JP2014088377A - Method of manufacturing alicyclic (meth)acrylate and alicyclic (meth)acrylate - Google Patents
Method of manufacturing alicyclic (meth)acrylate and alicyclic (meth)acrylate Download PDFInfo
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- JP2014088377A JP2014088377A JP2013207651A JP2013207651A JP2014088377A JP 2014088377 A JP2014088377 A JP 2014088377A JP 2013207651 A JP2013207651 A JP 2013207651A JP 2013207651 A JP2013207651 A JP 2013207651A JP 2014088377 A JP2014088377 A JP 2014088377A
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- Prior art keywords
- meth
- alicyclic
- acrylate
- group
- general formula
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- 125000002723 alicyclic group Chemical group 0.000 title claims abstract description 162
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 45
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims description 185
- -1 alicyclic diene compound Chemical class 0.000 claims abstract description 96
- 238000006243 chemical reaction Methods 0.000 claims abstract description 65
- 239000003054 catalyst Substances 0.000 claims abstract description 51
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 31
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 31
- 239000007848 Bronsted acid Substances 0.000 claims abstract description 22
- 125000000962 organic group Chemical group 0.000 claims abstract description 15
- 239000003930 superacid Substances 0.000 claims description 32
- 239000011347 resin Substances 0.000 claims description 27
- 229920005989 resin Polymers 0.000 claims description 27
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 17
- 150000002894 organic compounds Chemical class 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 13
- 229920000058 polyacrylate Polymers 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 8
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 18
- 150000001252 acrylic acid derivatives Chemical class 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 24
- 239000003112 inhibitor Substances 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 15
- 239000002994 raw material Substances 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000002253 acid Substances 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 238000005406 washing Methods 0.000 description 11
- YKPCEENRZZBDMC-DRNPGQERSA-N (2r,3r,4s,5r)-2-[6-[[(3s)-3-bicyclo[2.2.1]heptanyl]amino]purin-9-yl]-5-(hydroxymethyl)oxolane-3,4-diol Chemical compound O[C@@H]1[C@H](O)[C@@H](CO)O[C@H]1N1C2=NC=NC(N[C@@H]3C4CCC(C4)C3)=C2N=C1 YKPCEENRZZBDMC-DRNPGQERSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000003377 acid catalyst Substances 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 9
- 125000003342 alkenyl group Chemical group 0.000 description 9
- 239000003505 polymerization initiator Substances 0.000 description 9
- 125000003118 aryl group Chemical group 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000007664 blowing Methods 0.000 description 6
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 150000002430 hydrocarbons Chemical group 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- OJOWICOBYCXEKR-APPZFPTMSA-N (1S,4R)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound CC=C1C[C@@H]2C[C@@H]1C=C2 OJOWICOBYCXEKR-APPZFPTMSA-N 0.000 description 5
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 5
- 239000007983 Tris buffer Substances 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 238000010538 cationic polymerization reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 125000004093 cyano group Chemical group *C#N 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- 150000002484 inorganic compounds Chemical class 0.000 description 5
- 229910010272 inorganic material Inorganic materials 0.000 description 5
- 230000003472 neutralizing effect Effects 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 125000005129 aryl carbonyl group Chemical group 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 4
- CZNRFEXEPBITDS-UHFFFAOYSA-N 2,5-bis(2-methylbutan-2-yl)benzene-1,4-diol Chemical compound CCC(C)(C)C1=CC(O)=C(C(C)(C)CC)C=C1O CZNRFEXEPBITDS-UHFFFAOYSA-N 0.000 description 3
- 229910015900 BF3 Inorganic materials 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 125000005090 alkenylcarbonyl group Chemical group 0.000 description 3
- 125000005193 alkenylcarbonyloxy group Chemical group 0.000 description 3
- 125000005092 alkenyloxycarbonyl group Chemical group 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 3
- 125000005196 alkyl carbonyloxy group Chemical group 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 description 3
- 125000004104 aryloxy group Chemical group 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 150000004715 keto acids Chemical class 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- 238000012719 thermal polymerization Methods 0.000 description 3
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 2
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 description 2
- XONFSEOHZGSMJG-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4-nonafluoro-4-(1,1,2,2,3,3,4,4,4-nonafluorobutylsulfonylmethylsulfonyl)butane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)S(=O)(=O)CS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F XONFSEOHZGSMJG-UHFFFAOYSA-N 0.000 description 2
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 2
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-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
- 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 125000004448 alkyl carbonyl group Chemical group 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 125000005199 aryl carbonyloxy group Chemical group 0.000 description 2
- 150000007514 bases Chemical class 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002274 desiccant Substances 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- MAOBFOXLCJIFLV-UHFFFAOYSA-N (2-aminophenyl)-phenylmethanone Chemical class NC1=CC=CC=C1C(=O)C1=CC=CC=C1 MAOBFOXLCJIFLV-UHFFFAOYSA-N 0.000 description 1
- PQBXBTLPVVDKFY-UHFFFAOYSA-N 1,1,1,2,2-pentafluoro-2-(1,1,2,2,2-pentafluoroethylsulfonylmethylsulfonyl)ethane Chemical compound FC(F)(F)C(F)(F)S(=O)(=O)CS(=O)(=O)C(F)(F)C(F)(F)F PQBXBTLPVVDKFY-UHFFFAOYSA-N 0.000 description 1
- GKNWQHIXXANPTN-UHFFFAOYSA-N 1,1,2,2,2-pentafluoroethanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)F GKNWQHIXXANPTN-UHFFFAOYSA-N 0.000 description 1
- XBWQFDNGNOOMDZ-UHFFFAOYSA-N 1,1,2,2,3,3,3-heptafluoropropane-1-sulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)F XBWQFDNGNOOMDZ-UHFFFAOYSA-N 0.000 description 1
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 description 1
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- FBHVHYAIPSTHOY-UHFFFAOYSA-N 1-[bis(1,1,2,2,2-pentafluoroethylsulfonyl)methyl]-2,3,4,5,6-pentafluorobenzene Chemical compound FC1=C(F)C(F)=C(C(S(=O)(=O)C(F)(F)C(F)(F)F)S(=O)(=O)C(F)(F)C(F)(F)F)C(F)=C1F FBHVHYAIPSTHOY-UHFFFAOYSA-N 0.000 description 1
- CAKDDIRYHQGITO-UHFFFAOYSA-N 1-[bis(1,1,2,2,2-pentafluoroethylsulfonyl)methylsulfonyl]-1,1,2,2,2-pentafluoroethane Chemical compound FC(F)(F)C(F)(F)S(=O)(=O)C(S(=O)(=O)C(F)(F)C(F)(F)F)S(=O)(=O)C(F)(F)C(F)(F)F CAKDDIRYHQGITO-UHFFFAOYSA-N 0.000 description 1
- AEWJYVYTYSKYNH-UHFFFAOYSA-N 1-[bis(1,1,2,2,3,3,3-heptafluoropropylsulfonyl)methylsulfonyl]-1,1,2,2,3,3,3-heptafluoropropane Chemical compound FC(F)(F)C(F)(F)C(F)(F)S(=O)(=O)C(S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)F)S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)F AEWJYVYTYSKYNH-UHFFFAOYSA-N 0.000 description 1
- JCQFXEGCFPAWHH-UHFFFAOYSA-N 1-[bis(1,1,2,2,3,3,4,4,4-nonafluorobutylsulfonyl)methylsulfonyl]-1,1,2,2,3,3,4,4,4-nonafluorobutane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)S(=O)(=O)C(S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JCQFXEGCFPAWHH-UHFFFAOYSA-N 0.000 description 1
- RLLDXJXYMKTGPV-UHFFFAOYSA-N 1-[bis(trifluoromethylsulfonyl)methyl]-2,3,4,5,6-pentafluorobenzene Chemical compound FC1=C(F)C(F)=C(C(S(=O)(=O)C(F)(F)F)S(=O)(=O)C(F)(F)F)C(F)=C1F RLLDXJXYMKTGPV-UHFFFAOYSA-N 0.000 description 1
- UODCFUIMIBSEMF-UHFFFAOYSA-N 1-[bis(trifluoromethylsulfonyl)methyl]-3,5-bis(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC(C(S(=O)(=O)C(F)(F)F)S(=O)(=O)C(F)(F)F)=CC(C(F)(F)F)=C1 UODCFUIMIBSEMF-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- VYMSWGOFSKMMCE-UHFFFAOYSA-N 10-butyl-2-chloroacridin-9-one Chemical compound ClC1=CC=C2N(CCCC)C3=CC=CC=C3C(=O)C2=C1 VYMSWGOFSKMMCE-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、脂環式（メタ）アクリレートの製造方法に関する。より詳しくは、粘接着剤、塗料、インク、反応性希釈剤等の材料として好適に用いることができる脂環式（メタ）アクリレートの製造方法に関する。 The present invention relates to a method for producing an alicyclic (meth) acrylate. More specifically, the present invention relates to a method for producing an alicyclic (meth) acrylate that can be suitably used as a material such as an adhesive, paint, ink, and reactive diluent.
脂環式（メタ）アクリレートは、溶液重合系（粘接着剤、塗料等）や光硬化系（インク、反応性希釈剤、フォトレジスト、ハードコート剤等）において幅広く使用される重合性樹脂原料であり、工業的に重要な化合物である。
脂環式（メタ）アクリレートの製造方法としては、酸触媒を用いるノルボルネン類へのカルボン酸の付加反応が従来より知られており、特許文献、学術文献において多くの報告がある。このような製造方法で脂環式ジエン化合物と（メタ）アクリル酸から得られる脂環式（メタ）アクリレート（後述するＥＴＣＨＡとＥＮＢＡ）についても、１９８０年代アメリカにて香料として特許出願されている（特許文献１）。しかしながら、それ以外に当該脂環式（メタ）アクリレート（ＥＴＣＨＡとＥＮＢＡ）の製法や用途に関する文献は無く、中間体として使用された例が１件あるのみ（特許文献２）で、重合性樹脂材料として記載された文献も存在しない。
Cycloaliphatic (meth) acrylates are raw materials for polymerizable resins that are widely used in solution polymerization systems (adhesives, paints, etc.) and photocuring systems (inks, reactive diluents, photoresists, hard coat agents, etc.). It is an industrially important compound.
As a method for producing an alicyclic (meth) acrylate, an addition reaction of a carboxylic acid to norbornenes using an acid catalyst has been conventionally known, and there are many reports in patent literature and academic literature. A patent application was also filed as a fragrance in the United States in the 1980s for an alicyclic (meth) acrylate (ETCHA and ENBA described later) obtained from an alicyclic diene compound and (meth) acrylic acid by such a production method ( Patent Document 1). However, there is no other literature on the production method and use of the alicyclic (meth) acrylate (ETCHA and ENBA), and there is only one example used as an intermediate (Patent Document 2). There is also no literature described as.
従来の文献に記載の、ルイス酸触媒を用いる脂環式ジエン化合物への（メタ）アクリル酸の付加反応による脂環式（メタ）アクリレートの合成では、多量の触媒が使用されていた。そのため、脂環式（メタ）アクリレートを取得するためには、反応後に塩基性化合物を添加して酸触媒を中和し、多量の中和塩を除去するために水洗を行い、水分を除くために乾燥を行い、乾燥剤をろ別して蒸留するという多段工程が必要であった。例えば、特許文献１では、５．９モルパーセントの三フッ化ホウ素ジエチルエーテル錯体を使用し、重量比で３分の１以上のトルエンを添加して反応を実施し、６回もの水洗工程を経て乾燥工程を実施している。この製造方法では、工程数が多く煩雑であり、有機物を含む排水が大量に発生し、添加した溶媒を蒸留等によって分離する必要がある、といった課題があった。なお、当該化合物を含む脂環式（メタ）アクリレートは、１〜１．５程度の密度を有しており、粘度も３〜６センチポアズ程度で水層との分液性が悪いため、低密度かつ低粘度の溶媒で希釈せず水洗することは困難であった。例えば、特許文献２では５．６モルパーセントの三フッ化ホウ素テトラヒドロフラン錯体を使用し、溶媒を添加することなく反応と水洗を実施しているが、相分離に長時間を要するといった課題があった。更に三フッ化ホウ素を触媒とするこれらの製造方法により得られる脂環式（メタ）アクリレートは、後述する一般式（２）で表される構造のものと、一般式（３）で表される構造のものとのモル比が８／２前後の組成のもののみであった。
このように、従来の脂環式（メタ）アクリレートの製造方法は、工程の煩雑さ、排水の多さ、及び、一定の異性体組成の脂環式（メタ）アクリレートしか得られないといった点において、改善の余地があった。
In the synthesis of alicyclic (meth) acrylate by addition reaction of (meth) acrylic acid to an alicyclic diene compound using a Lewis acid catalyst described in the conventional literature, a large amount of catalyst has been used. Therefore, in order to obtain alicyclic (meth) acrylate, the basic compound is added after the reaction to neutralize the acid catalyst, and water washing is performed to remove a large amount of neutralized salt to remove moisture. It was necessary to carry out a multi-stage process of drying and then filtering off the desiccant and distilling it. For example, in Patent Document 1, 5.9 mole percent of boron trifluoride diethyl ether complex is used, and the reaction is carried out by adding 1/3 or more of toluene by weight, and after 6 washing steps. A drying process is performed. This manufacturing method has a problem that the number of steps is large and complicated, a large amount of waste water containing organic matter is generated, and the added solvent needs to be separated by distillation or the like. In addition, since the alicyclic (meth) acrylate containing the compound has a density of about 1 to 1.5, the viscosity is about 3 to 6 centipoise, and the liquid separation with the water layer is poor, so the density is low. And it was difficult to wash with water without diluting with a low viscosity solvent. For example, in Patent Document 2, 5.6 mole percent of boron trifluoride tetrahydrofuran complex is used and the reaction and water washing are performed without adding a solvent, but there is a problem that a long time is required for phase separation. . Furthermore, the alicyclic (meth) acrylate obtained by these production methods using boron trifluoride as a catalyst is represented by the structure represented by the general formula (2) described later and the general formula (3). Only the composition having a molar ratio of about 8/2 to that of the structure.
Thus, the conventional method for producing an alicyclic (meth) acrylate is complicated in terms of process, a large amount of waste water, and only alicyclic (meth) acrylate having a certain isomeric composition can be obtained. There was room for improvement.
本発明は、上記現状に鑑みてなされたものであり、煩雑な工程を経ることなく、また多量の排水を発生することなく、脂環式（メタ）アクリレートを製造することができ、様々な異性体組成の脂環式（メタ）アクリレートを製造することが可能な脂環式（メタ）アクリレートの製造方法を提供することを目的とする。 The present invention has been made in view of the above situation, and can produce alicyclic (meth) acrylates without going through complicated steps and without generating a large amount of waste water. It aims at providing the manufacturing method of the alicyclic (meth) acrylate which can manufacture the alicyclic (meth) acrylate of a body composition.
本発明者は、上述した種々の課題を解決できる脂環式（メタ）アクリレートの製造方法について種々検討し、ブレンステッド酸触媒に着目した。しかしながら、トリフルオロメタンスルホン酸等の強力なブレンステッド酸を触媒として使用すると、上記特許文献１で好適とされる１モルパーセント以上の触媒量では、良好な収率で目的とする脂環式（メタ）アクリレートを得ることはできなかった。本発明者は、この低収率の原因究明に取り組み、ブレンステッド酸を触媒とする脂環式ジエン化合物のカチオン重合が副反応として進行していることを突き止めた。そこで、この反応におけるカチオン重合を抑制するため鋭意検討を行った結果、脂環式ジエン化合物と（メタ）アクリル酸とを反応させて脂環式（メタ）アクリレートを製造する反応において、脂環式ジエン化合物に対して１モル％未満のブレンステッド酸触媒の存在下で脂環式ジエン化合物と（メタ）アクリル酸とを反応させることで、効率的な脂環式（メタ）アクリレートの生成が可能になることを見出した。このように低触媒量で反応させ、微量の中和剤で触媒の不活性化処理（もしくは吸着処理）を実施することで、水洗工程と乾燥工程を省略して脂環式（メタ）アクリレートを製造することに成功した。
なお、本発明者は、水洗工程を省略し工程を簡略化するため、三フッ化ホウ素の触媒量の低減も試みたが、脂環式ジエン化合物に対して１モルパーセント未満に減少させると、触媒活性が低下し反応の進行が遅くなり、０．５モルパーセント未満の触媒量では、脂環式ジエン化合物が完全に転化しないことを確認している。上記のように煩雑な工程を経ることなく、また多量の排水を発生することなく、高い収率で脂環式（メタ）アクリレートを製造することができる効果は、単に触媒の量を少なくすれば達成できるというものではなく、特定の触媒を選択し、当該触媒の最適な使用量を見出したことにより達成された効果である。更に本発明者は、この製造方法について検討し、酸触媒の種類、反応温度によって、生成する脂環式（メタ）アクリレートの組成が変化することを見出し、適切にこれらを選択することにより様々な異性体組成の脂環式（メタ）アクリレートを製造することに成功した。このように、上述した検討の結果、上記課題をみごとに解決することができることに想到し、本発明に到達したものである。
The present inventor has studied various methods for producing an alicyclic (meth) acrylate capable of solving the various problems described above, and has focused on the Bronsted acid catalyst. However, when a strong Bronsted acid such as trifluoromethanesulfonic acid is used as a catalyst, the target alicyclic (meta) group is obtained in a good yield at a catalyst amount of 1 mol percent or more, which is suitable in Patent Document 1 above. ) Acrylate could not be obtained. The present inventor tried to investigate the cause of this low yield, and found that cationic polymerization of an alicyclic diene compound using a Bronsted acid as a catalyst proceeds as a side reaction. Thus, as a result of intensive studies to suppress cationic polymerization in this reaction, in the reaction of producing an alicyclic (meth) acrylate by reacting an alicyclic diene compound with (meth) acrylic acid, Efficient production of alicyclic (meth) acrylate is possible by reacting alicyclic diene compound with (meth) acrylic acid in the presence of less than 1 mol% Bronsted acid catalyst with respect to diene compound. I found out that In this way, by reacting with a low catalyst amount and carrying out catalyst deactivation treatment (or adsorption treatment) with a small amount of neutralizing agent, the water washing step and the drying step are omitted, and the alicyclic (meth) acrylate is removed. Succeeded in manufacturing.
In addition, in order to omit the water washing process and simplify the process, the present inventor also tried to reduce the catalyst amount of boron trifluoride, but when reduced to less than 1 mole percent with respect to the alicyclic diene compound, It has been confirmed that the catalytic activity is lowered and the progress of the reaction is slow, and the alicyclic diene compound is not completely converted at a catalyst amount of less than 0.5 mole percent. The effect of producing an alicyclic (meth) acrylate in a high yield without going through complicated steps as described above and without generating a large amount of wastewater is simply by reducing the amount of the catalyst. This is not an effect that can be achieved, but the effect achieved by selecting a specific catalyst and finding the optimum amount of the catalyst. Furthermore, the present inventor has studied this production method, found that the composition of the alicyclic (meth) acrylate to be produced varies depending on the type of the acid catalyst and the reaction temperature, and variously selected these appropriately. An alicyclic (meth) acrylate having an isomeric composition was successfully produced. As described above, as a result of the above-described studies, the inventors have conceived that the above problems can be solved brilliantly, and have reached the present invention.
すなわち本発明は、下記一般式（１）； That is, the present invention provides the following general formula (1);
（式中、Ｒ１、Ｒ２は、同一又は異なって、水素原子又は１価の有機基を表す。）で表される脂環式ジエン化合物と（メタ）アクリル酸とを反応させる工程を含む脂環式（メタ）アクリレートの製造方法であって、該反応工程は、脂環式ジエン化合物に対して１モル％未満のブレンステッド酸触媒の存在下で脂環式ジエン化合物と（メタ）アクリル酸とを反応させる工程であり、該脂環式（メタ）アクリレートは、下記一般式（２）で表される構造の脂環式（メタ）アクリレート及び下記一般式（３）で表される構造の脂環式（メタ）アクリレートを含むことを特徴とする脂環式（メタ）アクリレートの製造方法である。 (Wherein R 1 and R 2 are the same or different and represent a hydrogen atom or a monovalent organic group), and a step of reacting (meth) acrylic acid with an alicyclic diene compound represented by A method for producing an alicyclic (meth) acrylate, wherein the reaction step comprises the step of forming an alicyclic diene compound and (meth) acrylic in the presence of less than 1 mol% Bronsted acid catalyst with respect to the alicyclic diene compound. This is a step of reacting with an acid, and the alicyclic (meth) acrylate has a structure represented by the following general formula (2) and a structure represented by the following general formula (3): It is a manufacturing method of alicyclic (meth) acrylate characterized by including this alicyclic (meth) acrylate.
（式中、Ｒ１、Ｒ２は、同一又は異なって、水素原子又は１価の有機基を表す。Ｒ３は、水素原子又はメチル基を表す。式（２）における脂環式骨格と（メタ）アクリロイルオキシ基との間の波線は、（メタ）アクリロイルオキシ基の配置が異なる立体異性体が存在することを表す。）
以下に本発明を詳述する。
なお、以下において記載する本発明の個々の好ましい形態を２つ以上組み合わせたものもまた、本発明の好ましい形態である。
(In the formula, R 1 and R 2 are the same or different and each represents a hydrogen atom or a monovalent organic group. R 3 represents a hydrogen atom or a methyl group. The alicyclic skeleton in the formula (2) and ( (The wavy line between the (meth) acryloyloxy group represents the presence of stereoisomers having different configurations of the (meth) acryloyloxy group).
The present invention is described in detail below.
A combination of two or more preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.
本発明の脂環式（メタ）アクリレートの製造方法は、上記一般式（１）で表される脂環式ジエン化合物と、（メタ）アクリル酸とを脂環式ジエン化合物に対して１モル％未満のブレンステッド酸触媒の存在下で反応させることで脂環式（メタ）アクリレートを製造するものである。本発明の脂環式（メタ）アクリレートの製造方法は、従来の方法に比べて以下のような種々の利点を有し、従来の方法よりも効率的かつ経済的に脂環式（メタ）アクリレートを製造することができる。なお、下記（Ｖ）の特徴については後述する。
（Ｉ）反応、水洗工程に溶媒を使用する必要がなく、溶媒の除去工程が不要である。
（ＩＩ）水洗工程を省略することで有機物を含む排水が発生しない。
（ＩＩＩ）乾燥工程が不要であり、乾燥剤およびろ過に必要な設備が不要である。
（ＶＩ）触媒費用低減と同時に、触媒が原因となる装置の腐食を抑えることも可能である。
（Ｖ）反応条件を選択することで様々な異性体組成の脂環式（メタ）アクリレートが製造できる。
The manufacturing method of the alicyclic (meth) acrylate of this invention is 1 mol% with respect to an alicyclic diene compound and the alicyclic diene compound represented by the said General formula (1), and (meth) acrylic acid. The alicyclic (meth) acrylate is produced by reacting in the presence of less than Bronsted acid catalyst. The production method of the alicyclic (meth) acrylate of the present invention has the following various advantages over the conventional method, and is more efficient and economical than the conventional method. Can be manufactured. The feature (V) below will be described later.
(I) There is no need to use a solvent in the reaction and water washing steps, and no solvent removal step is required.
(II) By omitting the washing step, wastewater containing organic matter is not generated.
(III) A drying step is unnecessary, and a desiccant and equipment necessary for filtration are unnecessary.
(VI) It is possible to suppress corrosion of the apparatus caused by the catalyst at the same time as reducing the catalyst cost.
(V) By selecting reaction conditions, alicyclic (meth) acrylates having various isomeric compositions can be produced.
本発明の脂環式（メタ）アクリレートの製造方法は、上記一般式（１）で表される脂環式ジエン化合物と、（メタ）アクリル酸とを脂環式ジエン化合物に対して１モル％未満のブレンステッド酸触媒の存在下で反応させる工程（以下、本発明における反応工程とも記載する）を含むものであるが、この工程を含む限り、その他の工程を含んでいてもよい。
また、上記一般式（１）で表される脂環式ジエン化合物、（メタ）アクリル酸、及び、ブレンステッド酸触媒は、それぞれ１種を用いてもよく、２種以上を用いてもよい。また、ブレンステッド酸触媒を用いる限り、ブレンステッド酸に該当しないルイス酸を含んでいてもよい。
The manufacturing method of the alicyclic (meth) acrylate of this invention is 1 mol% with respect to an alicyclic diene compound and the alicyclic diene compound represented by the said General formula (1), and (meth) acrylic acid. It includes a step of reacting in the presence of less Bronsted acid catalyst (hereinafter also referred to as a reaction step in the present invention). However, as long as this step is included, other steps may be included.
Moreover, 1 type may be used for the alicyclic diene compound represented by the said General formula (1), (meth) acrylic acid, and a Bronsted acid catalyst, respectively, and 2 or more types may be used for it. Moreover, as long as the Bronsted acid catalyst is used, a Lewis acid that does not correspond to the Bronsted acid may be included.
本発明における反応工程に使用するブレンステッド酸触媒の量は、触媒の種類や反応温度等の条件により適宜選択すればよいが、好ましくは、脂環式ジエン化合物に対して０．００００１〜０．２モル％である。このような割合で触媒を使用することで、反応後にブレンステッド酸触媒を除去する処理をより少量の塩基性化合物等により行うことが可能となる。より好ましくは、脂環式ジエン化合物に対して０．００００２〜０．１モル％であり、さらに好ましくは、０．００００５〜０．０５モル％である。 The amount of the Bronsted acid catalyst used in the reaction step in the present invention may be appropriately selected according to conditions such as the type of catalyst and reaction temperature, but is preferably 0.00001 to 0.001 with respect to the alicyclic diene compound. 2 mol%. By using the catalyst at such a ratio, it is possible to perform the treatment for removing the Bronsted acid catalyst after the reaction with a smaller amount of a basic compound or the like. More preferably, it is 0.00002-0.1 mol% with respect to an alicyclic diene compound, More preferably, it is 0.00005-0.05 mol%.
本発明における反応工程に使用するブレンステッド酸触媒は、脂環式ジエン化合物と（メタ）アクリル酸との反応条件においてブレンステッド酸として機能するものであれば特に制限されない。
ブレンステッド酸触媒としては、硫酸、過塩素酸等のオキソ酸、フッ化水素酸、フッ化ホウ素酸等の水素酸、りんタングステン酸等のヘテロポリ酸、フルオロスルホン酸、クロロスルホン酸等の無機スルホン酸、メタンスルホン酸、トリフルオロメタンスルホン酸等の有機スルホン酸、ピクリン酸等の強有機酸、カルボラン酸等の酸の他、反応系中にてこれらのブレンステッド酸を発生することが可能な前駆体を用いることができる。
The Bronsted acid catalyst used in the reaction step in the present invention is not particularly limited as long as it functions as a Bronsted acid under the reaction conditions of an alicyclic diene compound and (meth) acrylic acid.
Examples of Bronsted acid catalysts include oxo acids such as sulfuric acid and perchloric acid, hydrogen acids such as hydrofluoric acid and boroboric acid, heteropolyacids such as phosphotungstic acid, inorganic sulfones such as fluorosulfonic acid and chlorosulfonic acid. In addition to acids, organic sulfonic acids such as methanesulfonic acid and trifluoromethanesulfonic acid, strong organic acids such as picric acid, and acids such as carborane acid, precursors capable of generating these Bronsted acids in the reaction system The body can be used.
上記酸触媒の中でも、本発明における反応工程に使用するブレンステッド酸触媒は、超酸であることが好ましい。ブレンステッド酸触媒として超酸を用いることで、より少ない触媒量で脂環式ジエン化合物と（メタ）アクリル酸との反応を進行させることができるため、反応後の触媒の不活性化処理もより少量の中和剤により行うことが可能となる。
ここで、超酸とは、１００％硫酸よりも酸性が強い酸のことである。超酸については、Ｏｌａｈ Ｇｅｏｒｇｅ Ａ． ｅｔ ａｌ． “Ｓｕｐｅｒａｃｉｄ Ｃｈｅｍｉｓｔｒｙ” ２ｎｄ Ｅｄ． Ａ Ｊｏｈｎ Ｗｉｌｌｅｙ ＆ Ｓｏｎｓ， Ｉｎｃ．， Ｐｕｂｌｉｃａｔｉｏｎ ２００９、超酸の酸性度については、Ｊｏｕｒｎａｌ ｏｆ Ａｍｅｒｉｃａｎ Ｃｈｅｍｉｃａｌ Ｓｏｃｉｅｔｙ，１９９４，１１６，３０４７−３０５７を参考にすればよい。
Among the acid catalysts, the Bronsted acid catalyst used in the reaction step in the present invention is preferably a super acid. By using a superacid as a Bronsted acid catalyst, the reaction between the alicyclic diene compound and (meth) acrylic acid can proceed with a smaller amount of catalyst, so the catalyst deactivation treatment after the reaction is also more It becomes possible to carry out with a small amount of neutralizing agent.
Here, the super acid is an acid having a stronger acidity than 100% sulfuric acid. For superacids, see Ohla George A. et al. et al. “Superacid Chemistry” 2nd Ed. A John Willy & Sons, Inc. Publication 2009, Journal of American Chemical Society, 1994, 116, 3047-3057 may be referred to for the acidity of superacids.
上記超酸としては、無機化合物からなる超酸、有機化合物からなる超酸のいずれも用いることができる。
無機化合物からなる超酸としては、フルオロスルホン酸、クロロスルホン酸、過塩素酸、フッ化水素酸、りんタングステン酸等のヘテロポリ酸等が挙げられる。
As the superacid, either a superacid made of an inorganic compound or a superacid made of an organic compound can be used.
Examples of superacids made of inorganic compounds include heteropolyacids such as fluorosulfonic acid, chlorosulfonic acid, perchloric acid, hydrofluoric acid, and phosphotungstic acid.
有機化合物からなる超酸としては、下記一般式（４）〜（８）のいずれかで表される化合物及び／又はカルボラン酸、及び／又は、反応液中にてこれらを発生しうる前駆体、及び／又は、これらの活性点を含む部分構造を有する樹脂等を使用することができる。 As a superacid composed of an organic compound, a compound represented by any one of the following general formulas (4) to (8) and / or carborane acid, and / or a precursor capable of generating these in a reaction solution, And / or a resin having a partial structure including these active sites can be used.
（式（４）〜（８）中、Ｒｆは、パーフルオロアルキル基を表す。Ｒ４は、水素原子又は電子求引性の有機基を表し、ＲｆやＲ４が複数存在する場合には、複数のＲｆやＲ４は、同一であっても異なっていてもよい。ｍは、１〜２の数を表し、ｎは、１〜３の数を表す。）
上記一般式（４）〜（８）において、Ｒ４は水素原子又は電子求引性の有機基であれば特に限定されないが、具体的には、水素原子；トリフルオロメチル基、ペンタフルオロエチル基、ヘプタフルオロプロピル基、ノナフルオロブチル基等の炭素数１〜１０のパーフルオロアルキル基；トリフルオロメチルカルボニル基、ペンタフルオロエチルカルボニル基、ヘプタフルオロプロピルカルボニル基、ノナフルオロブチルカルボニル基等の炭素数１〜１０のパーフルオロアルキルカルボニル基（炭素数１〜１０のパーフルオロアルキル基が結合したカルボニル基）；ペンタフルオロフェニル基、４−トリフルオロメチルテトラフルオロフェニル基、３，５−ビス（トリフルオロメチル）フェニル基、３，５−ビス（トリフルオロメチル）トリフルオロフェニル基等のフッ素原子及び／又は炭素数１〜１０のパーフルオロアルキル基で置換されたフェニル基；４−ピリジル基；テトラフルオロ−４−ピリジル基；シアノ基；３，５−ジシアノフェニル基、２，４，６，−トリシアノフェニル基等のシアノ基置換フェニル基；２，４，６，−トリニトロフェニル基、３，５−ジニトロフェニル基等のニトロ基置換フェニル基等が挙げられる。
(In the formulas (4) to (8), R f represents a perfluoroalkyl group. R 4 represents a hydrogen atom or an electron-withdrawing organic group, and when there are a plurality of R f and R 4. And a plurality of R f and R 4 may be the same or different, m represents a number of 1 to 2, and n represents a number of 1 to 3.)
In the general formulas (4) to (8), R 4 is not particularly limited as long as R 4 is a hydrogen atom or an electron-withdrawing organic group, and specifically includes a hydrogen atom; a trifluoromethyl group, a pentafluoroethyl group. , A perfluoroalkyl group having 1 to 10 carbon atoms such as a heptafluoropropyl group and a nonafluorobutyl group; a carbon number such as a trifluoromethylcarbonyl group, a pentafluoroethylcarbonyl group, a heptafluoropropylcarbonyl group and a nonafluorobutylcarbonyl group 1-10 perfluoroalkylcarbonyl groups (carbonyl groups to which a C1-C10 perfluoroalkyl group is bonded); pentafluorophenyl group, 4-trifluoromethyltetrafluorophenyl group, 3,5-bis (trifluoro Methyl) phenyl group, 3,5-bis (trifluoromethyl) trif A phenyl group substituted with a fluorine atom such as a fluorophenyl group and / or a C 1-10 perfluoroalkyl group; a 4-pyridyl group; a tetrafluoro-4-pyridyl group; a cyano group; a 3,5-dicyanophenyl group; Examples include cyano group-substituted phenyl groups such as 2,4,6, -tricyanophenyl group; nitro group-substituted phenyl groups such as 2,4,6, -trinitrophenyl group and 3,5-dinitrophenyl group.
上記有機化合物からなる超酸の具体例としては、パーフルオロアルキルスルホン酸、ビス（パーフルオロアルキルスルホニル）アミン、トリス（パーフルオロアルキルスルホニル）メタン、トリス（パーフルオロアルキルカルボニル）メタン、トリス（パーフルオロアルキルスルホニル）フェノール等が挙げられる。より具体的には、トリフルオロメタンスルホン酸、ビス（トリフルオロメタンスルホニル）アミン、ビス（トリフルオロメタンスルホニル）メタン、トリス（トリフルオロメタンスルホニル）メタン、フェニルビス（トリフルオロメタンスルホニル）メタン、３，５−ビス（トリフルオロメチル）フェニルビス（トリフルオロメタンスルホニル）メタン、ペンタフルオロフェニルビス（トリフルオロメタンスルホニル）メタン、ペンタフルオロエタンスルホン酸、ビス（ペンタフルオロエタンスルホニル）アミン、ビス（ペンタフルオロエタンスルホニル）メタン、トリス（ペンタフルオロエタンスルホニル）メタン、フェニルビス（ペンタフルオロエタンスルホニル）メタン、３，５−ビス（トリフルオロメチル）フェニルビス（ペンタフルオロエタンスルホニル）メタン、ペンタフルオロフェニルビス（ペンタフルオロエタンスルホニル）メタン、ヘプタフルオロプロパンスルホン酸、ビス（ヘプタフルオロプロパンスルホニル）アミン、ビス（ヘプタフルオロプロパンスルホニル）メタン、トリス（ヘプタフルオロプロパンスルホニル）メタン、フェニルビス（ヘプタフルオロプロパンスルホニル）メタン、３，５−ビス（トリフルオロメチル）フェニルビス（ヘプタフルオロプロパンスルホニル）メタン、ペンタフルオロフェニルビス（ヘプタフルオロプロパンスルホニル）メタン、ノナフルオロブタンスルホン酸、ビス（ノナフルオロブタンスルホニル）アミン、ビス（ノナフルオロブタンスルホニル）メタン、トリス（ノナフルオロブタンスルホニル）メタン、フェニルビス（ノナフルオロブタンスルホニル）メタン、３，５−ビス（トリフルオロメチル）フェニルビス（ノナフルオロブタンスルホニル）メタン、ペンタフルオロフェニルビス（ノナフルオロブタンスルホニル）メタン、２，４，６−トリス（トリフルオロメタンスルホニル）フェノール、２，４，６−トリス（ペンタフルオロエタンスルホニル）フェノール、２，４，６−トリス（ヘプタフルオロプロパンスルホニル）フェノール、２，４，６−トリス（ノナフルオロブタンスルホニル）フェノール、カルボラン酸等が挙げられる。
上記有機化合物からなる超酸を発生しうる前駆体としては、有機化合物からなる超酸の金属塩、有機化合物からなる超酸のほう素化合物、有機化合物からなる超酸のケイ素化合物、有機化合物からなる超酸のりん化合物、パーフルオロアルカンスルホン酸エステル、パーフルオロアルカンスルホン酸無水物等が挙げられる。
Specific examples of superacids composed of the above organic compounds include perfluoroalkylsulfonic acid, bis (perfluoroalkylsulfonyl) amine, tris (perfluoroalkylsulfonyl) methane, tris (perfluoroalkylcarbonyl) methane, and tris (perfluoro). Alkylsulfonyl) phenol and the like. More specifically, trifluoromethanesulfonic acid, bis (trifluoromethanesulfonyl) amine, bis (trifluoromethanesulfonyl) methane, tris (trifluoromethanesulfonyl) methane, phenylbis (trifluoromethanesulfonyl) methane, 3,5-bis ( Trifluoromethyl) phenylbis (trifluoromethanesulfonyl) methane, pentafluorophenylbis (trifluoromethanesulfonyl) methane, pentafluoroethanesulfonic acid, bis (pentafluoroethanesulfonyl) amine, bis (pentafluoroethanesulfonyl) methane, tris ( Pentafluoroethanesulfonyl) methane, phenylbis (pentafluoroethanesulfonyl) methane, 3,5-bis (trifluoromethyl) phenylbis (pentafluoro) Oroethanesulfonyl) methane, pentafluorophenylbis (pentafluoroethanesulfonyl) methane, heptafluoropropanesulfonic acid, bis (heptafluoropropanesulfonyl) amine, bis (heptafluoropropanesulfonyl) methane, tris (heptafluoropropanesulfonyl) methane , Phenylbis (heptafluoropropanesulfonyl) methane, 3,5-bis (trifluoromethyl) phenylbis (heptafluoropropanesulfonyl) methane, pentafluorophenylbis (heptafluoropropanesulfonyl) methane, nonafluorobutanesulfonic acid, bis (Nonafluorobutanesulfonyl) amine, bis (nonafluorobutanesulfonyl) methane, tris (nonafluorobutanesulfonyl) methane, pheny Bis (nonafluorobutanesulfonyl) methane, 3,5-bis (trifluoromethyl) phenylbis (nonafluorobutanesulfonyl) methane, pentafluorophenylbis (nonafluorobutanesulfonyl) methane, 2,4,6-tris (trifluoro) Romethanesulfonyl) phenol, 2,4,6-tris (pentafluoroethanesulfonyl) phenol, 2,4,6-tris (heptafluoropropanesulfonyl) phenol, 2,4,6-tris (nonafluorobutanesulfonyl) phenol, And carborane acid.
Precursors capable of generating superacids composed of the above organic compounds include superacid metal salts composed of organic compounds, superacid boron compounds composed of organic compounds, superacid silicon compounds composed of organic compounds, and organic compounds. And superacid phosphorus compounds, perfluoroalkanesulfonic acid esters, perfluoroalkanesulfonic acid anhydrides, and the like.
また、上記有機化合物からなる超酸には、少量のルイス酸性化合物を添加し、触媒活性を向上させることもできる。たとえば、三フッ化ホウ素、五フッ化りん、五フッ化アンチモン、五フッ化タンタル、五フッ化ニオブ、ハロゲン化アルミニウム、トリス（ペンタフルオロフェニル）ボラン、トリス［３，５−ビス（トリフルオロメチル）フェニル］ボラン、トリフルオロメタンスルホン酸ほう素等の１種又は２種以上を使用することができる。
ルイス酸性化合物を添加する場合、有機化合物からなる超酸１モルに対して、ルイス酸性化合物を０．０１〜１モル添加することが好ましい。
In addition, a small amount of a Lewis acidic compound can be added to the superacid composed of the organic compound to improve the catalytic activity. For example, boron trifluoride, phosphorus pentafluoride, antimony pentafluoride, tantalum pentafluoride, niobium pentafluoride, aluminum halide, tris (pentafluorophenyl) borane, tris [3,5-bis (trifluoromethyl) ) Phenyl] borane, boron trifluoromethanesulfonate, or the like can be used.
When the Lewis acidic compound is added, it is preferable to add 0.01 to 1 mol of the Lewis acidic compound with respect to 1 mol of the superacid composed of the organic compound.
本発明の反応工程において超酸を使用する場合、超酸は、有機化合物からなる超酸であることが好ましい。有機化合物からなる超酸を本発明の反応工程に用いることで、極めて少ない触媒量においても高収率で脂環式（メタ）アクリレートを製造することができる。
無機化合物からなる超酸を用いた場合よりも有機化合物からなる超酸を用いた場合に高収率で脂環式（メタ）アクリレートが得られる理由については、以下のように考えられる。
無機化合物からなる超酸の多くは、酸化力を有するオキソ酸であり、このオキソ酸の作用により、反応原料である脂環式ジエン化合物や（メタ）アクリル酸、生成物である脂環式（メタ）アクリレートのオレフィン部分を酸化する副反応がおこり、脂環式（メタ）アクリレートの収率が低下するおそれがあるが、有機化合物からなる超酸を用いた場合にはこのような副反応がおこらないため、より高い収率で脂環式（メタ）アクリレートを製造することができると考えられる。
無機化合物からなる超酸であっても、酸化力を有していないものであれば、好適に用いることができるが、設備の腐食防止の点からフッ化物イオンを生じないものであることが好ましい。
When a superacid is used in the reaction step of the present invention, the superacid is preferably a superacid composed of an organic compound. By using a superacid composed of an organic compound in the reaction step of the present invention, an alicyclic (meth) acrylate can be produced in a high yield even with an extremely small amount of catalyst.
The reason why the alicyclic (meth) acrylate can be obtained in a higher yield when using a superacid composed of an organic compound than when using a superacid composed of an inorganic compound is considered as follows.
Most of superacids composed of inorganic compounds are oxo acids having oxidizing power. Due to the action of the oxo acids, alicyclic diene compounds and (meth) acrylic acids as reaction raw materials and alicyclic ( A side reaction that oxidizes the olefin part of the (meth) acrylate may occur and the yield of the alicyclic (meth) acrylate may decrease. However, when a superacid composed of an organic compound is used, such a side reaction may occur. Since it does not occur, it is thought that alicyclic (meth) acrylate can be manufactured with a higher yield.
Even superacids made of inorganic compounds can be suitably used as long as they do not have oxidizing power, but are preferably those that do not generate fluoride ions from the viewpoint of preventing corrosion of equipment. .
本発明の脂環式（メタ）アクリレートの製造方法では、反応条件を調整することで、生成物中の異性体組成（上記一般式（２）で表される構造の脂環式（メタ）アクリレートと、上記一般式（３）で表される構造の脂環式（メタ）アクリレートとのモル比）を変化させることができ、反応に使用する触媒の種類は、生成する脂環式（メタ）アクリレートの異性体組成に影響する重要な要素の１つである。
反応により生成する脂環式（メタ）アクリレートのうちの上記一般式（２）で表される構造の脂環式（メタ）アクリレートの割合を多く得ようとする場合には、ブレンステッド酸触媒のうち、上記一般式（５）で表される超酸を用いることが好ましく、上記一般式（３）で表される構造の脂環式（メタ）アクリレートの割合を多く得ようとする場合には、酸触媒のうち、上記一般式（４）で表される超酸を用いることが好ましい。
In the production method of the alicyclic (meth) acrylate of the present invention, by adjusting the reaction conditions, the isomer composition in the product (the alicyclic (meth) acrylate having the structure represented by the above general formula (2) And the molar ratio of the alicyclic (meth) acrylate having the structure represented by the general formula (3) can be changed, and the type of catalyst used in the reaction is the alicyclic (meth) to be produced. One of the important factors affecting the isomer composition of acrylates.
When a large proportion of the alicyclic (meth) acrylate having the structure represented by the general formula (2) in the alicyclic (meth) acrylate produced by the reaction is to be obtained, the Bronsted acid catalyst Among them, it is preferable to use a superacid represented by the above general formula (5), and in the case of obtaining a large proportion of the alicyclic (meth) acrylate having a structure represented by the above general formula (3). Among the acid catalysts, it is preferable to use a superacid represented by the general formula (4).
本発明の反応工程において使用される上記一般式（１）で表される脂環式ジエン化合物と（メタ）アクリル酸とのモル比としては、（脂環式ジエン化合物／（メタ）アクリル酸）＝１／１〜１／２であることが好ましい。より好ましくは、１／１〜１／１．２である。脂環式ジエン化合物に対し（メタ）アクリル酸を過剰に用いることによって、副反応である脂環式アクリレートのカチオン重合を抑制することができる。 The molar ratio of the alicyclic diene compound represented by the general formula (1) used in the reaction step of the present invention and (meth) acrylic acid is (alicyclic diene compound / (meth) acrylic acid). = 1/1 to 1/2 is preferable. More preferably, it is 1/1 to 1 / 1.2. By using (meth) acrylic acid in excess with respect to the alicyclic diene compound, it is possible to suppress cationic polymerization of the alicyclic acrylate, which is a side reaction.
本発明の反応工程において、反応原料および触媒の混合方法としては、脂環式ジエン化合物のカチオン重合やアクリロイル基のラジカル重合が開始しなければ特に制限されないが、触媒と（メタ）アクリル酸との混合液に脂環式ジエン化合物のみを滴下、もしくは触媒と（メタ）アクリル酸との混合液に（メタ）アクリル酸と脂環式ジエン化合物とを滴下する方法が好ましい。滴下速度は、実施する反応温度に合わせて制御され、３０〜３６０分で全量を滴下することが好ましく、６０〜２４０分で全量を滴下することがより好ましい。 In the reaction step of the present invention, the method of mixing the reaction raw material and the catalyst is not particularly limited as long as cationic polymerization of the alicyclic diene compound or radical polymerization of the acryloyl group does not start, but the catalyst and (meth) acrylic acid A method is preferred in which only the alicyclic diene compound is dropped into the mixed solution, or (meth) acrylic acid and the alicyclic diene compound are dropped into the mixed solution of the catalyst and (meth) acrylic acid. The dropping speed is controlled in accordance with the reaction temperature to be carried out, and the whole amount is preferably dropped in 30 to 360 minutes, and the whole amount is more preferably dropped in 60 to 240 minutes.
本発明の反応工程における反応温度は、２０〜１５０℃が好ましいが、反応温度は、生成する脂環式（メタ）アクリレートの異性体組成に影響する重要な要素の１つであるため、得ようとする異性体の組成によって、適宜選択すればよい。例えば、反応により生成する脂環式（メタ）アクリレートのうちの上記一般式（２）で表される構造の脂環式（メタ）アクリレートの割合を多く得ようとする場合は、低い温度（例えば、２０〜６０℃）で反応を行うことが好ましく、上記一般式（３）で表わされる構造の脂環式（メタ）アクリレートの割合を多く得ようとする場合は、高い温度（例えば、８０〜１２０℃）で反応を行うことが好ましい。 The reaction temperature in the reaction step of the present invention is preferably 20 to 150 ° C., but the reaction temperature is one of the important factors affecting the isomer composition of the alicyclic (meth) acrylate to be produced. May be appropriately selected depending on the composition of the isomer. For example, when trying to obtain a large proportion of the alicyclic (meth) acrylate having the structure represented by the general formula (2) in the alicyclic (meth) acrylate generated by the reaction, a low temperature (for example, The reaction is preferably carried out at 20 to 60 ° C., and when a large proportion of the alicyclic (meth) acrylate having the structure represented by the general formula (3) is to be obtained, a high temperature (for example, 80 to It is preferable to carry out the reaction at 120 ° C.
本発明の反応工程における反応時間は、反応原料や触媒量、反応温度等に応じて適宜設定することができるが、１〜２４時間であることが好ましい。より好ましくは、２〜１２時間である。
また、本発明の反応工程における反応圧力は、常圧、減圧、加圧のいずれの条件であってもよいが、常圧であることが好ましい。
なお、本発明の反応工程はラジカル重合防止の観点から、分子状酸素の存在下で実施されることが好ましい。
Although the reaction time in the reaction process of this invention can be suitably set according to the reaction raw material, the amount of catalyst, reaction temperature, etc., it is preferable that it is 1 to 24 hours. More preferably, it is 2 to 12 hours.
In addition, the reaction pressure in the reaction step of the present invention may be any of normal pressure, reduced pressure, and increased pressure, but is preferably normal pressure.
In addition, it is preferable that the reaction process of this invention is implemented in presence of molecular oxygen from a viewpoint of radical polymerization prevention.
本発明の反応工程における反応時には、重合禁止剤を添加しても添加しなくても良いが、８０℃以上で反応を実施する場合は重合禁止剤を添加することが望ましい。添加量としては、反応に用いる（メタ）アクリル酸に対して１〜１０００００ｐｐｍであればよい。
なお、反応原料として重合禁止剤が添加された（メタ）アクリル酸を用いる場合には、当該（メタ）アクリル酸に予め添加された重合禁止剤と、反応時に添加する重合禁止剤とを合わせて上記添加量となるようにすればよい。
During the reaction in the reaction step of the present invention, a polymerization inhibitor may or may not be added. However, when the reaction is carried out at 80 ° C. or higher, it is desirable to add a polymerization inhibitor. The addition amount may be 1 to 100,000 ppm with respect to (meth) acrylic acid used in the reaction.
In addition, when (meth) acrylic acid to which a polymerization inhibitor is added is used as a reaction raw material, a polymerization inhibitor added in advance to the (meth) acrylic acid and a polymerization inhibitor added during the reaction are combined. What is necessary is just to make it become the said addition amount.
上記重合禁止剤としては、ハイドロキノン、メチルハイドロキノン、トリメチルハイドロキノン、ｔ−ブチルハイドロキノン、２，５−ジ（ｔ−アミル）ヒドロキノン等のハイドロキノン系重合禁止剤；メトキノン、６−ｔ−ブチル−２，４−キシレノール、２，６−ジ−ｔ−ブチルフェノール、２，６−ジ−ｔ−ブチル−４−メトキシフェノール、２，２’−メチレンビス（４−メチル−６−ｔ−ブチルフェノール）等のフェノール系酸化防止剤；セバシン酸ビス（２，２，６，６−テトラメチルピペリジノキシ−４−イル）（ＥＣ３３１４Ａ）、４−ヒドロキシ−２，２，６，６−テトラメチルピペリジル−１−オキシル（４−Ｈ−ＴＥＭＰＯ）等のＮ−オキシル化合物系重合禁止剤；デカン二酸ビス（２，２，６，６−テトラメチルピペリジン−４−イル）等のヒンダードアミン系安定剤；ジフェニルアミン等の芳香族アミン系酸化防止剤；トリフェニルホスファイト等のリン系酸化防止剤；３，３’−チオジプロピオン酸ジミリスチル等の硫黄系酸化防止剤；Ｎ−ニトロソフェニルヒドロキシアミンアンモニウム塩（クペロン）等のＮ−ニトロソ化合物系重合禁止剤；有機酸銅塩やフェノチアジン等の１種又は２種以上を用いることができる。 Examples of the polymerization inhibitor include hydroquinone polymerization inhibitors such as hydroquinone, methylhydroquinone, trimethylhydroquinone, t-butylhydroquinone and 2,5-di (t-amyl) hydroquinone; methoquinone, 6-t-butyl-2,4 -Phenolic oxidation of xylenol, 2,6-di-t-butylphenol, 2,6-di-t-butyl-4-methoxyphenol, 2,2'-methylenebis (4-methyl-6-t-butylphenol) Inhibitor; bis (2,2,6,6-tetramethylpiperidinoxy-4-yl) sebacate (EC3314A), 4-hydroxy-2,2,6,6-tetramethylpiperidyl-1-oxyl ( N-oxyl compound-based polymerization inhibitors such as 4-H-TEMPO); Hindered amine stabilizers such as lysine-4-yl); aromatic amine antioxidants such as diphenylamine; phosphorus antioxidants such as triphenyl phosphite; sulfur systems such as dimyristyl 3,3′-thiodipropionate Antioxidants; N-nitroso compound-based polymerization inhibitors such as N-nitrosophenylhydroxyamine ammonium salt (cuperon); one or more of organic acid copper salts and phenothiazines can be used.
本発明の脂環式（メタ）アクリレートの製造方法では、反応工程を行った後、中和剤によって酸触媒を不活性化処理することで、水洗工程と乾燥工程を省略することができる。
水洗工程と乾燥工程とを省略することは製造工程の簡略化、廃棄物の削減の点から好ましい。このように、水洗工程を行わないことや、乾燥工程を行わないことは本発明の脂環式（メタ）アクリレートの製造方法の好適な実施形態の１つである。
In the manufacturing method of the alicyclic (meth) acrylate of this invention, after performing a reaction process, a water-washing process and a drying process can be abbreviate | omitted by inactivating an acid catalyst with a neutralizer.
It is preferable to omit the water washing step and the drying step from the viewpoint of simplifying the manufacturing process and reducing waste. Thus, it is one of the preferred embodiments of the method for producing an alicyclic (meth) acrylate of the present invention not to perform the water washing step or not to perform the drying step.
上記酸触媒の不活性化処理に用いる中和剤としては、硫酸塩、りん酸塩、スルホン酸塩、シュウ酸塩、カルボン酸塩、炭酸塩、ケイ酸塩、ほう酸塩、金属等の酸化物、三級アミン類等の１種又は２種以上を用いることができる。好ましくは、アルカリ金属の硫酸塩、アルカリ土類金属の硫酸塩、アルカリ金属のりん酸塩、アルカリ土類金属のりん酸塩、アルカリ金属のスルホン酸塩、アルカリ土類金属のスルホン酸塩、アルカリ金属のシュウ酸塩、アルカリ土類金属のシュウ酸塩等である。
中和剤は、中和する酸触媒の種類や量に応じて、酸触媒の中和に必要な量を適宜使用すればよい。
Examples of the neutralizing agent used for the deactivation treatment of the acid catalyst include sulfate, phosphate, sulfonate, oxalate, carboxylate, carbonate, silicate, borate, and metal oxides. 1 type, or 2 or more types, such as tertiary amines, can be used. Preferably, alkali metal sulfate, alkaline earth metal sulfate, alkali metal phosphate, alkaline earth metal phosphate, alkali metal sulfonate, alkaline earth metal sulfonate, alkali Metal oxalate, alkaline earth metal oxalate, and the like.
The neutralizing agent may be appropriately used in an amount necessary for neutralizing the acid catalyst according to the type and amount of the acid catalyst to be neutralized.
本発明の脂環式（メタ）アクリレートの製造方法は、上記反応工程の後に、得られた脂環式（メタ）アクリレートを精製する工程を含んでいてもよい。
精製工程において脂環式（メタ）アクリレートを精製する方法は特に制限されないが、蒸留が好ましい。
脂環式（メタ）アクリレートを蒸留により精製する場合、安定剤を添加して行ってもよい。安定剤としては、上記重合禁止剤と同じものを用いることができ、添加量も上記重合禁止剤と同様であることが好ましい。
なお、精製工程においてもラジカル重合防止の観点から、分子状酸素の存在下で実施されることが好ましい。
The manufacturing method of the alicyclic (meth) acrylate of this invention may include the process of refine | purifying the obtained alicyclic (meth) acrylate after the said reaction process.
The method for purifying the alicyclic (meth) acrylate in the purification step is not particularly limited, but distillation is preferred.
When purifying alicyclic (meth) acrylate by distillation, a stabilizer may be added. As the stabilizer, the same one as the polymerization inhibitor can be used, and the addition amount is preferably the same as that of the polymerization inhibitor.
The purification step is preferably carried out in the presence of molecular oxygen from the viewpoint of preventing radical polymerization.
本発明の脂環式（メタ）アクリレートの製造方法に反応原料として用いる脂環式ジエン化合物は、上記一般式（１）で表される構造のものである。上記一般式（１）で表される脂環式ジエン化合物は光学異性体を有する化合物である。本発明の脂環式（メタ）アクリレートの製造方法には、光学異性体のいずれか一方のみを用いてもよく、ラセミ体を用いてもよい。 The alicyclic diene compound used as a reaction raw material in the method for producing an alicyclic (meth) acrylate of the present invention has a structure represented by the above general formula (1). The alicyclic diene compound represented by the general formula (1) is a compound having an optical isomer. In the method for producing an alicyclic (meth) acrylate of the present invention, only one of optical isomers may be used, or a racemate may be used.
上記一般式（１）において、Ｒ１、Ｒ２は、同一又は異なって、水素原子又は１価の有機基を表すが、１価の有機基としては、炭素数１〜３０の直鎖状又は分岐状アルキル基、炭素数３〜３０の環状アルキル基、炭素数１〜３０の直鎖状又は分岐状アルケニル基、炭素数１〜３０の環状アルケニル基、炭素数１〜３０の直鎖状又は分岐状アルキニル基、炭素数６〜３０のアリール基等の炭素数１〜３０の炭化水素基；炭素数１〜３０のアルコキシ基又はアリールオキシ基、アルキルカルボニルオキシ基、アルケニルカルボニルオキシ基又はアリールカルボニルオキシ基、アルキルオキシカルボニル基、アルケニルオキシカルボニル基又はアリールオキシカルボニル基、アルキルカルボニル基、アルケニルカルボニル基又はアリールカルボニル基、シアノ基のいずれかによって置換された上記炭素数１〜３０の炭化水素基；炭素数１〜２０のオキシアルキレン基を繰り返し単位とするポリアルキレングリコール構造；炭素数１〜３０のアルキル基、アルケニル基又はアリール基によって置換されたカルボニル基；炭素数１〜３０のアルキル基、アルケニル基又はアリール基によって置換されたオキシカルボニル基等が挙げられる。 In the general formula (1), R 1 and R 2 are the same or different and each represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is a straight chain having 1 to 30 carbon atoms or Branched alkyl group, cyclic alkyl group having 3 to 30 carbon atoms, linear or branched alkenyl group having 1 to 30 carbon atoms, cyclic alkenyl group having 1 to 30 carbon atoms, linear chain having 1 to 30 carbon atoms, or A branched alkynyl group, a hydrocarbon group having 1 to 30 carbon atoms such as an aryl group having 6 to 30 carbon atoms; an alkoxy group having 1 to 30 carbon atoms, an aryloxy group, an alkylcarbonyloxy group, an alkenylcarbonyloxy group, or an arylcarbonyl group Oxy group, alkyloxycarbonyl group, alkenyloxycarbonyl group or aryloxycarbonyl group, alkylcarbonyl group, alkenylcarbonyl group or arylcarbonyl A hydrocarbon group having 1 to 30 carbon atoms substituted by any one of a group and a cyano group; a polyalkylene glycol structure having a repeating unit of an oxyalkylene group having 1 to 20 carbon atoms; an alkyl group having 1 to 30 carbon atoms; Examples thereof include a carbonyl group substituted by an alkenyl group or an aryl group; an oxycarbonyl group substituted by an alkyl group having 1 to 30 carbon atoms, an alkenyl group or an aryl group, and the like.
上記炭素数１〜３０のアルコキシ基又はアリールオキシ基、アルキルカルボニルオキシ基、アルケニルカルボニルオキシ基又はアリールカルボニルオキシ基、アルキルオキシカルボニル基、アルケニルオキシカルボニル基又はアリールオキシカルボニル基、アルキルカルボニル基、アルケニルカルボニル基又はアリールカルボニル基、シアノ基のいずれかによって置換された上記炭素数１〜３０の炭化水素基の具体例としては、炭素数１〜３０のアルコキシ基又はアリールオキシ基によって置換された炭素数１〜３０のアルキル基、アルケニル基又はアリール基；炭素数１〜３０のアルキルカルボニルオキシ基、アルケニルカルボニルオキシ基又はアリールカルボニルオキシ基によって置換された炭素数１〜３０のアルキル基、アルケニル基又はアリール基；炭素数１〜３０のアルキルオキシカルボニル基、アルケニルオキシカルボニル基又はアリールオキシカルボニル基によって置換された炭素数１〜３０のアルキル基、アルケニル基又はアリール基；炭素数１〜３０のアルキルカルボニル基、アルケニルカルボニル基又はアリールカルボニル基によって置換された炭素数１〜３０のアルキル基、アルケニル基又はアリール基；シアノ基によって置換された炭素数１〜３０のアルキル基、アルケニル基又はアリール基等が挙げられる。 C1-C30 alkoxy group or aryloxy group, alkylcarbonyloxy group, alkenylcarbonyloxy group or arylcarbonyloxy group, alkyloxycarbonyl group, alkenyloxycarbonyl group or aryloxycarbonyl group, alkylcarbonyl group, alkenylcarbonyl Specific examples of the hydrocarbon group having 1 to 30 carbon atoms substituted by any one of a group, an arylcarbonyl group and a cyano group include 1 carbon atom substituted by an alkoxy group having 1 to 30 carbon atoms or an aryloxy group -30 alkyl group, alkenyl group or aryl group; an alkyl group having 1-30 carbon atoms, an alkenyl group having 1-30 carbon atoms substituted by an alkylcarbonyloxy group, alkenylcarbonyloxy group or arylcarbonyloxy group having 1-30 carbon atoms Is an aryl group; an alkyl group having 1 to 30 carbon atoms, an alkenyl group or an aryl group substituted by an alkyloxycarbonyl group, alkenyloxycarbonyl group or aryloxycarbonyl group having 1 to 30 carbon atoms; alkyl having 1 to 30 carbon atoms C1-C30 alkyl group, alkenyl group or aryl group substituted by a carbonyl group, alkenylcarbonyl group or arylcarbonyl group; C1-C30 alkyl group, alkenyl group or aryl group substituted by cyano group, etc. Is mentioned.
上記炭素数１〜３０の炭化水素基の中でも、炭素数１〜６の炭化水素基が好ましく、より好ましくは、炭素数１〜３の炭化水素基である。
Ｒ１、Ｒ２としては、上述したものの中でも、エチル基、メチル基、水素原子が好ましい。より好ましくは、メチル基、水素原子である。
Among the hydrocarbon groups having 1 to 30 carbon atoms, hydrocarbon groups having 1 to 6 carbon atoms are preferable, and hydrocarbon groups having 1 to 3 carbon atoms are more preferable.
As R 1 and R 2 , among those described above, an ethyl group, a methyl group, and a hydrogen atom are preferable. More preferably, they are a methyl group and a hydrogen atom.
上記一般式（１）で表される脂環式ジエン化合物の具体例としては、５−アルキリデンー２−ノルボルネン等が挙げられる。好ましくは、５−エチリデンー２−ノルボルネン、５−プロピリデンー２−ノルボルネン、５−イソプロピリデンー２−ノルボルネン、５−メチリデンー２−ノルボルネン等が挙げられる。 Specific examples of the alicyclic diene compound represented by the general formula (1) include 5-alkylidene-2-norbornene. Preferable examples include 5-ethylidene-2-norbornene, 5-propylidene-2-norbornene, 5-isopropylidene-2-norbornene, and 5-methylidene-2-norbornene.
上記一般式（１）で表される脂環式ジエン化合物と反応させる（メタ）アクリル酸は、アクリル酸であってもメタクリル酸であってもよく、これらの混合物であってもよい。
また、上記一般式（１）で表される脂環式ジエン化合物と反応させる（メタ）アクリル酸は、脂環式ジエン化合物との反応工程において重合反応が進行することを抑制するため、重合禁止剤を含んでいてもよい。
重合禁止剤を含む場合、重合禁止剤の含有量は（メタ）アクリル酸に対して、１〜１００００ｐｐｍであることが好ましい。
重合禁止剤としては、上述したものと同様のものを用いることができる。
The (meth) acrylic acid to be reacted with the alicyclic diene compound represented by the general formula (1) may be acrylic acid, methacrylic acid, or a mixture thereof.
In addition, (meth) acrylic acid to be reacted with the alicyclic diene compound represented by the above general formula (1) inhibits the polymerization reaction from proceeding in the reaction step with the alicyclic diene compound. An agent may be included.
When a polymerization inhibitor is included, the content of the polymerization inhibitor is preferably 1 to 10,000 ppm with respect to (meth) acrylic acid.
As the polymerization inhibitor, the same ones as described above can be used.
本発明の脂環式（メタ）アクリレートの製造方法では、反応温度や使用する触媒等の製造条件を調整することで、生成する脂環式（メタ）アクリレートにおける上記一般式（２）で表される構造の脂環式（メタ）アクリレートと上記一般式（３）で表される構造の脂環式（メタ）アクリレートとのモル比（異性体組成）を変化させることが可能となり、例えば、当該異性体組成が８／２〜２／８である脂環式（メタ）アクリレートを製造することが可能である。
これは、当該異性体組成が８／２前後のものしか得られない従来の製造方法との大きな相違点であり、本発明の脂環式（メタ）アクリレートの製造方法の有利な点の１つである。
このような、本発明の脂環式（メタ）アクリレートの製造方法によって製造される脂環式（メタ）アクリレートであって、該脂環式（メタ）アクリレートは、下記一般式（２）で表される構造の脂環式（メタ）アクリレートと下記一般式（３）で表される構造の脂環式（メタ）アクリレートとを８／２〜２／８のモル比で含むことを特徴とする脂環式（メタ）アクリレートもまた、本発明の１つである。
下記一般式（２）で表される構造の脂環式（メタ）アクリレートと下記一般式（３）で表される構造の脂環式（メタ）アクリレートとの好ましいモル比は、７．５／２．５〜２／８であり、より好ましくは７．２／２．８〜２／８であり、更に好ましくは７／３〜２／８である。
In the manufacturing method of alicyclic (meth) acrylate of this invention, it is represented by the said General formula (2) in the alicyclic (meth) acrylate to produce | generate by adjusting manufacturing conditions, such as reaction temperature and the catalyst to be used. It is possible to change the molar ratio (isomer composition) of the alicyclic (meth) acrylate having a structure represented by the general formula (3) and the alicyclic (meth) acrylate having the structure represented by the general formula (3). It is possible to produce an alicyclic (meth) acrylate having an isomer composition of 8/2 to 2/8.
This is a significant difference from the conventional production method in which the isomer composition is only about 8/2, and is one of the advantages of the production method of the alicyclic (meth) acrylate of the present invention. It is.
Such an alicyclic (meth) acrylate produced by the method for producing an alicyclic (meth) acrylate of the present invention, wherein the alicyclic (meth) acrylate is represented by the following general formula (2). The alicyclic (meth) acrylate having the structure shown below and the alicyclic (meth) acrylate having the structure represented by the following general formula (3) are included at a molar ratio of 8/2 to 2/8. An alicyclic (meth) acrylate is also one aspect of the present invention.
The preferred molar ratio of the alicyclic (meth) acrylate having the structure represented by the following general formula (2) and the alicyclic (meth) acrylate having the structure represented by the following general formula (3) is 7.5 / 2.5 to 2/8, more preferably 7.2 / 2.8 to 2/8, and even more preferably 7/3 to 2/8.
（式中、Ｒ１、Ｒ２は、同一又は異なって、水素原子又は１価の有機基を表す。Ｒ３は、水素原子又はメチル基を表す。式（２）における脂環式骨格と（メタ）アクリロイルオキシ基との間の波線は、（メタ）アクリロイルオキシ基の配置が異なる立体異性体が存在することを表す。） (In the formula, R 1 and R 2 are the same or different and each represents a hydrogen atom or a monovalent organic group. R 3 represents a hydrogen atom or a methyl group. The alicyclic skeleton in the formula (2) and ( (The wavy line between the (meth) acryloyloxy group represents the presence of stereoisomers having different configurations of the (meth) acryloyloxy group).
本発明において、上記一般式（２）で表される構造の脂環式（メタ）アクリレートには、（メタ）アクリロイルオキシ基の配置が異なる立体異性体が存在する。これら立体異性体は、それぞれ下記一般式（２−１）、（２−２）で表される構造を有する。 In the present invention, the alicyclic (meth) acrylate having the structure represented by the general formula (2) includes stereoisomers having different (meth) acryloyloxy group arrangements. These stereoisomers have structures represented by the following general formulas (2-1) and (2-2), respectively.
上記一般式（３）で表される構造の脂環式（メタ）アクリレートでは、（メタ）アクリロイルオキシ基が脂環式骨格のいずれの位置に結合していてもよく、下記式（３−１）、（３−２）、（３−３）、（３−４）のような構造のものがある。 In the alicyclic (meth) acrylate having the structure represented by the general formula (3), the (meth) acryloyloxy group may be bonded to any position of the alicyclic skeleton, and the following formula (3-1) ), (3-2), (3-3), and (3-4).
上記一般式（２）で表される構造の脂環式（メタ）アクリレートや一般式（３）で表される構造の脂環式（メタ）アクリレートは、（メタ）アクリロイル基に由来する重合性二重結合を有しており、重合体の原料としても好適に用いることができる。
このような脂環式（メタ）アクリレートを含む単量体成分を重合して得られる脂環式（メタ）アクリレート重合体であって、該脂環式（メタ）アクリレートは、下記一般式（２）で表される構造の脂環式（メタ）アクリレート及び／又は下記一般式（３）で表される構造の脂環式（メタ）アクリレートを含むことを特徴とする脂環式（メタ）アクリレート重合体もまた、本発明の１つである。
The alicyclic (meth) acrylate having the structure represented by the general formula (2) and the alicyclic (meth) acrylate having the structure represented by the general formula (3) are polymerizable from a (meth) acryloyl group. It has a double bond and can be suitably used as a raw material for the polymer.
An alicyclic (meth) acrylate polymer obtained by polymerizing a monomer component containing such an alicyclic (meth) acrylate, wherein the alicyclic (meth) acrylate is represented by the following general formula (2) ) And / or an alicyclic (meth) acrylate having a structure represented by the following general formula (3): A polymer is also one aspect of the present invention.
（式中、Ｒ１、Ｒ２は、同一又は異なって、水素原子又は１価の有機基を表す。Ｒ３は、水素原子又はメチル基を表す。式（２）における脂環式骨格と（メタ）アクリロイルオキシ基との間の波線は、（メタ）アクリロイルオキシ基の配置が異なる立体異性体が存在することを表す。） (In the formula, R 1 and R 2 are the same or different and each represents a hydrogen atom or a monovalent organic group. R 3 represents a hydrogen atom or a methyl group. The alicyclic skeleton in the formula (2) and ( (The wavy line between the (meth) acryloyloxy group represents the presence of stereoisomers having different configurations of the (meth) acryloyloxy group).
上記脂環式（メタ）アクリレート重合体の原料となる単量体成分は、上記一般式（２）で表される構造の脂環式（メタ）アクリレート及び／又は上記一般式（３）で表される構造の脂環式（メタ）アクリレートのみを含むものであってもよく、その他の単量体を含むものであってもよい。
その他の単量体としては、上記脂環式（メタ）アクリレートと共重合が可能なものであれば特に限定されないが、単官能（メタ）アクリレート、２官能（メタ）アクリレート、３官能以上の（メタ）アクリレート、（メタ）アクリルアミド、（メタ）アクリロニトリル、スチレン等が挙げられる。
上記単官能（メタ）アクリレートとしては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、ｎ−ステアリル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、グリセリンモノ（メタ）アクリレート、グリシジル（メタ）アクリレート、ラウリル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ベンジル（メタ）アクリレート、フェノールエチレンオキサイド変性（ｎ＝２）（メタ）アクリレート、ノニルフェノールプロピレンオキサイド変性（ｎ＝２．５）（メタ）アクリレート、２−（メタ）アクリロイルオキシエチルアシッドホスフェート、フルフリル（メタ）アクリレート、カルビトール（メタ）アクリレート、ブトキシエチル（メタ）アクリレート、アリル（メタ）アクリレート、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、２−ヒドロキシブチル（メタ）アクリレート、２−フェノキシ−２−ヒドロキシプロピル（メタ）アクリレート、２−ヒドロキシ−３−フェノキシプロピル（メタ）アクリレート、３−クロロ−２−ヒドロキシプロピル（メタ）アクリレートが挙げられる。
上記２官能（メタ）アクリレートとしては、例えば、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、ジプロピレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、ブチレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、エチレンオキサイド変性ビスフェノールＡ型ジ（メタ）アクリレート、プロピレンオキサイド変性ビスフェノールＡ型ジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、グリセリンジ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレート、エチレングリコールジグリシジルエーテルジ（メタ）アクリレート、ジエチレングリコールジグリシジルエーテルジ（メタ）アクリレート、フタル酸ジグリシジルエステルジ（メタ）アクリレート、ヒドロキシピバリン酸変性ネオペンチルグリコールジ（メタ）アクリレート、１，９−ノナンジオールジアクリレート、トリシクロデカンジメタノールジアクリレート等が挙げられる。
上記３官能以上の（メタ）アクリレートとしては、例えば、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、トリ（メタ）アクリロイルオキシエトキシトリメチロールプロパン、グリセリンポリグリシジルエーテルポリ（メタ）アクリレート、トリス（２−アクリロイルオキシエチル）イソシアヌレート等が挙げられる。
The monomer component used as the raw material of the alicyclic (meth) acrylate polymer is represented by the alicyclic (meth) acrylate having the structure represented by the general formula (2) and / or the general formula (3). It may contain only the alicyclic (meth) acrylate having the structure described above, or may contain other monomers.
The other monomer is not particularly limited as long as it can be copolymerized with the above alicyclic (meth) acrylate, but it is monofunctional (meth) acrylate, bifunctional (meth) acrylate, trifunctional or higher ( Examples include meth) acrylate, (meth) acrylamide, (meth) acrylonitrile, and styrene.
Examples of the monofunctional (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, n-stearyl (meth) acrylate, and phenoxyethyl (meth) ) Acrylate, glycerin mono (meth) acrylate, glycidyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, phenol ethylene oxide modified (n = 2) ) (Meth) acrylate, nonylphenol propylene oxide modified (n = 2.5) (meth) acrylate, 2- (meth) acryloyloxyethyl acid phosphate, furfuryl (meth) acrylic , Carbitol (meth) acrylate, butoxyethyl (meth) acrylate, allyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, Examples include 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and 3-chloro-2-hydroxypropyl (meth) acrylate.
Examples of the bifunctional (meth) acrylate include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and propylene glycol di (meth). Acrylate, dipropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide modified bisphenol A type di (meth) acrylate, propylene oxide Modified bisphenol A type di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) acrylate, Intererythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, hydroxypivalic acid modified neopentyl glycol di (meth) ) Acrylate, 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate and the like.
Examples of the trifunctional or higher functional (meth) acrylate include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipenta Examples include erythritol hexa (meth) acrylate, tri (meth) acryloyloxyethoxytrimethylolpropane, glycerin polyglycidyl ether poly (meth) acrylate, and tris (2-acryloyloxyethyl) isocyanurate.
上記脂環式（メタ）アクリレート重合体の原料となる単量体成分中の上記一般式（２）又は一般式（３）で表される構造の脂環式（メタ）アクリレートの割合は、単量体成分全体１００質量％に対して、１０〜１００質量％であることが好ましい。このような割合で脂環式（メタ）アクリレートを含むことで、得られる重合体が脂環式（メタ）アクリレートに由来する特性を充分に発揮することができる。より好ましくは、単量体成分全体１００質量％に対して、２０〜１００質量％である。 The ratio of the alicyclic (meth) acrylate having the structure represented by the general formula (2) or the general formula (3) in the monomer component as a raw material of the alicyclic (meth) acrylate polymer is simply It is preferable that it is 10-100 mass% with respect to 100 mass% of the whole mass component. By including the alicyclic (meth) acrylate at such a ratio, the resulting polymer can sufficiently exhibit the characteristics derived from the alicyclic (meth) acrylate. More preferably, it is 20-100 mass% with respect to 100 mass% of the whole monomer component.
上記脂環式（メタ）アクリレート重合体の製造には、重合開始剤を用いることができる。
重合開始剤としては、熱重合開始剤、光重合開始剤のいずれも用いることができ、これらを併用してもよい。
上記熱重合開始剤としては、過酸化水素；過硫酸アンモニウム、過硫酸ナトリウム、過硫酸カリウム等の過硫酸塩；２，２′−アゾビス（２−アミジノプロパン）２塩酸塩、４，４′−アゾビス−（４−シアノバレリン酸）、２，２′−アゾビスイソブチロニトリル等のアゾ系化合物；過酢酸、過コハク酸、ｔ−ブチルヒドロペルオキシド、ジ−ｔ−ブチルペルオキシド、ベンゾイルペルオキシド、シクロヘキサノンペルオキシド等の有機過酸化物等の１種又は２種以上を用いることができる。
For the production of the alicyclic (meth) acrylate polymer, a polymerization initiator can be used.
As the polymerization initiator, either a thermal polymerization initiator or a photopolymerization initiator can be used, and these may be used in combination.
Examples of the thermal polymerization initiator include hydrogen peroxide; persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate; 2,2′-azobis (2-amidinopropane) dihydrochloride, 4,4′-azobis. Azo compounds such as-(4-cyanovaleric acid) and 2,2'-azobisisobutyronitrile; peracetic acid, persuccinic acid, t-butyl hydroperoxide, di-t-butyl peroxide, benzoyl peroxide, cyclohexanone peroxide 1 type, or 2 or more types, such as organic peroxides, etc. can be used.
上記光重合開始剤としては、ジエトキシアセトフェノン、４−（２−ヒドロキシエトキシ）フェニル−（２−ヒドロキシ−２−プロピル）ケトン、２−メチル−２−モルホリノ（４−チオメチルフェニル）プロパン−１−オン（チバ・ガイギー社製「イルガキュア９０７」）、２−ベンジル−２−ジメチルアミノ−１−（４−モルホリノフェニル）−ブタノン、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン（メルク社製「ダロキュア１１７３」）、１−ヒドロキシシクロヘキシルフェニルケトン（チバ・ガイギー社製「イルガキュア１８４」）等の分子内結合開裂型の光重合開始剤；ベンゾフェノン、ο−ベンゾイル安息香酸メチル及びο−ベンゾイル安息香酸アルキル、４−フェニルベンゾフェノン、等のベンゾフェノン系、２−イソプロピルチオキサントン、２，４−ジメチルチオキサントン等のチオキサントン系、ミヒラーケトン、４，４′−ジエチルアミノベンゾフェノン等のアミノベンゾフェノン系、１０−ブチル−２−クロロアクリドン、２−エチルアンスラキノン、９，１０−フェナンスレンキノン、カンファーキノン等の分子内水素引き抜き型光重合開始剤；トリフェニルスルホニウムヘキサフルオロアンチモネート、トリフェニルスルホニウムホスフェート、ｐ−（フェニルチオ）フェニルジフェニルスルホニウムヘキサフルオロアンチモネート、ｐ−（フェニルチオ）フェニルジフェニルスルホニウムヘキサフルオロホスフェート等の光カチオン重合開始剤等の１種又は２種以上を用いることができる。 Examples of the photopolymerization initiator include diethoxyacetophenone, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propane-1 -ON ("Irgacure 907" manufactured by Ciba-Geigy), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2-hydroxy-2-methyl-1-phenylpropan-1-one (Merck's “Darocur 1173”), 1-hydroxycyclohexyl phenyl ketone (Ciba Geigy's “Irgacure 184”) and other intramolecular bond cleavage type photopolymerization initiators; benzophenone, o-benzoyl methylbenzoate and -Benzophenones such as alkyl benzoylbenzoate, 4-phenylbenzophenone, etc. Thioxanthones such as 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, aminobenzophenones such as Michler's ketone, 4,4'-diethylaminobenzophenone, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9 , 10-phenanthrenequinone, camphorquinone, and other intramolecular hydrogen abstraction photopolymerization initiators; triphenylsulfonium hexafluoroantimonate, triphenylsulfonium phosphate, p- (phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, p- 1 type (s) or 2 or more types, such as photocationic polymerization initiators, such as (phenylthio) phenyl diphenylsulfonium hexafluorophosphate, can be used.
上記重合開始剤の使用量は、脂環式（メタ）アクリレート重合体の原料となる単量体成分１００質量％に対して０．０００１〜２０質量％であることが好ましい。より好ましくは、０．０１〜１０質量％である。
重合開始剤を２種以上用いる場合には、２種以上の重合開始剤の合計が上記割合であることが好ましい。
It is preferable that the usage-amount of the said polymerization initiator is 0.0001-20 mass% with respect to 100 mass% of monomer components used as the raw material of an alicyclic (meth) acrylate polymer. More preferably, it is 0.01-10 mass%.
When using 2 or more types of polymerization initiators, it is preferable that the total of 2 or more types of polymerization initiators is the said ratio.
本発明の脂環式（メタ）アクリレート重合体は、架橋されていても、架橋されていなくともよい。架橋されていない場合の重量平均分子量は、特に制限はないが、１０００以上、１０００００００以下であることが好ましい。
上記重量平均分子量は、ポリスチレン換算によるゲルパーミエーションクロマトグラフィ（ＧＰＣ装置、展開溶媒；クロロホルム）によって以下の装置、及び、測定条件で測定することができる。
高速ＧＰＣ装置：ＨＬＣ−８２２０ＧＰＣ（東ソー社製）
展開溶媒：クロロホルム
カラム：ＴＳＫ−ｇｅｌ ＧＭＨＸＬ ×２本
溶離液流量：１ｍｌ／ｍｉｎ
カラム温度：４０℃
The alicyclic (meth) acrylate polymer of the present invention may or may not be crosslinked. The weight average molecular weight when not crosslinked is not particularly limited, but is preferably 1000 or more and 10000000 or less.
The weight average molecular weight can be measured by gel permeation chromatography (GPC apparatus, developing solvent: chloroform) in terms of polystyrene under the following apparatus and measurement conditions.
High-speed GPC device: HLC-8220GPC (manufactured by Tosoh Corporation)
Developing solvent: Chloroform column: TSK-gel GMHXL x 2 Eluent flow rate: 1 ml / min
Column temperature: 40 ° C
上述したように、重合性の（メタ）アクリロイル基を有し、重合体の原料となる一般式（２）で表される構造の脂環式（メタ）アクリレートや一般式（３）で表される構造の脂環式（メタ）アクリレートは、硬化性樹脂の原料としても好適に用いることができる。これらの脂環式（メタ）アクリレートを原料として得られる硬化性樹脂は、ＵＶ硬化性や塗膜の硬度、耐溶剤性、可とう性、密着性等の種々の特性に優れた樹脂となる。
このような下記一般式（２）で表される構造の脂環式（メタ）アクリレート及び／又は下記一般式（３）で表される構造の脂環式（メタ）アクリレートを含むことを特徴とする硬化性樹脂用材料もまた、本発明の１つである。
As described above, it is represented by an alicyclic (meth) acrylate having a polymerizable (meth) acryloyl group and having a structure represented by the general formula (2), which is a raw material for the polymer, and the general formula (3). The alicyclic (meth) acrylate having a structure as described above can also be suitably used as a raw material for the curable resin. A curable resin obtained using these alicyclic (meth) acrylates as a raw material is a resin excellent in various properties such as UV curability, coating film hardness, solvent resistance, flexibility, and adhesion.
The alicyclic (meth) acrylate having the structure represented by the following general formula (2) and / or the alicyclic (meth) acrylate having the structure represented by the following general formula (3) are included. The curable resin material to be used is also one aspect of the present invention.
（式中、Ｒ１、Ｒ２は、同一又は異なって、水素原子又は１価の有機基を表す。Ｒ３は、水素原子又はメチル基を表す。式（２）における脂環式骨格と（メタ）アクリロイルオキシ基との間の波線は、（メタ）アクリロイルオキシ基の配置が異なる立体異性体が存在することを表す。） (In the formula, R 1 and R 2 are the same or different and each represents a hydrogen atom or a monovalent organic group. R 3 represents a hydrogen atom or a methyl group. The alicyclic skeleton in the formula (2) and ( (The wavy line between the (meth) acryloyloxy group represents the presence of stereoisomers having different configurations of the (meth) acryloyloxy group).
本発明の硬化性樹脂用材料は、一般式（２）で表される構造の脂環式（メタ）アクリレート、一般式（３）で表される構造の脂環式（メタ）アクリレートの少なくとも一方を含むものであればよいが、一般式（２）で表される構造の脂環式（メタ）アクリレートと一般式（３）で表される構造の脂環式（メタ）アクリレートの両方を含むものであることが好ましい。これら両方を含むものである場合、硬化性樹脂用材料中におけるこれらの比率を変えることで、得られる硬化性樹脂の特性を変化させることができる。例えば、一般式（２）で表される構造の脂環式（メタ）アクリレートの割合を増やすと、得られる硬化性樹脂が耐熱分解性、可とう性に特に優れたものとなり、一般式（３）で表される構造の脂環式（メタ）アクリレートの割合を増やすと、塗膜硬度、耐熱性、耐溶剤性に特に優れたものとなる。硬化性樹脂用材料中における一般式（２）で表される構造の脂環式（メタ）アクリレートと一般式（３）で表される構造の脂環式（メタ）アクリレートとのモル比は、求められる特性に応じて調整すればよい。
上記脂環式（メタ）アクリレート重合体の原料となる脂環式（メタ）アクリレートや、上記硬化性樹脂用材料に含まれる脂環式（メタ）アクリレートとしては、本発明の脂環式（メタ）アクリレートの製造方法により得られた脂環式（メタ）アクリレートを好適に用いることができる。
The curable resin material of the present invention is at least one of an alicyclic (meth) acrylate having a structure represented by the general formula (2) and an alicyclic (meth) acrylate having a structure represented by the general formula (3). The alicyclic (meth) acrylate having the structure represented by the general formula (2) and the alicyclic (meth) acrylate having the structure represented by the general formula (3) are included. It is preferable. When both are included, the characteristics of the resulting curable resin can be changed by changing these ratios in the curable resin material. For example, when the proportion of the alicyclic (meth) acrylate having the structure represented by the general formula (2) is increased, the resulting curable resin is particularly excellent in thermal decomposition resistance and flexibility, and the general formula (3 When the proportion of the alicyclic (meth) acrylate having a structure represented by) is increased, the coating film hardness, heat resistance, and solvent resistance are particularly excellent. The molar ratio of the alicyclic (meth) acrylate having the structure represented by the general formula (2) and the alicyclic (meth) acrylate having the structure represented by the general formula (3) in the curable resin material is as follows: What is necessary is just to adjust according to the characteristic calculated | required.
Examples of the alicyclic (meth) acrylate used as a raw material for the alicyclic (meth) acrylate polymer and the alicyclic (meth) acrylate contained in the curable resin material include the alicyclic (meta) of the present invention. ) The alicyclic (meth) acrylate obtained by the acrylate production method can be suitably used.
本発明の脂環式（メタ）アクリレートの製造方法は、上述の構成よりなり、少量の触媒かつ無溶媒で反応を行うことが可能であることから、従来の製造方法よりもより簡略な工程で、廃棄物（排水）を大幅に低減でき、触媒による装置の腐食も抑制することが可能な脂環式（メタ）アクリレートを製造することができる、効率的かつ経済的な製造方法である。 The production method of the alicyclic (meth) acrylate according to the present invention has the above-described configuration, and can perform the reaction with a small amount of catalyst and no solvent. Therefore, the production method is simpler than the conventional production method. This is an efficient and economical production method capable of producing an alicyclic (meth) acrylate capable of greatly reducing waste (drainage) and suppressing corrosion of the apparatus due to the catalyst.
以下に実施例を掲げて本発明を更に詳細に説明するが、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、特に断りのない限り、「部」は「重量部」を、「％」は「質量％」を意味するものとする。 The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “mass%”.
反応収率、及び、脂環式（メタ）アクリレートの異性体の比率は、ガスクロマトグラフィー（Ａｇｉｌｅｎｔ社製、６８５０）により測定した。 The reaction yield and the ratio of the alicyclic (meth) acrylate isomers were measured by gas chromatography (manufactured by Agilent, 6850).
１．脂環式（メタ）アクリレートの合成
実施例１
ガラス製フラスコにトリフルオロメタンスルホン酸６ｍｇとアクリル酸１４．４ｇを仕込み、７体積％酸素含有窒素を１０ｍｌ／ｍｉｎにて吹き込みながら、ボトムを８０℃のオイルバスに浸け撹拌した。アクリル酸２８８ｇ、５−エチリデン−２−ノルボルネン４８０ｇ、２，５−ジ（ｔ−ブチル）ヒドロキノン０．８ｇの混合液を徐々に滴下し、２時間かけて全量を加えた。滴下しながらオイルバス温度を徐々に上昇させ、１時間かけて１００℃まで到達させた。滴下後５時間、１００℃で撹拌を続けた後、反応液を４０℃まで冷却した。反応収率は９５ｍｏｌ％であった（ＥＴＣＨＡ／ＥＮＢＡ＝３／７（モル比））。ドデシルベンゼンスルホン酸ナトリウム０．８ｇを添加し４０℃で１時間撹拌し、ＥＣ３３１４Ａ０．８ｇを添加し、７体積％酸素含有窒素を１０ｍｌ／ｍｉｎで吹き込みながら１〜２ｋＰａ、１２０〜１６０℃にて蒸留を行った。得られた脂環式（メタ）アクリレートは６９１ｇ、合計収率は９０ｍｏｌ％であった（ＥＴＣＨＡ／ＥＮＢＡ＝３／７（モル比））。
なお、ＥＴＣＨＡとは、上記一般式（２−１）、（２−２）において、Ｒ１、Ｒ２のどちらか一方がメチル基で他方が水素原子であり、Ｒ３が水素原子である構造の脂環式（メタ）アクリレートであり、ＥＮＢＡとは、上記一般式（３−１）、（３−２）、（３−３）、（３−４）において、Ｒ１、Ｒ２のどちらか一方がメチル基で他方が水素原子であり、Ｒ３が水素原子である構造の脂環式（メタ）アクリレートである。
1. Synthesis example 1 of alicyclic (meth) acrylate
A glass flask was charged with 6 mg of trifluoromethanesulfonic acid and 14.4 g of acrylic acid, and the bottom was immersed in an oil bath at 80 ° C. and stirred while blowing nitrogen containing 7% by volume at 10 ml / min. A mixed solution of 288 g of acrylic acid, 480 g of 5-ethylidene-2-norbornene, and 0.8 g of 2,5-di (t-butyl) hydroquinone was gradually added dropwise, and the whole amount was added over 2 hours. While dripping, the oil bath temperature was gradually raised to reach 100 ° C. over 1 hour. Stirring was continued at 100 ° C. for 5 hours after the dropping, and then the reaction solution was cooled to 40 ° C. The reaction yield was 95 mol% (ETCHA / ENBA = 3/7 (molar ratio)). 0.8 g of sodium dodecylbenzenesulfonate was added and stirred at 40 ° C. for 1 hour, 0.8 g of EC3314A was added, and 7 vol% oxygen-containing nitrogen was blown at 10 ml / min and distilled at 1 to 2 kPa and 120 to 160 ° C. Went. The obtained alicyclic (meth) acrylate was 691 g, and the total yield was 90 mol% (ETCHA / ENBA = 3/7 (molar ratio)).
Note that ETCHA is a structure in which, in the above general formulas (2-1) and (2-2), one of R 1 and R 2 is a methyl group, the other is a hydrogen atom, and R 3 is a hydrogen atom. ENBA is any one of R 1 and R 2 in the general formulas (3-1), (3-2), (3-3), and (3-4). One of them is an alicyclic (meth) acrylate having a structure in which one is a methyl group, the other is a hydrogen atom, and R 3 is a hydrogen atom.
実施例２
ガラス製フラスコにビス（トリフルオロメタンスルホニル）アミン１１２ｍｇとアクリル酸７．２ｇを仕込み、７体積％酸素含有窒素を１０ｍｌ／ｍｉｎにて吹き込みながら、ボトムを３０℃のオイルバスに浸け撹拌した。アクリル酸２８８ｇ、５−エチリデン−２−ノルボルネン４８０ｇ、２，５−ジ（ｔ−ブチル）ヒドロキノン０．８ｇの混合液を徐々に滴下した。滴下しながら、オイルバス温度を徐々に上昇させ、ボトム内温が３５〜４５℃の範囲を維持しながら、２時間かけて全量を加えた。滴下後５時間、４０℃で撹拌を続けた。反応収率は９０ｍｏｌ％であった（ＥＴＣＨＡ／ＥＮＢＡ＝７／３（モル比））。ドデシルベンゼンスルホン酸ナトリウム０．８ｇを添加し４０℃で１時間撹拌し、ＥＣ３３１４Ａ０．８ｇを添加し、７体積％酸素含有窒素を１０ｍｌ／ｍｉｎで吹き込みながら１〜２ｋＰａ、１２０〜１６０℃にて蒸留を行った。得られた脂環式（メタ）アクリレートは６５２ｇ、合計収率は８５ｍｏｌ％であった（ＥＴＣＨＡ／ＥＮＢＡ＝７／３（モル比））。
Example 2
A glass flask was charged with 112 mg of bis (trifluoromethanesulfonyl) amine and 7.2 g of acrylic acid, and the bottom was immersed in an oil bath at 30 ° C. and stirred while blowing 7% by volume of oxygen-containing nitrogen at 10 ml / min. A mixed solution of 288 g of acrylic acid, 480 g of 5-ethylidene-2-norbornene and 0.8 g of 2,5-di (t-butyl) hydroquinone was gradually added dropwise. While dripping, the oil bath temperature was gradually raised, and the entire amount was added over 2 hours while maintaining the bottom internal temperature in the range of 35 to 45 ° C. Stirring was continued at 40 ° C. for 5 hours after the dropping. The reaction yield was 90 mol% (ETCHA / ENBA = 7/3 (molar ratio)). 0.8 g of sodium dodecylbenzenesulfonate was added and stirred at 40 ° C. for 1 hour, 0.8 g of EC3314A was added, and 7 vol% oxygen-containing nitrogen was blown at 10 ml / min and distilled at 1 to 2 kPa and 120 to 160 ° C. Went. The obtained alicyclic (meth) acrylate was 652 g, and the total yield was 85 mol% (ETCHA / ENBA = 7/3 (molar ratio)).
実施例３〜７、比較例１〜７
触媒とアクリル酸とを反応器に仕込み、４０℃で撹拌しながら脂環式ジエン化合物を１時間かけて滴下したのち、４０℃に保持したまま所定の時間熟成した。使用した触媒の種類と量、熟成時間（反応時間）、及び、得られた脂環式（メタ）アクリレートの収率を表１に示す。
Examples 3-7, Comparative Examples 1-7
The catalyst and acrylic acid were charged into the reactor, and the alicyclic diene compound was added dropwise over 1 hour while stirring at 40 ° C., and then aged for a predetermined time while maintaining the temperature at 40 ° C. Table 1 shows the type and amount of the catalyst used, the aging time (reaction time), and the yield of the obtained alicyclic (meth) acrylate.
表の収率の欄で、「−」は、カチオン重合による高粘度化により収率の分析が不可能であったことを意味する。
表１に記載の触媒のうち、ＴｆＯＨ、Ｔｆ２ＮＨ、及び、ＴＰＡはそれぞれ以下のものである。
ＴｆＯＨ：トリフルオロメタンスルホン酸
Ｔｆ２ＮＨ：ビス（トリフルオロメタンスルホニル）アミン
ＴＰＡ：タングストリン酸
In the yield column of the table, “-” means that the yield could not be analyzed due to high viscosity by cationic polymerization.
Among the catalysts described in Table 1, TfOH, Tf 2 NH, and TPA are as follows.
TfOH: trifluoromethanesulfonic acid Tf 2 NH: bis (trifluoromethanesulfonyl) amine TPA: tungstophosphoric acid
実施例８
ガラス製フラスコにトリフルオロメタンスルホン酸３ｍｇとメタクリル酸４．３ｇを仕込み、７％酸素含有窒素を２ｍｌ／ｍｉｎにて吹き込みながら、ボトムを８０℃のオイルバスに浸け撹拌した。メタクリル酸４３．０ｇ、５−エチリデン−２−ノルボルネン６０．１ｇ、２，５−ジ（ｔ−アミル）ヒドロキノン０．１ｇの混合液を徐々に滴下し、２時間かけて全量を加えた。滴下しながらオイルバス温度を徐々に上昇させ、２時間かけて１００℃まで到達させた。滴下後２時間、１００℃で撹拌を続けた後、反応液を６０℃まで冷却した。反応収率は９５ｍｏｌ％であった（ＥＴＣＨＭＡ／ＥＮＢＭＡ＝２／８）。りん酸二水素一ナトリウム２４ｍｇを添加し６０℃で１時間撹拌し、ＥＣ３３１４Ａ０．１ｇを添加し、７％酸素含有窒素を２ｍｌ／ｍｉｎで吹き込みながら１〜２ｋＰａ、１２０〜１６０℃にて蒸留を行った。得られた脂環式（メタ）アクリレートは９２．６ｇ、合計収率は９０ｍｏｌ％であった（ＥＴＣＨＭＡ／ＥＮＢＭＡ＝２／８）。
なお、ＥＴＣＨＭＡとは、上記一般式（２−１）、（２−２）において、Ｒ１、Ｒ２のどちらか一方がメチル基で他方が水素原子であり、Ｒ３がメチル基である構造の脂環式（メタ）アクリレートであり、ＥＮＢＭＡとは、上記一般式（３−１）、（３−２）、（３−３）、（３−４）において、Ｒ１、Ｒ２のどちらか一方がメチル基で他方が水素原子であり、Ｒ３がメチル基である構造の脂環式（メタ）アクリレートである。
Example 8
A glass flask was charged with 3 mg of trifluoromethanesulfonic acid and 4.3 g of methacrylic acid, and the bottom was immersed in an oil bath at 80 ° C. and stirred while blowing nitrogen containing 7% at 2 ml / min. A mixed solution of 43.0 g of methacrylic acid, 60.1 g of 5-ethylidene-2-norbornene and 0.1 g of 2,5-di (t-amyl) hydroquinone was gradually added dropwise, and the whole amount was added over 2 hours. While dripping, the oil bath temperature was gradually raised to reach 100 ° C. over 2 hours. Stirring was continued at 100 ° C. for 2 hours after the dropping, and then the reaction solution was cooled to 60 ° C. The reaction yield was 95 mol% (ETCHMA / ENBMA = 2/8). Add 24 mg of monosodium dihydrogen phosphate, stir at 60 ° C. for 1 hour, add 0.1 g of EC3314A, perform distillation at 1-2 kPa, 120-160 ° C. while blowing 7% oxygen-containing nitrogen at 2 ml / min. It was. The obtained alicyclic (meth) acrylate was 92.6 g, and the total yield was 90 mol% (ETCHMA / ENBMA = 2/8).
Note that ETCHMA is a structure in which, in the above general formulas (2-1) and (2-2), one of R 1 and R 2 is a methyl group, the other is a hydrogen atom, and R 3 is a methyl group. ENBMA is any of R 1 and R 2 in the general formulas (3-1), (3-2), (3-3), and (3-4). One of them is a alicyclic (meth) acrylate having a structure in which one is a methyl group, the other is a hydrogen atom, and R 3 is a methyl group.
実施例９
ガラス製フラスコにビス（トリフルオロメタンスルホニル）アミン１４ｍｇとメタクリル酸８．６ｇを仕込み、７％酸素含有窒素を２ｍｌ／ｍｉｎにて吹き込みながら、ボトムを３０℃のオイルバスに浸け撹拌した。アクリル酸４３．０ｇ、５−エチリデン−２−ノルボルネン６０．１ｇ、２，５−ジ（ｔ−アミル）ヒドロキノン０．１ｇの混合液を徐々に滴下した。滴下しながら、オイルバス温度を徐々に上昇させ、ボトム内温が３０〜４０℃の範囲を維持しながら、４時間かけて全量を加えた。滴下後２時間、５０℃で撹拌を続けた。反応収率は８２ｍｏｌ％であった（ＥＴＣＨＭＡ／ＥＮＢＭＡ＝６／４）。りん酸二水素一ナトリウム２４ｍｇを添加し６０℃で２時間撹拌し、ＥＣ３３１４Ａ０．１ｇを添加し、７％酸素含有窒素を２ｍｌ／ｍｉｎで吹き込みながら１〜２ｋＰａ、１２０〜１６０℃にて蒸留を行った。得られた脂環式（メタ）アクリレートは７９．１ｇ、合計収率は７７ｍｏｌ％であった（ＥＴＣＨＭＡ／ＥＮＢＭＡ＝６／４）。
Example 9
A glass flask was charged with 14 mg of bis (trifluoromethanesulfonyl) amine and 8.6 g of methacrylic acid, and the bottom was immersed in an oil bath at 30 ° C. and stirred while blowing 7% oxygen-containing nitrogen at 2 ml / min. A mixed solution of 43.0 g of acrylic acid, 60.1 g of 5-ethylidene-2-norbornene, and 0.1 g of 2,5-di (t-amyl) hydroquinone was gradually added dropwise. While dripping, the oil bath temperature was gradually raised, and the whole amount was added over 4 hours while maintaining the bottom internal temperature in the range of 30 to 40 ° C. Stirring was continued at 50 ° C. for 2 hours after the dropping. The reaction yield was 82 mol% (ETCHMA / ENBMA = 6/4). Add 24 mg of monosodium dihydrogen phosphate and stir at 60 ° C. for 2 hours, add 0.1 g of EC3314A, perform distillation at 1 to 2 kPa and 120 to 160 ° C. while blowing 7% oxygen-containing nitrogen at 2 ml / min. It was. The obtained alicyclic (meth) acrylate was 79.1 g, and the total yield was 77 mol% (ETCHMA / ENBMA = 6/4).
実施例１０〜１１、比較例８〜９
触媒とメタクリル酸とを反応器に仕込み、４０℃で撹拌しながら脂環式ジエン化合物を１時間かけて滴下したのち、４０℃に保持したまま所定の時間熟成した。使用した触媒の種類と量、熟成時間（反応時間）、及び、得られた脂環式（メタ）アクリレートの収率を表２に示す。
Examples 10-11, Comparative Examples 8-9
The catalyst and methacrylic acid were charged into the reactor, and the alicyclic diene compound was added dropwise over 1 hour while stirring at 40 ° C., followed by aging for a predetermined time while maintaining the temperature at 40 ° C. Table 2 shows the type and amount of the catalyst used, the aging time (reaction time), and the yield of the obtained alicyclic (meth) acrylate.
２．脂環式（メタ）アクリレート樹脂の物性評価
実施例１２〜１４、比較例１０
上記実施例で合成した脂環式アクリレートを用いて、ＥＴＣＨＡとＥＮＢＡの含有率（ｍｏｌ％）の異なる３種類の樹脂用材料１〜３を調製した。各樹脂用材料の異性体組成を表３に示す。これら樹脂用材料１〜３と、比較用に脂環式アクリレートの代表的化合物であるイソボルニルアクリレート（ＩＢＯＡ）とから以下の方法で樹脂を製造し、得られた樹脂の各種物性評価を行った。評価結果を表４に示す。なお、樹脂用材料１〜３から得られた樹脂をそれぞれ樹脂１〜３とし、ＩＢＯＡから得られた樹脂を樹脂４とした。
評価方法：試料１００部に光重合開始剤３部（イルガキュア１８４：ＢＡＳＦ社製）と熱重合開始剤３部（カヤカルボＢｉｃ−７５：化薬アクゾ社製）を添加し、平均膜厚３０μｍの塗膜を作成し、ＵＶ照射（６６Ｊ／ｃｍ２）、ポストキュア（２００℃、２時間）を行ったのち、硬化膜について各種物性を実施した。
2. Evaluation of physical properties of alicyclic (meth) acrylate resin Examples 12 to 14 and Comparative Example 10
Using the alicyclic acrylate synthesized in the above examples, three types of resin materials 1 to 3 having different contents (mol%) of ETCHA and ENBA were prepared. Table 3 shows the isomer composition of each resin material. A resin is produced from these resin materials 1 to 3 and isobornyl acrylate (IBOA), which is a representative compound of alicyclic acrylate, for comparison, and the physical properties of the obtained resin are evaluated. It was. The evaluation results are shown in Table 4. The resins obtained from the resin materials 1 to 3 were designated as resins 1 to 3, respectively, and the resin obtained from IBOA was designated as resin 4.
Evaluation method: 3 parts of a photopolymerization initiator (Irgacure 184: manufactured by BASF) and 3 parts of a thermal polymerization initiator (Kayacarbo Bic-75: manufactured by Kayaku Akzo) are added to 100 parts of a sample, and an average film thickness of 30 μm is applied. A film was prepared, and after UV irradiation (66 J / cm 2 ) and post-cure (200 ° C., 2 hours), various physical properties of the cured film were implemented.
表４に示す各種物性の評価は以下の基準により行った。
ＵＶ硬化性：タックレスまでの照射時間 ○：１０秒以内、△：３０秒以内、×：３０秒超
硬度：鉛筆硬度試験 ○：Ｈ以上、△：ＨＢ〜Ｂ、×：２Ｂ以下
耐熱分解性：５％重量減少温度 ○：３００℃以上、△：２８０℃以上、×：２８０℃未満
耐熱性：Ｔｇ（ＤＳＣ） ○：８０℃以上、△：６０℃以上、×：６０℃未満
耐溶剤性：アセトン拭き取り ○：影響なし、△：白濁する、×：溶ける
可とう性：フィルム剥ぎ取り ○：やや脆い、△：脆い、×：非常に脆い
Various physical properties shown in Table 4 were evaluated according to the following criteria.
UV curing property: Irradiation time until tackless ○: within 10 seconds, Δ: within 30 seconds, ×: over 30 seconds Hardness: pencil hardness test ○: H or higher, Δ: HB to B, X: 2B or lower Thermal decomposition resistance: 5% weight loss temperature ○: 300 ° C. or higher, Δ: 280 ° C. or higher, ×: less than 280 ° C. Heat resistance: Tg (DSC) ○: 80 ° C. or higher, Δ: 60 ° C. or higher, x: less than 60 ° C. Solvent resistance: Acetone wiping ○: No effect, Δ: Cloudy, ×: Melting flexibility: Film peeling ○: Slightly brittle, Δ: Brittle, ×: Very brittle
実施例１〜１１、比較例１〜９の結果から、本発明の脂環式（メタ）アクリレートの製造方法により製造することで、少量の触媒量で、水洗工程や乾燥工程を行うことなく高い収率で脂環式（メタ）アクリレートが得られることが確認された。中でも、有機化合物からなる超酸を触媒として少量用いた場合に特に高い収率で脂環式（メタ）アクリレートが得られることが確認された。
また、実施例１、２、８、９の結果から、使用する触媒や反応温度を変化させることで、生成する脂環式（メタ）アクリレートの異性体組成を変化させることが可能であることが確認された。
更に実施例１２〜１４、比較例１０の結果から、イソボルニルアクリレート（ＩＢＯＡ）と比較して、本発明の脂環式アクリレートが優れた性能を有することが明らかになった。また、ＥＴＣＨＡを主成分とする樹脂用材料１から得られた樹脂では耐熱分解性と可とう性に優れた硬化物が得られ、ＥＮＢＡを主成分とする樹脂用材料３から得られた樹脂では硬度、耐熱性、耐溶剤性に優れた硬化物が得られた。すなわち、ＥＴＣＨＡとＥＮＢＡとは異なる特徴を有する重合性脂環式アクリレートであり、どちらかの成分に偏った組成の脂環式アクリレートを得る価値は大きいことが確認された。
From the results of Examples 1 to 11 and Comparative Examples 1 to 9, by the production method of the alicyclic (meth) acrylate of the present invention, it is high without performing a water washing step and a drying step with a small amount of catalyst. It was confirmed that alicyclic (meth) acrylate was obtained in a yield. In particular, it was confirmed that alicyclic (meth) acrylates can be obtained in a particularly high yield when a small amount of a superacid composed of an organic compound is used as a catalyst.
In addition, from the results of Examples 1, 2, 8, and 9, it is possible to change the isomer composition of the alicyclic (meth) acrylate to be produced by changing the catalyst used and the reaction temperature. confirmed.
Furthermore, from the results of Examples 12 to 14 and Comparative Example 10, it was revealed that the alicyclic acrylate of the present invention has superior performance as compared with isobornyl acrylate (IBOA). In addition, the resin obtained from the resin material 1 containing ETCHA as a main component provides a cured product having excellent thermal decomposition resistance and flexibility, and the resin obtained from the resin material 3 containing ENBA as a main component is used. A cured product having excellent hardness, heat resistance, and solvent resistance was obtained. That is, it was confirmed that ETCHA and ENBA are polymerizable alicyclic acrylates having different characteristics, and it is highly valuable to obtain an alicyclic acrylate having a composition biased toward either component.
Claims (5)
該反応工程は、脂環式ジエン化合物に対して１モル％未満のブレンステッド酸触媒の存在下で脂環式ジエン化合物と（メタ）アクリル酸とを反応させる工程であり、
該脂環式（メタ）アクリレートは、下記一般式（２）で表される構造の脂環式（メタ）アクリレート及び下記一般式（３）で表される構造の脂環式（メタ）アクリレートを含むことを特徴とする脂環式（メタ）アクリレートの製造方法。
The reaction step is a step of reacting the alicyclic diene compound and (meth) acrylic acid in the presence of less than 1 mol% Bronsted acid catalyst with respect to the alicyclic diene compound,
The alicyclic (meth) acrylate includes an alicyclic (meth) acrylate having a structure represented by the following general formula (2) and an alicyclic (meth) acrylate having a structure represented by the following general formula (3). The manufacturing method of the alicyclic (meth) acrylate characterized by including.
該脂環式（メタ）アクリレートは、下記一般式（２）で表される構造の脂環式（メタ）アクリレートと下記一般式（３）で表される構造の脂環式（メタ）アクリレートとを８／２〜２／８のモル比で含むことを特徴とする脂環式（メタ）アクリレート。
The alicyclic (meth) acrylate includes an alicyclic (meth) acrylate having a structure represented by the following general formula (2), an alicyclic (meth) acrylate having a structure represented by the following general formula (3), and In a molar ratio of 8/2 to 2/8.
該脂環式（メタ）アクリレートは、下記一般式（２）で表される構造の脂環式（メタ）アクリレート及び／又は下記一般式（３）で表される構造の脂環式（メタ）アクリレートを含むことを特徴とする脂環式（メタ）アクリレート重合体。
The alicyclic (meth) acrylate is an alicyclic (meth) acrylate having a structure represented by the following general formula (2) and / or an alicyclic (meth) having a structure represented by the following general formula (3). An alicyclic (meth) acrylate polymer comprising an acrylate.
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| US4435316A (en) * | 1982-07-08 | 1984-03-06 | International Flavors & Fragrances Inc. | Norbornyl esters and uses thereof in augmenting or enhancing the organoleptic properties of a consumable material and process for preparing same |
| JPS63120708A (en) * | 1986-11-11 | 1988-05-25 | Nippon Petrochem Co Ltd | Novel ethylene copolymer |
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| WO2009063716A1 (en) * | 2007-11-13 | 2009-05-22 | Konica Minolta Opto, Inc. | Plastic optical device material and plastic optical device |
| JP2012072334A (en) * | 2010-09-30 | 2012-04-12 | Sanyo Chem Ind Ltd | Composition for inkjet printing ink |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4435316A (en) * | 1982-07-08 | 1984-03-06 | International Flavors & Fragrances Inc. | Norbornyl esters and uses thereof in augmenting or enhancing the organoleptic properties of a consumable material and process for preparing same |
| JPS63120708A (en) * | 1986-11-11 | 1988-05-25 | Nippon Petrochem Co Ltd | Novel ethylene copolymer |
| JPH07188397A (en) * | 1993-12-27 | 1995-07-25 | San Petrochem:Kk | Production of crosslinked resin, polymeric compound for crosslinking and polymer composition for crosslinking |
| WO2009063716A1 (en) * | 2007-11-13 | 2009-05-22 | Konica Minolta Opto, Inc. | Plastic optical device material and plastic optical device |
| JP2012072334A (en) * | 2010-09-30 | 2012-04-12 | Sanyo Chem Ind Ltd | Composition for inkjet printing ink |
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