylate selected from the general formulas (3-1), (3-2), (3-3), (3-4) and (3-5) thus obtained. Although it is usually highly pure as it is, the purity can be further improved by purifying with the purification means. Further, when the alicyclic imide (meth) acrylate contains a carbon-carbon unsaturated bond in the alicyclic skeleton in the molecule, a hydrogenation reaction may be applied as described above. A polymer using hydrogenated alicyclic imide (meth) acrylate has good heat resistance and a high softening point.
本発明に係る脂環イミド（メタ）アクリレートは、分子中に重合性二重結合を有するので、単独で重合させ、若しくは他の重合性モノマーと共重合させることにより、各種の、油性ないし水性の重合体組成物とすることができる。 Since the alicyclic imide (meth) acrylate according to the present invention has a polymerizable double bond in the molecule, various kinds of oily or aqueous can be obtained by polymerizing alone or copolymerizing with other polymerizable monomers. It can be set as a polymer composition.
他の重合性モノマーとしては、例えば、アクリル酸アルキルエステル〔（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸ヒドロキシエチル、（メタ）アクリル酸イソボルニル等〕、芳香族系モノマー〔スチレン、α−メチルスチレン、ビニルトルエン、インデン、メチルインデン等〕、アニオン性ビニルモノマーやその中和塩〔（メタ）アクリル酸、クロトン酸、マレイン酸、イタコン酸、フマル酸、ムコン酸、シトラコン酸、ビニルスルホン酸、スチレンスルホン酸、（メタ）アリルスルホン酸、２−アクリルアミド−２−メチルプロパンスルホン酸等や、これらの中和塩〕、第三級アミノ基含有ビニルモノマー〔アリルアミン、Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジエチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジメチルアミノプロピル（メタ）アクリルアミド、Ｎ，Ｎ−ジエチルアミノプロピル（メタ）アクリルアミド等〕、該第三級アミノ基含有ビニルモノマーを四級化剤〔メチルクロライド、ベンジルクロライド、ジメチル硫酸、エピクロルヒドリン等〕で第四級化してなるカチオン性ビニルモノマー、多官能ビニルモノマー〔ジビニルベンゼン、トリプロピレングリコールジアクリレート、テトラエチレングリコールジアクリレート、トリメチロールプロパントリアクリレート、ジトリメチロールプロパンテトラアクリレート、ビスフェノールＡテトラエチレングリコールジアクリレート、ヘキサメチレングリコールジアクリレート、１，９−ノナンジオールジアクリレート、ペンタエリスリトールテトラアクリレート、ジペンタエリスリトールヘキサアクリレート、Ｎ−ビニルピロリドン、（メタ）アクリルアミドＮ−ビニルホルムアミド、４−ヒドロキシブチルビニルエーテル、ジエチレングリコールジビニルエーテル等〕、酢酸ビニルなどのモノマーが挙げられ、これらは１種を単独で、あるいは２種以上を組み合わせて用いることができる。 Other polymerizable monomers include, for example, alkyl acrylate esters [methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, hydroxyethyl (meth) acrylate, isobornyl (meth) acrylate Etc.], aromatic monomers (styrene, α-methylstyrene, vinyltoluene, indene, methylindene, etc.), anionic vinyl monomers and neutralized salts thereof ((meth) acrylic acid, crotonic acid, maleic acid, itaconic acid, Fumaric acid, muconic acid, citraconic acid, vinyl sulfonic acid, styrene sulfonic acid, (meth) allyl sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, etc., and neutralized salts thereof], containing tertiary amino group Vinyl monomer [allylamine, N, N-dimethylaminoethyl (meth) acrylate , N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide, etc.], and the tertiary amino group-containing vinyl monomer is quaternized. Cationic vinyl monomers and polyfunctional vinyl monomers (divinylbenzene, tripropylene glycol diacrylate, tetraethylene glycol diacrylate, trimethylolpropane) that are quaternized with agents such as methyl chloride, benzyl chloride, dimethyl sulfate, epichlorohydrin, etc. Triacrylate, ditrimethylolpropane tetraacrylate, bisphenol A tetraethylene glycol diacrylate, hexamethylene glycol diacrylate, 1,9-nonanediol diacrylate , Pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, N-vinyl pyrrolidone, (meth) acrylamide N-vinyl formamide, 4-hydroxybutyl vinyl ether, diethylene glycol divinyl ether, etc.], and vinyl acetate. One species can be used alone, or two or more species can be used in combination.
なお、本発明の脂環イミド（メタ）アクリレートと前記その他のモノマーを共重合させる場合において、両者の重量比は、得られる重合体組成物の用途に応じて適宜決定することができるが、例えば前者：後者で８０：２０〜１０：９０程度である。 In addition, in the case of copolymerizing the alicyclic imide (meth) acrylate of the present invention and the other monomer, the weight ratio of the two can be appropriately determined according to the use of the resulting polymer composition. The former: the latter is about 80:20 to 10:90.
重合方法は特に制限されず、例えば活性エネルギー線（紫外線や電子線）を照射したり（光重合）、加熱したりする方法（加熱重合）を採用できる。また、重合は、前記溶媒の存在下または不存在下で行うこともできる。 The polymerization method is not particularly limited, and for example, a method of irradiating active energy rays (ultraviolet rays or electron beams) (photopolymerization) or heating (heat polymerization) can be employed. The polymerization can also be performed in the presence or absence of the solvent.
光重合の際には、各種公知の光重合開始剤を用いることができる。具体的には、例えば、アセトフェノン類〔アセトフェノン、２，２−ジメトキシ−２−フェニルアセトフェノン、２，２−ジエトキシ−２−フェニルアセトフェノン、１，１−ジクロロアセトフェノン、１−ヒドロキシシクロヘキシルフェニルケトン、２−メチル−１−[４−（メチルチオ）フェニル]−２−モルフォリノ−プロパン−１−オンおよびＮ，Ｎ−ジメチルアミノアセトフェノン等〕、ベンゾフェノン類〔ベンゾフェノン、メチルベンゾフェノン、４，４’−ジクロロベンゾフェノン、４，４’−ビスジエチルアミノベンゾフェノン、ミヒラーズケトンおよび４−ベンゾイル−４’−メチルジフェニルサルファイド等〕、チオキサントン類〔２，４−ジメチルチオキサントン、２，４−ジエチルチオキサントン、２−クロロチオキサントンおよび２，４−ジイソプロピルチオキサントン等のチオキサントン〕、アントラキノン類〔２−メチルアントラキノン、１−クロロアントラキノンおよび２−アミルアントラキノン等〕、ベンゾイン類〔ベンゾイン、ベンゾインメチルエーテルおよびベンゾインプロピルエーテル等〕が挙げられ、これらは１種を単独で、あるいは２種以上を組み合わせて用いることができる。また、必要に応じてＮ，Ｎ−ジメチルアミノ安息香酸エチルエステル、Ｎ，Ｎ−ジメチルアミノ安息香酸イソアミルエステル、トリエチルアミンおよびトリエタノールアミン等の光増感剤を併用することもできる。なお、該光重合開始剤や該光増感剤の使用量はいずれも、重合体組成物の固形分重量に対し、通常０．０１〜１０重量％程度である。 In the photopolymerization, various known photopolymerization initiators can be used. Specifically, for example, acetophenones [acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2- Methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one and N, N-dimethylaminoacetophenone, etc.], benzophenones [benzophenone, methylbenzophenone, 4,4′-dichlorobenzophenone, 4 , 4′-bisdiethylaminobenzophenone, Michler's ketone, 4-benzoyl-4′-methyldiphenyl sulfide, etc.], thioxanthones [2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxone] Thioxanthones such as N, and 2,4-diisopropylthioxanthone], anthraquinones [2-methylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, etc.], benzoins [benzoin, benzoin methyl ether, benzoin propyl ether, etc.] These can be used singly or in combination of two or more. Further, if necessary, photosensitizers such as N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, triethylamine and triethanolamine can be used in combination. In addition, both the usage-amount of this photoinitiator and this photosensitizer are about 0.01 to 10 weight% normally with respect to the solid content weight of a polymer composition.
また熱重合の際には、各種公知の熱重合開始剤を用いることができる。具体的には、例えば、有機過酸化物〔１，１−ビス（ｔ−ブチルパーオキシ）２−メチルシクロヘキサン、１，１−ビス（ｔ−ヘキシルパーオキシ）−３，３，５−トリメチルシクロヘキサン、１，１−ビス（ｔ−ヘキシルパーオキシ）シクロヘキサン、１，１−ビス（ｔ−ブチルパーオキシ）−３，３，５−トリメチルシクロヘキサン、１，１−ビス（ｔ−ブチルパーオキシ）シクロヘキサン等〕、アゾ系化合物〔１，１’−アゾビス（シクロヘキサン−１−カルボニトリル）、２−（カルバモイルアゾ）イソブチロニトリル、２−フェニルアゾ−４−メトキシ−２，４−ジメチルバレロニトリル、アゾジ−ｔ−オクタンおよびアゾジ−ｔ−ブタン等〕が挙げられ、これらは１種を単独で、あるいは２種以上を組み合わせて用いることができる。なお、前記有機過酸化物は還元剤と組み合わせることによりレドックス系開始剤としてもよい。該熱重合開始剤の使用量は、重合体組成物の固形分重量に対して、通常０．０１〜１０重量％程度である。 In the thermal polymerization, various known thermal polymerization initiators can be used. Specifically, for example, organic peroxide [1,1-bis (t-butylperoxy) 2-methylcyclohexane, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane Etc.], azo compounds [1,1′-azobis (cyclohexane-1-carbonitrile), 2- (carbamoylazo) isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, azodi -T-octane and azodi-t-butane, etc.], and these can be used alone or in combination of two or more. That. In addition, the said organic peroxide is good also as a redox-type initiator by combining with a reducing agent. The usage-amount of this thermal-polymerization initiator is about 0.01 to 10 weight% normally with respect to the solid content weight of a polymer composition.
その他、重合反応時には前記重合禁止剤や重合禁止措置を適用することもできる。 In addition, the polymerization inhibitor and the polymerization prohibition measure can be applied during the polymerization reaction.
本発明の重合体組成物には、その用途に応じて各種添加剤を適用することができる。具体的には、例えば、耐熱性、密着性、硬度などの特性を向上する目的で無機充填剤〔シリカ粉末、アルミナ、ジルコン、ケイ酸カルシウム、炭酸カルシウム等〕を適用できるほか、着色剤〔フタロシアニン・ブルー、フタロシアニングリーン、アイオジン・グリーン、ジスアゾイエロー、クリスタルバイオレット、酸化チタン、カーボンブラック、ナフタレンブラック等〕、難燃剤〔三酸化アンチモン、リン酸エステル、赤リンおよびメラミン樹脂をはじめとする含窒素化合物等〕、消泡剤〔シリコーン系、フッ素系、高分子系等〕、密着性付与剤〔イミダゾール類、チアゾール類、トリアゾール類、シランカップリング剤等〕、応力緩和剤〔シリコーンオイル、シリコーンゴム粉末等〕、光安定剤〔ヒンダードアミン系化合物等〕、帯電防止剤、レベリング剤などを用いることができる。また、前記溶媒を希釈溶剤として用いることもできる。 Various additives can be applied to the polymer composition of the present invention depending on its use. Specifically, for example, inorganic fillers (silica powder, alumina, zircon, calcium silicate, calcium carbonate, etc.) can be applied for the purpose of improving properties such as heat resistance, adhesion, and hardness, and colorants (phthalocyanine).・ Blue, Phthalocyanine Green, Iodine Green, Disazo Yellow, Crystal Violet, Titanium Oxide, Carbon Black, Naphthalene Black, etc.), Flame Retardant [antimony trioxide, phosphate ester, red phosphorus, melamine resin and other nitrogen-containing compounds Etc.], antifoaming agents (silicone-based, fluorine-based, polymer-based, etc.), adhesion-imparting agents (imidazoles, thiazoles, triazoles, silane coupling agents, etc.), stress relieving agents (silicone oil, silicone rubber powder) Etc.), light stabilizers (hindered amine compounds, etc.), charging Or the like can be used stop, leveling agents. Moreover, the said solvent can also be used as a dilution solvent.
なお、各重合反応は各種溶媒、例えば、アルコール系溶媒（メタノール、エタノール等）、芳香族系溶媒（ベンゼン、トルエン、キシレン等）、ケトン系溶媒（アセトン、メチルエチルケトン等）、エーテル系溶媒（ＴＨＦ等）の存在下または不存在下で行うことできる。 Each polymerization reaction can be carried out in various solvents such as alcohol solvents (methanol, ethanol, etc.), aromatic solvents (benzene, toluene, xylene, etc.), ketone solvents (acetone, methyl ethyl ketone, etc.), ether solvents (THF, etc.). ) In the presence or absence.
また、活性エネルギー線としては、例えば、紫外線や電子線が挙げられる。紫外線の光源としては、例えば低圧水銀灯、高圧水銀灯、メタルハライドランプ、キセノンランプ、無電極放電ランプおよびカーボンアークランプ等が挙げられる。また、電子線源としては、
例えばコックロフトワルトシン型、バンデグラフ型または共振変圧器型の照射装置が挙げ
られる。
Moreover, as an active energy ray, an ultraviolet-ray and an electron beam are mentioned, for example. Examples of the ultraviolet light source include a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, an electrodeless discharge lamp, and a carbon arc lamp. As an electron beam source,
For example, a Cockloft-Waltsin type, a bandegraph type or a resonant transformer type irradiation device may be mentioned.
以下に、実施例を挙げて本発明を更に具体的に説明するが、本発明はこれらの実施例のみに限定されるものではない。なお、スペクトル測定には次の装置を使用した。
１Ｈ−ＮＭＲ、１３Ｃ−ＮＭＲ：ＢＲＵＫＥＲＡＲＸ３００（ブルカーバイオスピン社製）
ＩＲ：ＡＶＡＴＡＲ３６０（ＴｈｅｒｍｏＮｉｃｏｌｅｔ社製）
ガスクロマトグラフィー（ＧＣ）：５８９０ＳＥＲＩＥＳ II（ＨＥＷＬＥＴＴ社製）
Hereinafter, the present invention will be described more specifically by way of examples. However, the present invention is not limited to these examples. In addition, the following apparatus was used for the spectrum measurement.
1 H-NMR, 13 C-NMR: BRUKERARX300 (manufactured by Bruker BioSpin)
IR: AVATAR 3 60 (ThermoNicolet Co., Ltd.)
Gas chromatography (GC): 5890 SERIES II (made by HEWLETT)
実施例１
温度計、滴下ロート、窒素ガス導入口、攪拌機を備えた反応容器に、無水マレイン酸１７９．９ｇと脱水トルエン３５０ｍＬを仕込み、系内を窒素置換した。次いで、無水マレイン酸を５０℃で溶解し、攪拌下にα−テルピネン（和光純薬（株）製、純度９０％）２７７．８ｇを、系内の温度が６０℃程度になるように水浴で発熱を抑えながら滴下した。滴下終了後、系内の温度が下がりはじめたら、６０℃で加熱攪拌しながらディールス・アルダー反応を６時間行った。反応終了後、溶媒および未反応原料を減圧留去・除去して固体を採取し、これを減圧乾燥することにより、脂環式ジカルボン酸無水物（以下、α−テルピネン酸無水物という）を４１７．１ｇ得た。なお、このものの純度（ＧＣ法による測定値をいう。以下、同様）は９６．９％であった。
Example 1
A reaction vessel equipped with a thermometer, a dropping funnel, a nitrogen gas inlet, and a stirrer was charged with 179.9 g of maleic anhydride and 350 mL of dehydrated toluene, and the system was purged with nitrogen. Next, maleic anhydride was dissolved at 50 ° C., and 277.8 g of α-terpinene (manufactured by Wako Pure Chemical Industries, Ltd., purity 90%) was stirred in a water bath so that the temperature in the system was about 60 ° C. The solution was added dropwise while suppressing heat generation. When the temperature in the system began to drop after completion of the dropwise addition, Diels-Alder reaction was performed for 6 hours while heating and stirring at 60 ° C. After completion of the reaction, the solvent and unreacted raw material were removed by distillation under reduced pressure to collect a solid, which was dried under reduced pressure to obtain alicyclic dicarboxylic acid anhydride (hereinafter referred to as α-terpinenic acid anhydride) 417. 0.1 g was obtained. In addition, the purity (referred to as a measured value by the GC method, hereinafter the same) of this product was 96.9%.
次に、ディーンスターク分水器（ジムロート冷却管）、温度計、滴下ロート、窒素ガス導入口、攪拌機を備えた反応容器に、前記α−テルピネン酸無水物１８０．０ｇ、脱水トルエン２００ｍＬを仕込み、系内を窒素置換した。次いで、室温で系内を攪拌しつつ、エタノールアミン４５．３ｇを滴下した。滴下終了後、反応系を１０６〜１１０℃まで昇温して、ディーンスターク分水器により水を系内から留去しながら、イミド化反応を２０時間行った。その際、共沸除去したトルエンおよびエタノールアミンを系内に補充しながらイミド化反応を行った。反応終了後、溶媒を減圧留去してから、ｎ−ヘキサンを加えて再結晶を行った。次いで、得られた結晶を減圧乾燥することにより、脂環式マレイミド化合物２０７．０ｇを得た。このものの純度は９７．２％であった。 Next, a reaction vessel equipped with a Dean-Stark water separator (Dimroth condenser), thermometer, dropping funnel, nitrogen gas inlet, and stirrer was charged with 180.0 g of the α-terpinenic acid anhydride and 200 mL of dehydrated toluene, The system was replaced with nitrogen. Next, 45.3 g of ethanolamine was added dropwise while stirring the system at room temperature. After completion of the dropwise addition, the reaction system was heated to 106 to 110 ° C., and an imidization reaction was performed for 20 hours while distilling water from the system with a Dean-Stark water separator. At that time, imidization reaction was performed while replenishing toluene and ethanolamine azeotropically removed into the system. After completion of the reaction, the solvent was distilled off under reduced pressure, and n-hexane was added for recrystallization. Subsequently, the obtained crystal was dried under reduced pressure to obtain 207.0 g of an alicyclic maleimide compound. The purity of this product was 97.2%.
次に、ディーンスターク分水器（ジムロート冷却管）、温度計、滴下ロート、空気バブリング用導入管、攪拌機を備えた反応容器に、当該脂環式マレイミド化合物１５０．０ｇ、ヒドロキノン１．８５ｇ、トルエン３００ｍＬを仕込み、ｐ−トルエンスルホン酸３．７０ｇ、アクリル酸１８５．１ｇを添加して攪拌した。次いで、反応系を空気でバブリングしながら１０６〜１１０℃まで昇温して、ディーンスターク分水器で水を系内から留去しながらエステル化反応を２１時間行った。その際、反応の進行はＧＣで追跡した。また、反応を促進させ、完結させる目的でｐ−トルエンスルホン酸を系内に添加しながら反応を行った。次いで、反応溶液を室温まで冷却し、分液ロートを用いてイオン交換水、炭酸水素ナトリウム水溶液での洗浄を３回繰り返し、更に減圧下にトルエンを留去し、脂環イミドアクリレート（Ａ−１）（以下、化合物Ａ−１という）１２８．７ｇを得た。なお、このものの純度は９２．４％であった。 Next, 150.0 g of the alicyclic maleimide compound, 1.85 g of hydroquinone, toluene in a reaction vessel equipped with a Dean-Stark water separator (Dimroth condenser), a thermometer, a dropping funnel, an air bubbling introduction tube, and a stirrer. 300 mL was charged, and 3.70 g of p-toluenesulfonic acid and 185.1 g of acrylic acid were added and stirred. Next, the temperature of the reaction system was raised to 106 to 110 ° C. while bubbling with air, and the esterification reaction was carried out for 21 hours while water was distilled away from the system using a Dean-Stark water separator. At that time, the progress of the reaction was followed by GC. In addition, the reaction was carried out while adding p-toluenesulfonic acid into the system for the purpose of promoting and completing the reaction. Next, the reaction solution was cooled to room temperature, washed with ion-exchanged water and an aqueous sodium hydrogen carbonate solution three times using a separatory funnel, and further toluene was distilled off under reduced pressure to obtain an alicyclic imide acrylate (A-1 ) (Hereinafter referred to as Compound A-1) 128.7 g. The purity of this product was 92.4%.
１ Ｈ−ＮＭＲ（３００ＭＨｚ、溶媒ＣＤＣｌ ３ 、δ（ｐｐｍ））：６．３６、６．１０、５．８６、４．２０、３．７１、２．９３、２．５４、１．４７、１．２７、１．０９、０．９７
１３ Ｃ−ＮＭＲ（３００ＭＨｚ、溶媒ＣＤＣｌ ３ 、δ（ｐｐｍ））：１７７．１０、１６５．６１、１３５．０９、１３５．３６、１３１．２０、１２８．００、１２７．８９、６０．９３、５０．０９、４６．２３、４３．５０、３６．８５、３４．１８、２９．５２、２２．８０、１８．３０、１６．７８
ＩＲ（ｎｅａｔ）：２９６０、１７２６、１７０２、１６９２、１４００、１１８２ｃｍ−１
1 H-NMR (300 MHz, solvent CDCl 3 , δ (ppm)) : 6.36, 6.10, 5.86, 4.20, 3.71, 2.93, 2.54, 1.47, 1 .27, 1.09, 0.97
13 C-NMR (300 MHz, solvent CDCl 3 , δ (ppm)): 177.10, 165.61, 135.09, 135.36, 131.20, 128.00, 127.89, 60.93, 50 .09, 46.23, 43.50, 36.85, 34.18, 29.52, 22.80, 18.30, 16.78
IR (neat) : 2960, 1726, 1702, 1692, 1400, 1182 cm −1
実施例２
温度計、水素バルーンを備えた反応容器に、実施例１で得られたα−テルピネン酸無水物１８０．０ｇ、パラジウムカーボン１８．０ｇ、脱水ＴＨＦ２００ｍＬを仕込み、攪拌下に、５０℃で３０時間水素化反応を行った。反応終了後、反応系を室温まで冷却し、濾過によりパラジウムカーボンを除去した後、減圧下にＴＨＦを留去した。次いで、得られた固体を減圧乾燥して、水素化α−テルピネン酸無水物１６３．４ｇを得た。
なお、このものの純度は９８．６％であった。
Example 2
A reaction vessel equipped with a thermometer and a hydrogen balloon was charged with 180.0 g of α-terpinenic acid anhydride obtained in Example 1, 18.0 g of palladium carbon, and 200 mL of dehydrated THF, and hydrogenated at 50 ° C. for 30 hours with stirring. The reaction was carried out. After completion of the reaction, the reaction system was cooled to room temperature, palladium carbon was removed by filtration, and then THF was distilled off under reduced pressure. Subsequently, the obtained solid was dried under reduced pressure to obtain 163.4 g of hydrogenated α-terpinenic acid anhydride.
The purity of this product was 98.6%.
次に、ディーンスターク分水器（ジムロート冷却管）、温度計、滴下ロート、窒素ガス導入口、攪拌機を備えた反応容器に、前記水素化α−テルピネン酸無水物１１８．９ｇ、脱水トルエン２００ｍＬを仕込み、系内を窒素置換した。その後、室温において、攪拌状態の反応系に、エタノールアミン３０．７ｇを滴下した。滴下終了後、系内の発熱が落ち着いたら、反応系を１０６〜１１０℃まで昇温して、ディーンスターク分水器で水を系内から留去しながらイミド化反応を８時間行った。その際、水と共に留去したトルエンおよびエタノールアミンを系内に補充しながら反応を行った。反応終了後、溶媒を減圧下に留去し、次いでｎ−ヘキサンを加えて再結晶を行った。その後、得られた結晶を減圧乾燥することにより、脂環式マレイミド化合物１１９．６ｇを得た。なお、このものの純度は９８．９％であった。 Next, 118.9 g of the hydrogenated α-terpinenic acid anhydride and 200 mL of dehydrated toluene were placed in a reaction vessel equipped with a Dean-Stark water separator (Dimroth condenser), thermometer, dropping funnel, nitrogen gas inlet, and stirrer. The system was purged with nitrogen. Thereafter, 30.7 g of ethanolamine was added dropwise to the stirred reaction system at room temperature. When the heat generation in the system settled after completion of the dropwise addition, the reaction system was heated to 106 to 110 ° C., and an imidization reaction was carried out for 8 hours while distilling water from the system with a Dean-Stark water separator. At that time, the reaction was carried out while replenishing toluene and ethanolamine distilled off together with water. After completion of the reaction, the solvent was distilled off under reduced pressure, and then n-hexane was added for recrystallization. Thereafter, the obtained crystal was dried under reduced pressure to obtain 119.6 g of an alicyclic maleimide compound. The purity of this product was 98.9%.
次に、ディーンスターク分水器（ジムロート冷却管）、温度計、滴下ロート、空気バブリング用導入管、攪拌機を備えた反応容器に、当該脂環式マレイミド化合物１１９．５ｇ、ヒドロキノン０．５６ｇ、トルエン４００ｍＬを仕込み、ｐ−トルエンスルホン酸８．１４ｇ、アクリル酸１４６．４ｇを添加して攪拌した。次いで、反応系を空気でバブリングしながら１０６〜１１０℃まで昇温し、ディーンスターク分水器で水を系内から留去しながらエステル化反応を７時間行った。次いで、反応溶液を室温まで冷却し、分液ロートを用いてイオン交換水、炭酸水素ナトリウム水溶液での洗浄を３回繰り返し、更に減圧下にトルエンを留去し、脂環イミドアクリレート（Ａ−２）（以下、化合物Ａ−２という）１０９．１ｇを得た。なお、このものの純度は９７．０％であった。 Next, 119.5 g of the alicyclic maleimide compound, 0.56 g of hydroquinone, toluene are added to a reaction vessel equipped with a Dean-Stark water separator (Dimroth condenser), a thermometer, a dropping funnel, an introduction tube for air bubbling, and a stirrer. 400 mL was charged, and 8.14 g of p-toluenesulfonic acid and 146.4 g of acrylic acid were added and stirred. Next, the reaction system was heated to 106 to 110 ° C. while bubbling with air, and the esterification reaction was carried out for 7 hours while distilling water from the system with a Dean-Stark water separator. Next, the reaction solution was cooled to room temperature, washed with ion-exchanged water and an aqueous sodium hydrogen carbonate solution three times using a separatory funnel, and further toluene was distilled off under reduced pressure to obtain an alicyclic imide acrylate (A-2 ) (Hereinafter referred to as Compound A-2) 109.1 g was obtained. The purity of this product was 97.0%.
１ Ｈ−ＮＭＲ（３００ＭＨｚ、溶媒ＣＤＣｌ ３ 、δ（ｐｐｍ））：６．３９、６．１０、５．８３、４．３２、３．８３、２．９４、２．５４、１．４７、１．１３、０．９７、０．８１
１３ Ｃ−ＮＭＲ（３００ＭＨｚ、溶媒ＣＤＣｌ ３ 、δ（ｐｐｍ））：１７８．１９、１３１．３３、１３１．０６、１２８．０５、１２７．８６、６１．０８、５９．５７、４８．７７、４４．８２、３７．１３、３３．９２、３１．０７、２８．９９、２６．３６、２５．２６、２２．９３、１７．３０、１６．９１
ＩＲ（ｎｅａｔ）：２９４９、１７２６、１７０２、１６９２、１３９６、１１８２ｃｍ−１
1 H-NMR (300 MHz, solvent CDCl 3 , δ (ppm)) : 6.39, 6.10, 5.83, 4.32, 3.83, 2.94, 2.54, 1.47, 1 .13, 0.97, 0.81
13 C-NMR (300 MHz, solvent CDCl 3 , δ (ppm)) : 178.19, 131.33, 131.06, 128.05, 127.86, 61.08, 59.57, 48.77, 44 .82, 37.13, 33.92, 31.07, 28.99, 26.36, 25.26, 22.93, 17.30, 16.91
IR (neat) : 2949, 1726, 1702, 1692, 1396, 1182 cm −1
実施例３
温度計、滴下ロート、窒素ガス導入口、攪拌機を備えた反応容器に、無水マレイン酸３０９．８ｇと脱水トルエン２５０ｍＬを仕込み、系内を窒素置換した。次いで、無水マレイン酸を５０℃で溶解し、攪拌下にミルセン（アルドリッチ製、純度９０％）５０３．４ｇを、系内の温度が６０℃程度になるように水浴で発熱を抑えながら滴下した。滴下終了後、系内の温度が下がりはじめたら、６０℃で加熱攪拌しながらディールス・アルダー反応を３時間行った。反応終了後、副生物を濾過で分離後、溶媒および未反応原料を減圧留去・除去して淡黄色液体を採取し、これを減圧乾燥することにより、脂環式ジカルボン酸無水物（以下、ミルセン酸無水物という）を６４６．９ｇ得た。なお、このものの純度は９０．２％であった。
Example 3
A reaction vessel equipped with a thermometer, a dropping funnel, a nitrogen gas inlet, and a stirrer was charged with 309.8 g of maleic anhydride and 250 mL of dehydrated toluene, and the system was purged with nitrogen. Next, maleic anhydride was dissolved at 50 ° C., and 503.4 g of myrcene (manufactured by Aldrich, purity 90%) was added dropwise with stirring while suppressing heat generation in a water bath so that the temperature in the system was about 60 ° C. When the temperature in the system began to drop after completion of the dropwise addition, Diels-Alder reaction was carried out for 3 hours while heating and stirring at 60 ° C. After completion of the reaction, by-products are separated by filtration, the solvent and unreacted raw material are distilled off under reduced pressure to remove a pale yellow liquid, and this is dried under reduced pressure to obtain an alicyclic dicarboxylic acid anhydride (hereinafter, 646.9 g of myrsenic anhydride was obtained. The purity of this product was 90.2%.
次に、ディーンスターク分水器（ジムロート冷却管）、温度計、滴下ロート、窒素ガス導入口、攪拌機を備えた反応容器に、前記ミルセン酸無水物１７５．０ｇ、脱水トルエン２００ｍＬを仕込み、系内を窒素置換した。次いで、室温で系内を攪拌しつつ、エタノールアミン４５．６ｇを滴下した。滴下終了後、反応系を１０６〜１１０℃まで昇温して、ディーンスターク分水器により水を系内から留去しながら、イミド化反応を１２時間行った。反応終了後、溶媒を減圧留去してから、得られた淡黄色粘性固体を減圧乾燥することにより、脂環式マレイミド化合物１８９．４ｇを得た。このものの純度は８８．０％であった。 Next, 175.0 g of myrsenic anhydride and 200 mL of dehydrated toluene were charged into a reaction vessel equipped with a Dean-Stark water separator (Dimroth condenser), thermometer, dropping funnel, nitrogen gas inlet, and stirrer. Was replaced with nitrogen. Next, 45.6 g of ethanolamine was added dropwise while stirring the system at room temperature. After completion of the dropwise addition, the reaction system was heated to 106 to 110 ° C., and an imidization reaction was performed for 12 hours while water was distilled away from the system using a Dean-Stark water separator. After completion of the reaction, the solvent was distilled off under reduced pressure, and the obtained pale yellow viscous solid was dried under reduced pressure to obtain 189.4 g of an alicyclic maleimide compound. The purity of this product was 88.0%.
次に、ディーンスターク分水器（ジムロート冷却管）、温度計、滴下ロート、空気バブリング用導入管、攪拌機を備えた反応容器に、当該脂環式マレイミド化合物１６０．０ｇ、ヒドロキノン１．７３ｇ、トルエン２００ｍＬを仕込み、ｐ−トルエンスルホン酸９．６６ｇ、アクリル酸１７３．７ｇを添加して攪拌した。次いで、反応系を空気でバブリングしながら１０６〜１１０℃まで昇温し、ディーンスターク分水器で水を系内から留去しながらエステル化反応を２１時間行った。その際、反応の進行はＧＣで追跡した。次いで、反応溶液を室温まで冷却し、分液ロートを用いてイオン交換水、炭酸水素ナトリウム水溶液での洗浄を３回繰り返し、更に減圧下にトルエンを留去し、脂環イミドアクリレート（Ａ−３）（以下、化合物Ａ−３という）１３２．５ｇを得た。なお、このものの純度は８９．０％であった。 Next, 160.0 g of the alicyclic maleimide compound, 1.73 g of hydroquinone, toluene are added to a reaction vessel equipped with a Dean-Stark water separator (Dimroth condenser), a thermometer, a dropping funnel, an air bubbling introduction tube, and a stirrer. 200 mL was charged, and 9.66 g of p-toluenesulfonic acid and 173.7 g of acrylic acid were added and stirred. Next, the reaction system was heated to 106-110 ° C. while bubbling with air, and the esterification reaction was carried out for 21 hours while water was distilled off from the system using a Dean-Stark water separator. At that time, the progress of the reaction was followed by GC. Next, the reaction solution was cooled to room temperature, washed with ion-exchanged water and an aqueous sodium hydrogen carbonate solution three times using a separatory funnel, and further toluene was distilled off under reduced pressure to obtain an alicyclic imide acrylate (A-3). ) (Hereinafter referred to as Compound A-3) 132.5 g was obtained. The purity of this product was 89.0%.
１ Ｈ−ＮＭＲ（３００ＭＨｚ、溶媒ＣＤＣｌ ３ 、δ（ｐｐｍ））：６．４０、６．０６、５．８２、５．５６、５．０２、４．２８、３．７７、３．０６、２．５２、２．２２、１．６７、１．５８、１．２７、１．０１、０．９４、０．７６
１３ Ｃ−ＮＭＲ（３００ＭＨｚ、溶媒ＣＤＣｌ ３ 、δ（ｐｐｍ））：１７９．７６、１６５．７０、１４０．３０、１３１．３０、１２７．８７、１２３．４９、１１９．７３、６０．９８、３９．２４、３７．２６、２７．４９、２５．９１、２４．０４、１９．３２、１７．６５
ＩＲ（ｎｅａｔ）：２９２９、１７０１、１３９８、１１８２ｃｍ−１
1 H-NMR (300 MHz, solvent CDCl 3 , δ (ppm)) : 6.40, 6.06, 5.82, 5.56, 5.02, 4.28, 3.77, 3.06, 2 .52, 2.22, 1.67, 1.58, 1.27, 1.01, 0.94, 0.76
13 C-NMR (300 MHz, solvent CDCl 3 , δ (ppm)): 179.76, 165.70, 140.30, 131.30, 127.87, 123.49, 119.73, 60.98, 39 .24, 37.26, 27.49, 25.91, 24.04, 19.32, 17.65
IR (neat) : 2929, 1701, 1398, 1182 cm −1
実施例４
温度計、水素バルーンを備えた反応容器に、実施例３で得られたミルセン酸無水物２００．０ｇ、パラジウムカーボン１５．０ｇ、脱水ＴＨＦ２００ｍＬを仕込み、攪拌下に、５０℃で７２時間水素化反応を行った。反応終了後、反応系を室温まで冷却し、濾過によりパラジウムカーボンを除去した後、減圧下にＴＨＦを留去した。次いで、得られた固体を減圧乾燥して、水素化ミルセン酸無水物１９８．０ｇを得た。なお、このものの純度は９０．６％であった。
Example 4
A reaction vessel equipped with a thermometer and a hydrogen balloon was charged with 200.0 g of myrsenic anhydride obtained in Example 3, 15.0 g of palladium carbon, and 200 mL of dehydrated THF, and the hydrogenation reaction was performed at 50 ° C. for 72 hours with stirring. Went. After completion of the reaction, the reaction system was cooled to room temperature, palladium carbon was removed by filtration, and then THF was distilled off under reduced pressure. Next, the obtained solid was dried under reduced pressure to obtain 198.0 g of hydrogenated myrsenic anhydride. The purity of this product was 90.6%.
次に、ディーンスターク分水器（ジムロート冷却管）、温度計、滴下ロート、窒素ガス導入口、攪拌機を備えた反応容器に、前記水素化ミルセン酸無水物１９８．０ｇ、脱水トルエン２００ｍＬを仕込み、系内を窒素置換した。その後、室温において、攪拌状態の反応系に、エタノールアミン５２．５ｇを滴下した。滴下終了後、系内の発熱が落ち着いたら、反応系を１０６〜１１０℃まで昇温し、ディーンスターク分水器で水を系内から留去しながらイミド化反応を６時間行った。反応終了後、室温に戻し、窒素ガス導入口を空気バブリング用導入管に取り替え、ヒドロキノン２．１９ｇ、ｐ−トルエンスルホン酸１１．４１ｇ、アクリル酸２１８．９ｇを添加して攪拌した。次いで、反応系を空気でバブリングしながら１０６〜１１０℃まで昇温し、ディーンスターク分水器で水を系内から留去しながらエステル化反応を１２時間行った。次いで、反応溶液を室温まで冷却し、分液ロートを用いてイオン交換水、炭酸水素ナトリウム水溶液での洗浄を３回繰り返し、更に減圧下にトルエンを留去し、脂環イミドアクリレート（Ａ−４）（以下、化合物Ａ−４という）２０６．０ｇを得た。なお、このものの純度は８５．６％であった。 Next, in a reaction vessel equipped with a Dean-Stark water separator (Dimroth condenser), a thermometer, a dropping funnel, a nitrogen gas inlet, and a stirrer, 198.0 g of the hydrogenated myrsenic acid anhydride and 200 mL of dehydrated toluene were charged. The system was replaced with nitrogen. Thereafter, 52.5 g of ethanolamine was added dropwise to the stirred reaction system at room temperature. When the heat generation in the system was settled after the completion of the dropping, the reaction system was heated to 106 to 110 ° C., and an imidization reaction was carried out for 6 hours while distilling water from the system with a Dean-Stark water separator. After completion of the reaction, the temperature was returned to room temperature, the nitrogen gas inlet was replaced with an air bubbling inlet, 2.19 g of hydroquinone, 11.41 g of p-toluenesulfonic acid, and 218.9 g of acrylic acid were added and stirred. Next, the temperature of the reaction system was raised to 106 to 110 ° C. while bubbling with air, and the esterification reaction was carried out for 12 hours while distilling water from the system with a Dean-Stark water separator. Next, the reaction solution was cooled to room temperature, washed with ion-exchanged water and an aqueous sodium hydrogen carbonate solution three times using a separatory funnel, and further toluene was distilled off under reduced pressure to obtain an alicyclic imide acrylate (A-4). ) (Hereinafter referred to as Compound A-4) 206.0 g. The purity of this product was 85.6%.
１ Ｈ−ＮＭＲ（３００ＭＨｚ、溶媒ＣＤＣｌ ３ 、δ（ｐｐｍ））：６．３４、６．０７、５．８２、４．３３、３．８１、２．８７、２．２２、１．６７、１．５８、１．２７、１．２２、１．１５、０．８６
１３ Ｃ−ＮＭＲ（３００ＭＨｚ、溶媒ＣＤＣｌ ３ 、δ（ｐｐｍ））：１７９．８６、１６５．６８、１３２．２０、１２７．８５、６０．９６、３９．７０、３６．８９、３４．０１、２８．７３、２７．８３、２４．２６、２２．５２
ＩＲ（ｎｅａｔ）：２９２７、１７０８、１３９７、１１８２ｃｍ−１
1 H-NMR (300 MHz, solvent CDCl 3 , δ (ppm)): 6.34, 6.07, 5.82, 4.33, 3.81, 2.87, 2.22, 1.67, 1 .58, 1.27, 1.22, 1.15, 0.86
13 C-NMR (300 MHz, solvent CDCl 3 , δ (ppm)): 179.86, 165.68, 132.20, 127.85, 60.96, 39.70, 36.89, 34.01, 28 .73, 27.83, 24.26, 22.52
IR (neat) : 2927, 1708, 1397, 1182 cm −1
比較例１
ディーンスターク分水器（ジムロート冷却管）、温度計、滴下ロート、窒素ガス導入口、攪拌機を備えた反応容器にテトラヒドロ無水フタル酸（商品名「リカシッドＴＨ」、新日本理化（株）製）２００．０ｇ、脱水トルエンを１８５．０ｇを仕込み、系内を窒素置換した。次いで、反応容器を室温で攪拌しつつエタノールアミン８０．３ｇを滴下した。滴下終了後、還流温度（１１０℃）まで加熱し、水をトルエンで共沸除去しつつ６時間反応を行うことにより、環イミド化合物を得た。このものは純度９９．１％であった（ＧＣ法による）。
Comparative Example 1
Tetrahydrophthalic anhydride (trade name “Licacid TH”, manufactured by Shin Nippon Rika Co., Ltd.) 200 in a reaction vessel equipped with a Dean Stark water separator (Dimroth condenser), thermometer, dropping funnel, nitrogen gas inlet, and stirrer 0.0 g and 185.0 g of dehydrated toluene were charged, and the system was purged with nitrogen. Next, 80.3 g of ethanolamine was added dropwise while stirring the reaction vessel at room temperature. After completion of the dropwise addition, the mixture was heated to the reflux temperature (110 ° C.) and reacted for 6 hours while removing water azeotropically with toluene to obtain a cyclic imide compound. This had a purity of 99.1% (according to GC method).
次いで、上記の反応溶液を室温まで戻し、窒素ガス導入口を空気バブリング用導入管に変更し、メトキノン２．５７ｇ、ｐ−トルエンスルホン酸１５ｇ、アクリル酸１８５．９ｇを添加し攪拌した。系内で空気をバブリングしながら、還流温度（１０６〜１１０℃）まで加熱昇温し、ディーンスターク分水器で水を系内から留去しながら反応を１６時間行った。次いで、反応溶液を４０℃以下まで冷却し、分液ロートを用いてイオン交換水、炭酸水素ナトリウム水溶液での洗浄を繰り返し、減圧濃縮でトルエンを留去し、脂環イミドアクリレートＢ（以下、化合物Ｂという）を得た。このものは純度９３．１％であった（ＧＣ法による）。なお、当該化合物Ｂの各スペクトル測定値および構造は、以下のようになる。 Next, the reaction solution was returned to room temperature, the nitrogen gas inlet was changed to an air bubbling inlet tube, 2.57 g of methoquinone, 15 g of p-toluenesulfonic acid, and 185.9 g of acrylic acid were added and stirred. While bubbling air in the system, the temperature was raised to the reflux temperature (106 to 110 ° C.), and the reaction was carried out for 16 hours while water was distilled from the system with a Dean-Stark water separator. Next, the reaction solution is cooled to 40 ° C. or lower, washed repeatedly with ion-exchanged water and aqueous sodium hydrogen carbonate solution using a separatory funnel, and toluene was distilled off by concentration under reduced pressure to obtain alicyclic imide acrylate B (hereinafter referred to as compound). B)). This had a purity of 93.1% (by the GC method). In addition, each spectrum measurement value and structure of the compound B are as follows.
１ Ｈ−ＮＭＲ（３００ＭＨｚ、溶媒ＣＤＣｌ 3 、δ（ｐｐｍ））：５．８７、６．３７、６．０６、４．２６、３．７９、３．１０、２．５６、２．２０
ＩＲ（ｎｅａｔ）：１６５３、１７０３、１７２５、１１８２、１４０１ｃｍ-1
1 H-NMR (300 MHz, solvent CDCl 3 , δ (ppm)): 5.87, 6.37, 6.06, 4.26, 3.79, 3.10, 2.56, 2.20
IR (neat): 1653, 1703, 1725, 1182, 1401 cm −1
比較例２
ディーンスターク分水器（ジムロート冷却管）、温度計、滴下ロート、窒素ガス導入口、攪拌機を備えた反応容器に無水コハク酸(和光純薬（株）製)１５０．０ｇ、脱水トルエンを１５０．０ｇ仕込み、系内を窒素置換した。次いで、反応容器を室温で攪拌しつつエタノールアミン８９．７ｇを滴下した。滴下終了後、還流温度（１１０℃）まで加熱し、水をトルエンで共沸除去しつつ３時間反応を行い、イミド化合物を得た。このものは純度９７．０％であった（ＧＣ法による）。
Comparative Example 2
In a reaction vessel equipped with a Dean-Stark water separator (Dimroth condenser), thermometer, dropping funnel, nitrogen gas inlet, and stirrer, 150.0 g of succinic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.) and 150. dehydrated toluene. 0 g was charged and the inside of the system was replaced with nitrogen. Next, 89.7 g of ethanolamine was added dropwise while stirring the reaction vessel at room temperature. After completion of the dropwise addition, the mixture was heated to the reflux temperature (110 ° C.) and reacted for 3 hours while removing water azeotropically with toluene to obtain an imide compound. This had a purity of 97.0% (according to GC method).
次いで、上記の反応溶液を室温まで戻し、窒素ガス導入口を空気バブリング用導入管に変え、メトキノン３．０ｇ、ｐ−トルエンスルホン酸３０．０ｇ、アクリル酸３７８．０ｇを添加し攪拌した。次いで、系内を空気でバブリングしながら還流温度（１０６〜１１０℃）まで加熱昇温し、ディーンスターク分水器で水を系内から留去しながら反応を１６時間行った。次いで、反応溶液を４０℃以下まで冷却し、分液ロートを用いてイオン交換水、炭酸水素ナトリウム水溶液での洗浄を繰り返し、減圧濃縮でトルエンを留去し、イミドアクリレートＣ（以下、化合物Ｃという）を得た。このものは純度８７．０％であった（ＧＣ法による）。なお、当該化合物Ｃの各スペクトル測定値および構造は、以下のようになる。 Next, the reaction solution was returned to room temperature, the nitrogen gas inlet was changed to an air bubbling inlet tube, 3.0 g of methoquinone, 30.0 g of p-toluenesulfonic acid, and 378.0 g of acrylic acid were added and stirred. Next, the system was heated to reflux temperature (106 to 110 ° C.) while bubbling with air, and the reaction was carried out for 16 hours while water was distilled from the system with a Dean-Stark water separator. Next, the reaction solution is cooled to 40 ° C. or lower, repeatedly washed with ion-exchanged water and an aqueous sodium hydrogen carbonate solution using a separatory funnel, and toluene is distilled off by concentration under reduced pressure to obtain imide acrylate C (hereinafter referred to as Compound C). ) This had a purity of 87.0% (according to GC method). In addition, each spectrum measurement value and structure of the compound C are as follows.
１ Ｈ−ＮＭＲ（３００ＭＨｚ、溶媒ＣＤＣｌ 3 、δ（ｐｐｍ））：６．７８、６．３６、５．８７、４．３２、３．８４、２．７２
ＩＲ（ｎｅａｔ）：１７００、１４０１、１１８４、１１１２ｃｍ-1
1 H-NMR (300 MHz, solvent CDCl 3 , δ (ppm)): 6.78, 6.36, 5.87, 4.32, 3.84, 2.72
IR (neat): 1700, 1401, 1184, 1112 cm −1
以下、比較用の化合物Ｄ〜Ｇを示す。 Hereinafter, Comparative Compounds D to G are shown.
化合物Ｄ（商品名「アロニックスＭ１４０」、東亞合成（株）製） Compound D (trade name “Aronix M140”, manufactured by Toagosei Co., Ltd.)
実施例５
前記化合物Ａ−１を５０部、トルエン５０部、アゾビスイソブチロニトリルを０．９部（該Ａに対して３ｍｏｌ％）を混合し、熱重合用組成物Ａを調製した。次いでこれを、窒素雰囲気下、８０℃、５時間の条件で重合させた。次いで、得られた各重合物を、ヘキサンを用いて再沈精製して未反応の化合物を除去し、更に減圧乾燥することによって（１３３３Ｐａ、８０℃、５時間）、重合体Ａ−１を得た。当該重合体Ａ−１は、下記耐熱性試験に供した。
Example 5
50 parts of the compound A-1, 50 parts of toluene, and 0.9 part of azobisisobutyronitrile (3 mol% with respect to A) were mixed to prepare a composition A for thermal polymerization. Subsequently, this was polymerized under conditions of 80 ° C. and 5 hours in a nitrogen atmosphere. Subsequently, each polymer obtained was purified by reprecipitation using hexane to remove unreacted compounds, and further dried under reduced pressure (1333 Pa, 80 ° C., 5 hours) to obtain a polymer A-1. It was. The polymer A-1 was subjected to the following heat resistance test.
実施例６〜８
実施例５と同様の方法で、前記化合物Ａ−２〜Ａ−４についても重合体Ａ−２〜Ａ−４を作製し、それぞれを下記耐熱性試験に供した。
Examples 6-8
Polymers A-2 to A-4 were prepared for the compounds A-2 to A-4 in the same manner as in Example 5, and each was subjected to the following heat resistance test.
（耐熱性の評価）
前記重合体Ａ−１〜Ａ−４について、市販の熱重量測定装置（ＴＧ−ＤＴＡ）および示差走査熱量分析装置（ＤＳＣ）（製品名「２０００Ｓ システムＷＳ００２」、マック・サイエンス社製）を用いて、熱分解開始温度およびＴｇを求めた。なお、測定条件、および数値の算出法は以下の通りである。結果を表１に示す。
(Evaluation of heat resistance)
About the said polymers A-1 to A-4, using a commercially available thermogravimetric measuring device (TG-DTA) and a differential scanning calorimeter (DSC) (product name “2000S system WS002”, manufactured by Mac Science). The thermal decomposition onset temperature and Tg were determined. The measurement conditions and the numerical value calculation method are as follows. The results are shown in Table 1.
・ＴＧ−ＤＴＡ：室温から１０℃／ｍｉｎで昇温して８００℃までサンプルを加熱した際にチャート上に出現した屈曲点における温度を、熱分解開始温度とした。
・ＤＳＣ：−５０℃から１０℃／ｍｉｎで昇温して２００℃までサンプルを加熱した後、再度−５０℃まで冷却し、再び２００℃まで加熱した際に得られる、２サイクル目の曲線から、接線法により屈曲点を算出して、Ｔｇとした。
TG-DTA: The temperature at the bending point that appeared on the chart when the sample was heated from room temperature at 10 ° C./min and heated to 800 ° C. was defined as the thermal decomposition start temperature.
DSC: From the second cycle curve obtained when the sample was heated from -50 ° C. at 10 ° C./min to 200 ° C., then cooled again to −50 ° C., and again heated to 200 ° C. The inflection point was calculated by the tangent method and set as Tg.
実施例９
前記化合物Ａ−３を８０部、ウレタンアクリレート（商品名「アロニックスＭ−１６００」、東亞合成（株）製）２０部を６０℃で混合し、更に１−ヒドロキシシクロヘキシルフェニルケトン（商品名「イルガキュア１８４」、チバ・スペシャリティ・ケミカルズ（株）製）３部を６０℃で添加して混合することにより、光重合用組成物Ａ’を得た。次いでこれを、ガラス板上に載置したＰＥＴフィルムに膜厚が硬化後に約２００μｍとなるように塗布した。次いで、当該ＰＥＴフィルムをガラス板に載せたまま、ＨＯ２−Ｌ２１型水銀ランプを設置した紫外線照射装置（製品名「ＵＢ０２２−５Ｂ」、アイグラフィックス株式会社製）に１０回通過させて紫外線重合を行い、重合体（硬化被膜）Ａ’−３を得た。
Example 9
80 parts of Compound A-3 and 20 parts of urethane acrylate (trade name “Aronix M-1600”, manufactured by Toagosei Co., Ltd.) were mixed at 60 ° C., and further 1-hydroxycyclohexyl phenyl ketone (trade name “Irgacure 184”). 3 parts of Ciba Specialty Chemicals Co., Ltd.) was added at 60 ° C. and mixed to obtain composition A ′ for photopolymerization. Subsequently, this was apply | coated to PET film mounted on the glass plate so that a film thickness might be set to about 200 micrometers after hardening. Next, while the PET film is placed on the glass plate, it is passed through an ultraviolet irradiation apparatus (product name “UB022-5B”, manufactured by Eye Graphics Co., Ltd.) having a HO2-L21 type mercury lamp 10 times to carry out ultraviolet polymerization. And a polymer (cured coating) A′-3 was obtained.
なお、紫外線照射装置は、ランプ高さが１０ｃｍ、コンベアスピード１０ｍ／ｍｉｎ、紫外線照射強度が１３０ｍＪ／ｃｍ２である。なお、硬化の完了は、紫外線照射のパス後、被膜の表面を指でこすり、タック（粘着性）がなくなった時点をもって判断した。 The ultraviolet irradiation device has a lamp height of 10 cm, a conveyor speed of 10 m / min, and an ultraviolet irradiation intensity of 130 mJ / cm 2 . The completion of the curing was judged when the surface of the coating was rubbed with a finger after the ultraviolet irradiation pass and tack (adhesiveness) disappeared.
実施例１０
実施例９において、前記化合物Ａ−３の代わりにＡ−４を用いた他は同様にして光重合用組成物Ａ’−４を調製し、各組成物を前記同様の工程で紫外線重合させ、重合体（硬化被膜）Ａ’−４を得た。
Example 10
In Example 9, a photopolymerizable composition A′-4 was prepared in the same manner except that A-4 was used instead of the compound A-3, and each composition was subjected to ultraviolet polymerization in the same process as described above. Polymer (cured film) A′-4 was obtained.
比較例３〜５
実施例９において、前記化合物Ａ−３の代わりに前記化合物Ｂ〜Ｄを用いた他は同様にして光重合用組成物Ｂ’〜Ｄ’を調製し、各組成物を前記同様の工程で紫外線重合させ、重合体（硬化被膜）Ｂ’〜Ｄ’を得た。
Comparative Examples 3-5
In Example 9, photopolymerizable compositions B ′ to D ′ were prepared in the same manner except that the compounds B to D were used in place of the compound A-3, and each composition was subjected to ultraviolet rays in the same manner as described above. Polymerization was performed to obtain polymers (cured coatings) B ′ to D ′.
（吸水性の評価）
重合体（硬化被膜）Ａ’−３を有するＰＥＴフィルムを縦４５ｍｍ×横６ｍｍの短冊状に切り取り、ＰＥＴフィルムから剥がした硬化被膜を試験片とした。この試験片を１２０℃で２４時間乾燥してその重量（Ｗ０）を測り、次いでこれを４０℃の水浴に２４時間浸した後に水分を十分ふき取ってその重量（Ｗ１）を測り、その重量変化（Ｗ１−Ｗ０）／Ｗ０×１００を硬化被膜の吸水率（％）として評価した。また、前記重合体（硬化被膜）Ａ’−３、Ａ’−４、ならびに重合体（硬化被膜）Ｂ’、Ｃ’およびＤ’についても同様にして吸水率を評価した。結果を表２に示す。
(Evaluation of water absorption)
A PET film having a polymer (cured film) A′-3 was cut into strips of 45 mm in length × 6 mm in width and peeled off from the PET film was used as a test piece. The test piece was dried at 120 ° C. for 24 hours and weighed (W 0 ), then immersed in a 40 ° C. water bath for 24 hours and then thoroughly wiped to measure its weight (W 1 ). The change (W 1 −W 0 ) / W 0 × 100 was evaluated as the water absorption rate (%) of the cured coating. Further, the water absorption rate of the polymers (cured coatings) A′-3 and A′-4 and the polymers (cured coatings) B ′, C ′ and D ′ were evaluated in the same manner. The results are shown in Table 2.
実施例１１〜１２、比較例６〜８
前記光重合用組成物Ａ’−３の１ｇをメチルエチルケトンで希釈し、３０重量％の溶液とした。次いで、バーコーターＮｏ．１２を用いて、当該溶液を膜厚が硬化後に約３μｍとなるようにＰＥＴフィルムに塗工し、８０℃で１分間乾燥した後、前記同様の方法で紫外線重合させ、重合体（硬化被膜）Ａ’’−３を作成した。次いで、該重合体Ａ’’−３について、鉛筆硬度（ＪＩＳ−Ｋ−５４００）、およびＴｇを評価した。また、前記光重合用組成物Ａ’−４ならびにＢ’〜Ｄ’についても同様にして重合体Ａ’’−４ならびにＢ’’〜Ｄ’’を作成し、鉛筆硬度を評価した。結果を表３に示す。
Examples 11-12, Comparative Examples 6-8
1 g of the photopolymerization composition A′-3 was diluted with methyl ethyl ketone to obtain a 30% by weight solution. Next, bar coater No. 12 was applied to a PET film so that the film thickness was about 3 μm after curing, dried at 80 ° C. for 1 minute, and then UV-polymerized in the same manner as described above to obtain a polymer (cured film). A ″ -3 was created. The polymer A ″ -3 was then evaluated for pencil hardness (JIS-K-5400) and Tg. Further, for the photopolymerization compositions A′-4 and B ′ to D ′, polymers A ″ -4 and B ″ to D ″ were similarly prepared, and pencil hardness was evaluated. The results are shown in Table 3.
Claims (10)
［工程（Ｉ）］
下記一般式（４−１）で示される脂環式ジカルボン酸または下記一般式（４−２）で示される脂環式ジカルボン酸無水物に、
下記一般式（５）で示されるモノアミン化合物を反応させて、下記一般式（６）で示される脂環式マレイミド化合物を製造する工程。
［工程（ＩＩ）］
前記一般式（６）で表される脂環式マレイミド化合物に、下記一般式（７）で示すビニル化合物を反応させる工程。
[Step (I)]
To the alicyclic dicarboxylic acid represented by the following general formula (4-1) or the alicyclic dicarboxylic acid anhydride represented by the following general formula (4-2),
A step of reacting a monoamine compound represented by the following general formula (5) to produce an alicyclic maleimide compound represented by the following general formula (6).
[Step (II)]
A step of reacting the alicyclic maleimide compound represented by the general formula (6) with a vinyl compound represented by the following general formula (7).
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