JP2006315960A - Tricyclodecanediol di(meth)acrylate and method for producing the same - Google Patents
Tricyclodecanediol di(meth)acrylate and method for producing the same Download PDFInfo
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- JP2006315960A JP2006315960A JP2005137252A JP2005137252A JP2006315960A JP 2006315960 A JP2006315960 A JP 2006315960A JP 2005137252 A JP2005137252 A JP 2005137252A JP 2005137252 A JP2005137252 A JP 2005137252A JP 2006315960 A JP2006315960 A JP 2006315960A
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- acrylic acid
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 19
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 18
- 229910001868 water Inorganic materials 0.000 abstract description 18
- 239000003513 alkali Substances 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 description 33
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000005886 esterification reaction Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 238000006386 neutralization reaction Methods 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 11
- 238000005809 transesterification reaction Methods 0.000 description 11
- 230000018044 dehydration Effects 0.000 description 10
- 238000006297 dehydration reaction Methods 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- -1 acrylic ester Chemical class 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 230000032050 esterification Effects 0.000 description 8
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 7
- 239000003112 inhibitor Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- 125000004386 diacrylate group Chemical group 0.000 description 4
- 229910001882 dioxygen Inorganic materials 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- 238000010894 electron beam technology Methods 0.000 description 3
- 239000012776 electronic material Substances 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000013307 optical fiber Substances 0.000 description 3
- 230000005693 optoelectronics Effects 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- ZFFBIQMNKOJDJE-UHFFFAOYSA-N 2-bromo-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(Br)C(=O)C1=CC=CC=C1 ZFFBIQMNKOJDJE-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 235000002597 Solanum melongena Nutrition 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000006103 coloring component Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 150000002009 diols Chemical class 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
- 150000002148 esters Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 239000012567 medical material Substances 0.000 description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical class C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- OPLCSTZDXXUYDU-UHFFFAOYSA-N 2,4-dimethyl-6-tert-butylphenol Chemical compound CC1=CC(C)=C(O)C(C(C)(C)C)=C1 OPLCSTZDXXUYDU-UHFFFAOYSA-N 0.000 description 1
- QYXHDJJYVDLECA-UHFFFAOYSA-N 2,5-diphenylcyclohexa-2,5-diene-1,4-dione Chemical compound O=C1C=C(C=2C=CC=CC=2)C(=O)C=C1C1=CC=CC=C1 QYXHDJJYVDLECA-UHFFFAOYSA-N 0.000 description 1
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical class OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
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- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003847 radiation curing Methods 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229940032330 sulfuric acid Drugs 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
本発明は、熱、紫外線照射、電子線照射等により容易に重合しうる新規なトリシクロデカンジオールジ（メタ）アクリレート及びその製造方法に関する。 The present invention relates to a novel tricyclodecanediol di (meth) acrylate that can be easily polymerized by heat, ultraviolet irradiation, electron beam irradiation, and the like, and a method for producing the same.
紫外線硬化型または電子線硬化型樹脂には、硬化性成分として種々の（メタ）アクリル酸エステルが使用されている。これらの光硬化性樹脂組成物を利用した用途として、従来からプラスチック、紙、木、無機質素材等における塗料、インキ、接着剤として用いられている。最近では、半導体、液晶に代表される電子材料分野や光ファイバー、光学レンズ等に代表されるオプトエレクトロニクス分野、さらには医療分野等に拡大してきている。 Various (meth) acrylic acid esters are used as the curable component in the ultraviolet curable resin or the electron beam curable resin. Conventionally, these photocurable resin compositions have been used as paints, inks and adhesives in plastics, paper, wood, inorganic materials, and the like. Recently, the field has expanded to the field of electronic materials typified by semiconductors and liquid crystals, the field of optoelectronics typified by optical fibers and optical lenses, and the field of medicine.
そのような中で、特にジシクロペンタジエン誘導体のような脂環式骨格を有する（メタ）アクリル酸エステルは、優れた硬化性、耐水性、可とう性、耐アルカリ性を有することで知られている。さらに、優れた硬化性を示すジシクロペンタジエンのジ（メタ）アクリル酸誘導体としては、現在までのところトリシクロデカンジメチロールジ（メタ）アクリレートのみが知られている（特許文献１及び特許文献２参照）。しかし，トリシクロデカンジメチロールジ（メタ）アクリレートでは、必ずしも十分な硬化性、耐水性等を得られるとは言えない。
Among these, (meth) acrylic acid esters having an alicyclic skeleton such as dicyclopentadiene derivatives are known for having excellent curability, water resistance, flexibility and alkali resistance. . Furthermore, as a di (meth) acrylic acid derivative of dicyclopentadiene exhibiting excellent curability, only tricyclodecane dimethylol di (meth) acrylate is known so far (
本発明は、上記の問題を解決し得る新規なトリシクロデカンジオールジ（メタ）アクリレートとその製造方法を提供するものである。 The present invention provides a novel tricyclodecanediol di (meth) acrylate that can solve the above problems and a method for producing the same.
本発明は、［１］ 一般式（Ｉ）で表されるトリシクロデカンジオールジ（メタ）アクリレートに関する。 The present invention relates to [1] tricyclodecanediol di (meth) acrylate represented by the general formula (I).
また、本発明は、［２］ 下式（ＩＩ）で表されるトリシクロデカンジオールと一般式（ＩＩＩ）で表される（メタ）アクリル酸又は（メタ）アクリル酸エステルとを触媒存在下で反応させることを特徴とする上記［１］に記載の一般式（Ｉ）のトリシクロデカンジオールジ（メタ）アクリレートの製造方法に関する。
The present invention also provides [2] tricyclodecanediol represented by the following formula (II) and (meth) acrylic acid or (meth) acrylic ester represented by the general formula (III) in the presence of a catalyst. The present invention relates to a method for producing a tricyclodecanediol di (meth) acrylate of the general formula (I) according to the above [1], characterized by reacting.
また、本発明は、［３］ 式（ＩＩ）で表されるトリシクロデカンジオールと（メタ）アクリル酸とを触媒存在下で反応させることを特徴とする上記［２］に記載のトリシクロデカンジオールジ（メタ）アクリレートの製造方法に関する。
本発明では、トリシクロデカンジオールを原料として用い、エステル交換法、脱水エステル化法のいずれかの方法により一般式（Ｉ）で表されるトリシクロデカンジオールジ（メタ）アクリレートを製造することができる。
エステル交換法及び脱水エステル化法では、重合禁止剤及び触媒存在下、式（ＩＩ）で表されるアルコールと一般式（ＩＩＩ）で表される（メタ）アクリル酸エステル又は（メタ）アクリル酸とを反応させる。
[3] The tricyclodecane according to [2], wherein the tricyclodecanediol represented by the formula (II) and (meth) acrylic acid are reacted in the presence of a catalyst. The present invention relates to a method for producing diol di (meth) acrylate.
In the present invention, tricyclodecanediol di (meth) acrylate represented by the general formula (I) can be produced by using either a transesterification method or a dehydration esterification method using tricyclodecanediol as a raw material. it can.
In the transesterification method and dehydration esterification method, in the presence of a polymerization inhibitor and a catalyst, an alcohol represented by the formula (II) and a (meth) acrylic acid ester or (meth) acrylic acid represented by the general formula (III) React.
本発明のトリシクロデカンジオールジ（メタ）アクリレートは、優れた硬化性、耐水性、可とう性、耐アルカリ性を有し、トリシクロデカンジオールと（メタ）アクリル酸又は（メタ）アクリル酸エステルとを触媒存在下で反応させて製造することができる。本発明のトリシクロデカンジオールジ（メタ）アクリレートは、塗料・コーティング材料及び土木建築材料だけでなく、半導体・液晶に用いられる電子材料、また、光ファイバー、光学レンズ等に代表されるオプトエレクトロニクス材料、さらには医療材料として使用することができる。 The tricyclodecanediol di (meth) acrylate of the present invention has excellent curability, water resistance, flexibility and alkali resistance, and tricyclodecanediol and (meth) acrylic acid or (meth) acrylic acid ester Can be produced in the presence of a catalyst. The tricyclodecanediol di (meth) acrylate of the present invention is not only a paint / coating material and civil engineering / building material, but also an electronic material used for semiconductors / liquid crystals, an optoelectronic material represented by an optical fiber, an optical lens, etc. Furthermore, it can be used as a medical material.
本発明のトリシクロデカンジオールジ（メタ）アクリレート及びその製造方法の実施の形態について詳細に説明する。 Embodiments of the tricyclodecanediol di (meth) acrylate and the production method thereof of the present invention will be described in detail.
本発明のトリシクロデカンジオールジ（メタ）アクリレートは、エステル交換法により式（ＩＩ）で表されるトリシクロデカンジオールと一般式（ＩＩＩ）で表される（メタ）アクリル酸エステルをエステル化反応させて製造することができる。反応に際しては、一般式（ＩＩＩ）で表される（メタ）アクリル酸エステルを、式（ＩＩ）で表されるトリシクロデカンジオールに対して過剰に使用することが、反応を短時間に終わらせるため及び反応転化率を向上させるために好ましい。また、一般式（ＩＩＩ）で表される（メタ）アクリル酸エステルとして、アクリル酸及びメタクリル酸のメチル、エチル、プロピル、ブチルエステル等が用いられる。このうち、メタクリル酸エステルの場合は、メチルエステルが好ましく、アクリル酸エステルの場合は、メチル、エチル、ブチルエステルの中から適宜選ばれる。 The tricyclodecanediol di (meth) acrylate of the present invention is an esterification reaction of tricyclodecanediol represented by the formula (II) and (meth) acrylic acid ester represented by the general formula (III) by a transesterification method. Can be manufactured. In the reaction, the (meth) acrylic acid ester represented by the general formula (III) is used excessively with respect to the tricyclodecanediol represented by the formula (II) to complete the reaction in a short time. Therefore, it is preferable for improving the reaction conversion rate. In addition, as the (meth) acrylic acid ester represented by the general formula (III), methyl, ethyl, propyl, butyl ester or the like of acrylic acid and methacrylic acid is used. Among these, in the case of methacrylic acid ester, methyl ester is preferable, and in the case of acrylic acid ester, it is appropriately selected from methyl, ethyl and butyl esters.
エステル交換法においては、トリシクロデカンジオール１モルに対して、（メタ）アクリル酸エステルを３〜１５モルの範囲で使用することでき、好ましくは３〜１２モル、より好ましくは４〜８モルの範囲で使用することができる。トリシクロデカンジオール１モルに対して、（メタ）アクリル酸エステルの使用量が３モル未満であると反応が遅くなり、未反応のトリシクロデカンジオールが残りやすい傾向がある。一方、（メタ）アクリル酸エステルの使用量が１５モルを超えると生産性が悪くなり、反応終了後に過剰の（メタ）アクリル酸エステルを回収する工程に長時間を要する傾向がある。 In the transesterification method, (meth) acrylic acid ester can be used in the range of 3 to 15 mol, preferably 3 to 12 mol, more preferably 4 to 8 mol, per 1 mol of tricyclodecanediol. Can be used in a range. When the amount of (meth) acrylic acid ester used is less than 3 moles relative to 1 mole of tricyclodecanediol, the reaction becomes slow and unreacted tricyclodecanediol tends to remain. On the other hand, when the amount of the (meth) acrylic acid ester used exceeds 15 mol, the productivity tends to be poor, and it takes a long time to recover the excess (meth) acrylic acid ester after the reaction.
このエステル交換反応に使用される触媒としては、水酸化リチウム、水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物、炭酸リチウム、炭酸ナトリウム、炭酸カリウム等のアルカリ金属炭酸化物、リチウムメトキシド、ナトリウムメトキシド、ナトリウムエトキシド、カリウム−ｔ−ブトキシド等のアルカリ金属アルコキシド、リチウムアミド、ナトリウムアミド、カリウムアミド等のアルカリ金属アミド、及びオルトチタン酸テトラメチル、オルトチタン酸テトラエチル、オルトチタン酸テトラプロピル、オルトチタン酸テトライソプロピル、オルトチタン酸テトラブチル等のオルトチタン酸アルキルがあげられる。これらの中でも、触媒の取り扱いの容易さからアルカリ金属アミドまたはチタン酸アルキル（炭素原子数１〜４のアルキル）が好ましい。 Catalysts used in this transesterification include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, alkali metal carbonates such as lithium carbonate, sodium carbonate and potassium carbonate, lithium methoxide, Alkali metal alkoxides such as sodium methoxide, sodium ethoxide, potassium tert-butoxide, alkali metal amides such as lithium amide, sodium amide, potassium amide, and tetramethyl orthotitanate, tetraethyl orthotitanate, tetrapropyl orthotitanate And alkyl orthotitanate such as tetraisopropyl orthotitanate and tetrabutyl orthotitanate. Among these, alkali metal amide or alkyl titanate (alkyl having 1 to 4 carbon atoms) is preferable because of easy handling of the catalyst.
また、本発明のトリシクロデカンジオールジ（メタ）アクリレートは、脱水エステル化法により式（ＩＩ）で表されるトリシクロデカンジオールと一般式（ＩＩＩ）で表される（メタ）アクリル酸をエステル化反応させて製造することができる。
このとき、トリシクロデカンジオール１モルに対して（メタ）アクリル酸を１〜３モルの範囲内で使用することが好ましく、１．２〜２モルの範囲内がより好ましい。アクリル酸が１モル未満であると反応が遅くなり、未反応のトリシクロデカンジオールが残る傾向にある。一方、（メタ）アクリル酸が３モルを超えると、生産性が悪くなる傾向にある。
Further, the tricyclodecanediol di (meth) acrylate of the present invention is obtained by esterifying tricyclodecanediol represented by the formula (II) and (meth) acrylic acid represented by the general formula (III) by a dehydration esterification method. It can be produced by a reaction.
At this time, it is preferable to use (meth) acrylic acid within a range of 1 to 3 mol, and more preferably within a range of 1.2 to 2 mol, relative to 1 mol of tricyclodecanediol. If the acrylic acid is less than 1 mole, the reaction is slow and unreacted tricyclodecanediol tends to remain. On the other hand, when (meth) acrylic acid exceeds 3 mol, the productivity tends to deteriorate.
脱水エステル化反応に使用される触媒としては、硫酸、ベンゼンスルホン酸、メタンスルホン酸、パラトルエンスルホン酸、イオン交換樹脂などの酸性触媒が使用できるが、合成時に副生成物がほとんど生じない点でパラトルエンスルホン酸が好ましい。 As the catalyst used in the dehydration esterification reaction, an acidic catalyst such as sulfuric acid, benzenesulfonic acid, methanesulfonic acid, paratoluenesulfonic acid, ion exchange resin, etc. can be used, but by-products are hardly generated during synthesis. Paratoluenesulfonic acid is preferred.
本発明における触媒の使用量は、（メタ）アクリル酸エステルまたは（メタ）アクリル酸とトリシクロデカンジオール（トリシクロデカノール）の合計量に対して０．０１〜１０重量％の範囲であることが好ましく、０．１〜５．０重量％の範囲であることがより好ましい。触媒の使用量が（メタ）アクリル酸エステルまたは（メタ）アクリル酸とトリシクロデカンジオール（トリシクロデカノール）の合計量に対して０．０１重量％未満であると反応の進行が遅くなる傾向があり、５．０重量％を超えても特に効果がない傾向がある。エステル交換反応において、特にオルトチタン酸テトラアルキル類を触媒として使用する場合には、反応系中の水分が多いと触媒活性が失われやすいので、予め触媒を加える前に反応混合物を加熱還流して系内の水分を少なくしておくか、反応中に水分混入を防ぐことが好ましい。 The amount of the catalyst used in the present invention is in the range of 0.01 to 10% by weight with respect to the total amount of (meth) acrylic acid ester or (meth) acrylic acid and tricyclodecanediol (tricyclodecanol). Is preferable, and the range of 0.1 to 5.0% by weight is more preferable. When the amount of the catalyst used is less than 0.01% by weight based on the total amount of (meth) acrylic acid ester or (meth) acrylic acid and tricyclodecanediol (tricyclodecanol), the progress of the reaction tends to be slow Even if it exceeds 5.0% by weight, there is a tendency not to be particularly effective. In the transesterification reaction, especially when tetraalkyl orthotitanate is used as a catalyst, the catalytic activity tends to be lost if there is a lot of water in the reaction system, so the reaction mixture is heated to reflux before adding the catalyst beforehand. It is preferable to reduce the moisture in the system or prevent moisture from entering during the reaction.
本発明の脱水エステル化反応では、有機溶剤としてベンゼン、トルエン、キシレンを単独または二種以上を組み合わせて用いることができ、取り扱いの点からトルエン単独が好ましい。また、エステル交換反応においても、不活性溶媒を適宜使用することができる。例えば、ベンゼン、トルエン、キシレン、ヘキサン、ヘプタン、オクタン、イソオクタン、シクロヘキサン等の炭化水素類やジオキサン等のエーテル類などが挙げられる。 In the dehydration esterification reaction of the present invention, benzene, toluene and xylene can be used alone or in combination of two or more as the organic solvent, and toluene alone is preferred from the viewpoint of handling. Also in the transesterification reaction, an inert solvent can be appropriately used. Examples thereof include hydrocarbons such as benzene, toluene, xylene, hexane, heptane, octane, isooctane and cyclohexane, and ethers such as dioxane.
本発明の反応系においては、重合禁止剤を添加することが望ましい。重合禁止剤としては、ヒドロキノン、ヒドロキノンモノメチルエーテル、ｔ−ブチルカテコール、ｔ−ブチルヒドロキンン、２，４−ジメチル−６−ｔ−ブチルフェノール、２，６−ｔ−ブチル−ｐ−クレゾール、パラベンゾキノン、２，５−ジフェニルパラベンゾキノン、フェノチアジン、ジフェニルアミン等が使用される。製品の貯蔵時及び使用時に着色の少ない重合禁止剤として、ヒドロキノンモノメチルエーテルが好ましい。 In the reaction system of the present invention, it is desirable to add a polymerization inhibitor. As the polymerization inhibitor, hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, t-butylhydroquinone, 2,4-dimethyl-6-t-butylphenol, 2,6-t-butyl-p-cresol, parabenzoquinone, 2,5-diphenylparabenzoquinone, phenothiazine, diphenylamine and the like are used. Hydroquinone monomethyl ether is preferred as a polymerization inhibitor that is less colored during storage and use of the product.
本発明における重合禁止剤の使用量は、トリシクロデカンジオールに対して５〜２０００ｐｐｍが好ましく、１０〜５００ｐｐｍがより好ましい。重合禁止剤の使用量がトリシクロデカンジオールに対して５ｐｐｍ未満であると重合禁止の添加効果が十分でない傾向があり、また、２０００ｐｐｍを超えると製品（トリシクロデカンジオールジ（メタ）アクリレート）をポリマ化する際に、ポリマ化を阻害する傾向がある。 The amount of the polymerization inhibitor used in the present invention is preferably 5 to 2000 ppm, more preferably 10 to 500 ppm, based on tricyclodecanediol. If the amount of the polymerization inhibitor used is less than 5 ppm relative to tricyclodecanediol, the addition effect of polymerization inhibition tends to be insufficient, and if it exceeds 2000 ppm, the product (tricyclodecanediol di (meth) acrylate) When polymerizing, there is a tendency to inhibit polymerization.
本発明においては、反応液の重合防止のために、分子状酸素を吹き込んで反応させることが望ましい。分子状酸素としては、希釈された状態で使用することが好ましく、好適なものとして空気が用いられる。また、分子状酸素の吹き込みは、原料の（メタ）アクリル酸エステルまたは（メタ）アクリル酸が蒸発して蒸気として存在したり、上部の釜壁等に凝縮した（メタ）アクリル酸エステルまたは（メタ）アクリル酸の重合を防止するためにも好ましい。分子状酸素の使用量としては、反応器の形状や攪拌動力によっても影響を受けるが、トリシクロデカンジオール１モルに対して５〜５００ｍｌ／分（空気の場合、２５〜２５００ｍｌ／分）の速度で吹き込むことが好ましい。 In the present invention, in order to prevent polymerization of the reaction solution, it is desirable to react by blowing molecular oxygen. The molecular oxygen is preferably used in a diluted state, and air is preferably used. In addition, the blowing of molecular oxygen is caused by the vaporization of (meth) acrylic acid ester or (meth) acrylic acid as a raw material or the presence of vapor or condensation of (meth) acrylic acid ester or (metha ) Also preferred for preventing polymerization of acrylic acid. The amount of molecular oxygen used is affected by the shape of the reactor and the stirring power, but the rate is 5 to 500 ml / min (25 to 2500 ml / min in the case of air) with respect to 1 mol of tricyclodecanediol. It is preferable to blow in.
反応は、常圧又は減圧下６０〜１３０℃で行うことが好ましい。反応の形態としては、トリシクロデカンジオールと（メタ）アクリル酸を反応させる脱水エステル化、もしくはトリシクロデカンジオールと（メタ）アクリル酸エステルを反応させるエステル交換法等の当業者間で一般的に知られている方法を採用できる。脱水エステル化法では、原料アルコールの転化率を高めるために副生する水を共沸溶媒と共に除去する必要がある。この点で、油水分離装置を用いることが好ましい。また、エステル交換法では、原料アルコールの転化率を高めるため、副生する低級アルコールを系外に留去する必要がある。この点で、精留塔の付いた回分式反応槽を使用することが好ましい。 The reaction is preferably performed at 60 to 130 ° C. under normal pressure or reduced pressure. As a form of reaction, it is common among those skilled in the art such as dehydration esterification in which tricyclodecanediol and (meth) acrylic acid are reacted, or transesterification method in which tricyclodecanediol and (meth) acrylic acid ester are reacted. Known methods can be employed. In the dehydration esterification method, it is necessary to remove by-product water together with the azeotropic solvent in order to increase the conversion rate of the raw alcohol. In this respect, it is preferable to use an oil-water separator. Moreover, in the transesterification method, in order to increase the conversion rate of raw material alcohol, it is necessary to distill off the by-produced lower alcohol out of the system. In this respect, it is preferable to use a batch reactor equipped with a rectification column.
エステル交換法において、得られる製品の色相改善等のために反応終了後の反応液をアルカリ処理することもできる。アルカリ処理に使用するアルカリとしては、水酸化リチウム、水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物、炭酸リチウム、炭酸ナトリウム、炭酸カリウム等のアルカリ金属炭酸塩等の塩基性化合物を固形のまま使用する方法と、水溶液として使用する方法とがある。また、ナトリウムメトキシド、ナトリウムエトキシド、カリウムｔ−ブトキシド等のアルカリ金属アルコキシドを固形又はアルコール溶液として使用することもできる。さらには、リチウムアミド、ナトリウムアミド、カリウムアミド等のアルカリ金属アミドを使用することもできる。また、酸化マグネシウム、シリカマグネシア、塩基性イオン交換樹脂等の固形アルカリも使用することができる。 In the transesterification method, the reaction solution after completion of the reaction can be subjected to alkali treatment in order to improve the hue of the product obtained. As the alkali used for the alkali treatment, basic compounds such as alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, and alkali metal carbonates such as lithium carbonate, sodium carbonate and potassium carbonate are solid. There are a method of using it as it is and a method of using it as an aqueous solution. Alkali metal alkoxides such as sodium methoxide, sodium ethoxide, potassium t-butoxide and the like can also be used as a solid or alcohol solution. Furthermore, alkali metal amides such as lithium amide, sodium amide, and potassium amide can also be used. Moreover, solid alkalis, such as magnesium oxide, a silica magnesia, a basic ion exchange resin, can also be used.
本発明の脱水エステル化法では、反応終了後の反応液から未反応のアクリル酸、触媒、不純物、着色成分等を除去するために中和洗浄される。中和洗浄は公知の方法を採用することができるが、本発明の化合物は特に中和時のエステル分解（ケン化）が起こりやすい。そこで、アルカリ水溶液で中和を行う前に、水又は中性塩水溶液で洗浄を行うことが好ましい。 In the dehydration esterification method of the present invention, neutralization washing is performed to remove unreacted acrylic acid, catalyst, impurities, coloring components and the like from the reaction solution after completion of the reaction. Although neutralization washing can employ a known method, the compound of the present invention is particularly susceptible to ester decomposition (saponification) during neutralization. Therefore, it is preferable to perform washing with water or a neutral salt aqueous solution before neutralization with the alkaline aqueous solution.
脱水エステル化法において、中和の前に行う水洗には、食塩、硫安等の水溶液又は水が用いられ、この中で食塩水がより好ましい。中和の前に行う水洗に用いられる水溶液又は水の量は反応が終了した反応液に対して２〜３０重量％で行うことが好ましく、５〜１５重量％がより好ましい。さらに、この洗浄用の水溶液の濃度は０〜３０重量％で行うことが好ましく、１５〜２０重量％がより好ましい。 In the dehydration esterification method, an aqueous solution such as sodium chloride or ammonium sulfate or water is used for washing with water before neutralization, and among these, saline is more preferable. The amount of the aqueous solution or water used for the water washing performed before the neutralization is preferably 2 to 30% by weight, more preferably 5 to 15% by weight with respect to the reaction solution after the reaction. Furthermore, the concentration of the aqueous solution for washing is preferably 0 to 30% by weight, and more preferably 15 to 20% by weight.
脱水エステル化法における中和には例えば、水酸化カリウム、水酸化ナトリウム、炭酸カリウム、炭酸ナトリウム等のアルカリ性の水溶液が用いられる。中和に用いられるアルカリ性物質はエステル化反応が終了した反応液の中和当量の１．０１〜１．５倍として中和を行うことが好ましい。アルカリ性物質が、１．０１倍未満であると中和が不十分である傾向があり、１．５倍を超えると廃水が増え、エステル分解（ケン化）が起こる傾向がある。ここで用いるアルカリ水溶液の濃度は１重量％以上で行うことが好ましく、５〜１５重量％がより好ましい。 For neutralization in the dehydration esterification method, for example, an alkaline aqueous solution such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate or the like is used. The alkaline substance used for neutralization is preferably neutralized by 1.01 to 1.5 times the neutralization equivalent of the reaction liquid in which the esterification reaction has been completed. If the alkaline substance is less than 1.01 times, neutralization tends to be insufficient, and if it exceeds 1.5 times, waste water increases and ester decomposition (saponification) tends to occur. The concentration of the alkaline aqueous solution used here is preferably 1% by weight or more, and more preferably 5 to 15% by weight.
上記生成物の中和後、さらに反応液を水洗する。水洗の量はｐＨで管理し、ｐＨ８以下とすることが好ましい。ｐＨの管理を怠ると、アクリル酸、触媒、不純物、着色成分等が完全に除去できないことがある。 After neutralization of the product, the reaction solution is further washed with water. The amount of water washing is controlled by pH and is preferably pH 8 or less. If the pH is neglected, acrylic acid, catalyst, impurities, coloring components, etc. may not be completely removed.
本発明のトリシクロデカンジオールジ（メタ）アクリレートは、放射線又は熱的手段による硬化性成分として有用である。放射線硬化は、イオン化または電子線のような微粒子照射、または紫外線放射のような化学線により行う。化学線により硬化する場合は、各種の光増感剤または光重合開始剤を包含させて行われる。また、熱硬化は一般的な方法により行われる。 The tricyclodecanediol di (meth) acrylate of the present invention is useful as a curable component by radiation or thermal means. Radiation curing is performed by fine particle irradiation such as ionization or electron beam, or actinic radiation such as ultraviolet radiation. When curing by actinic radiation, it is carried out by including various photosensitizers or photopolymerization initiators. Moreover, thermosetting is performed by a general method.
本発明のトリシクロデカンジオールジ（メタ）アクリレートは、単独又は他の単量体、例えば、脂肪族又は芳香族アクリレートや不飽和基含有樹脂、不飽和ポリエステル、ポリエステルアクリレート、エポキシアクリレート、ウレタンアクリレートなどの樹脂と組み合わせて使用することができる。 The tricyclodecanediol di (meth) acrylate of the present invention is used alone or in other monomers, such as aliphatic or aromatic acrylates, unsaturated group-containing resins, unsaturated polyesters, polyester acrylates, epoxy acrylates, urethane acrylates, etc. It can be used in combination with other resins.
本発明のトリシクロデカンジオールジ（メタ）アクリレートは、塗料・コーティング材料及び土木建築材料だけでなく、半導体・液晶に用いられる電子材料、また光ファイバー、光学レンズ等に代表されるオプトエレクトロニクス材料、さらには医療材料として使用できる。 The tricyclodecanediol di (meth) acrylate of the present invention is not only a paint / coating material and civil engineering / building material, but also an electronic material used in semiconductors / liquid crystals, an optoelectronic material typified by an optical fiber, an optical lens, etc. Can be used as medical material.
次に実施例を挙げて具体的に説明するが、本発明はこれらにより制限されるものではない。 EXAMPLES Next, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.
＜実施例１＞
攪拌機、温度計、空気導入管、及び精留塔（１５段）を取り付けた１リットルフラスコに、式（ＩＩ）で表されるトリシクロデカンジオール３５０ｇ（２．０８モル）、一般式（ＩＩＩ）で表される（メタ）アクリル酸又は（メタ）アクリル酸エステルとしてメタクリル酸メチル８５０ｇ（８．５０モル）、重合禁止剤としてヒドロキノンモノメチルエーテル０．１３ｇを仕込み、常圧下、乾燥空気を１００ｍｌ／分の速度で吹き込みながら加熱還流し、系内の水分を除去した。次に、触媒としてオルトチタン酸イソプロピル（チタンテトライソプロポキシド）３．５ｇを加え、エステル交換反応を行った。始めは反応混合物を加熱還流し、精留塔塔頂温度はメタクリル酸メチルの沸点である１００℃であったが、反応の進行と共に、メタノールとメタクリル酸メチルの共沸混合物の沸点に近づいたので、塔頂温度が６５℃になるように還流比を調節してメタノールをメタクリル酸メチルの共沸物として留去しながら反応を行った。触媒を加えて３時間程経過した頃から塔頂温度が上昇し始め約９０℃まで上昇したので、それに合わせて還流比を徐々に大きくし、最終的には還流比を１５にして反応を続けた。反応開始後５時間目の反応液をガスクロマトグラフィ分析したところ、原料であるトリシクロデカンジオールは検出されず、トリシクロデカンジオールモノメタクリレートが６％（面積％）、目的生成物であるトリシクロデカンジオールジメタクリレートが９４％（面積％）となったので反応を終了した。反応液を７５℃まで冷却し、１７重量％食塩水１２０ｇを加えて触媒を加水分解し不溶化した。３０分静置後、デカンテーションにより有機層を１リットルのナス型フラスコにとり、ロータリーエバポレーターを用いて過剰なメタクリル酸メチルを減圧下留去して吸引ろ過によりナスフラスコ内液をろ過したところ、淡黄色透明のトリシクロデカンジオールジメタクリレートを得た。この時、収量は５９５ｇ（収率９４％）であった。
これをＮＭＲとフーリエ変換赤外線（ＦＴ−ＩＲ）を用いて分析した結果、下記のスペクトルが得られた。
ＮＭＲ（６０ＭＨｚ）：１．６９−２．５４ （１２Ｈ， ｍ），４．６９−５．１４ （２Ｈ， ｍ），５．６１ （２Ｈ， ｍ），６．１８ （４Ｈ， ｍ）
ＩＲ（ｆｉｌｍ）： ２９６２， １７２４， １４０６， １２９６， １２７５， １１９８， １０４９， ９８４， ８１２ ｃｍ−２
<Example 1>
In a 1 liter flask equipped with a stirrer, a thermometer, an air inlet tube, and a rectifying column (15 stages), 350 g (2.08 mol) of tricyclodecanediol represented by the formula (II), a general formula (III) As a (meth) acrylic acid or (meth) acrylic acid ester represented by the formula, methacrylic acid methyl 850 g (8.50 mol) was charged as a polymerization inhibitor, hydroquinone monomethyl ether 0.13 g. The mixture was heated to reflux while blowing at a rate of 5 to remove water in the system. Next, 3.5 g of isopropyl orthotitanate (titanium tetraisopropoxide) was added as a catalyst to conduct a transesterification reaction. At first, the reaction mixture was heated to reflux, and the top temperature of the rectifying column was 100 ° C., the boiling point of methyl methacrylate, but as the reaction progressed, it approached the boiling point of the azeotrope of methanol and methyl methacrylate. The reaction was carried out while distilling off methanol as an azeotrope of methyl methacrylate by adjusting the reflux ratio so that the tower top temperature was 65 ° C. Since about 3 hours have passed since the catalyst was added, the tower top temperature started to rise to about 90 ° C, and the reflux ratio was gradually increased accordingly. Finally, the reaction was continued at a reflux ratio of 15. It was. A gas chromatographic analysis of the reaction solution at 5 hours after the start of the reaction revealed that the raw material tricyclodecanediol was not detected, tricyclodecanediol monomethacrylate was 6% (area%), and the target product tricyclodecane. Since the diol dimethacrylate was 94% (area%), the reaction was terminated. The reaction solution was cooled to 75 ° C., and 120 g of 17% by weight saline was added to hydrolyze and insolubilize the catalyst. After standing for 30 minutes, the organic layer was taken into a 1 liter eggplant-shaped flask by decantation, excess methyl methacrylate was distilled off under reduced pressure using a rotary evaporator, and the solution in the eggplant flask was filtered by suction filtration. A yellow transparent tricyclodecanediol dimethacrylate was obtained. At this time, the yield was 595 g (yield 94%).
As a result of analyzing this using NMR and Fourier transform infrared (FT-IR), the following spectrum was obtained.
NMR (60 MHz): 1.69-2.54 (12H, m), 4.69-5.14 (2H, m), 5.61 (2H, m), 6.18 (4H, m)
IR (film): 2962, 1724, 1406, 1296, 1275, 1198, 1049, 984, 812 cm −2
＜実施例２＞
攪拌機、温度計、空気導入管、Ｄｅａｎ−Ｓｔａｒｋトラップ及び冷却管を取り付けた１リットルフラスコにトリシクロデカンジオール３５０ｇ（２．０８モル）、アクリル酸１９５ｇ（２．７０モル）、トルエン４００ｇ、パラトルエンスルホン酸３５ｇ及びヒドロキノンモノメチルエーテル０．１７ｇを仕込んだ。系内の圧力を７０．６ＫＰａに調節し、乾燥空気を１００ｍｌ／分の導入量で吹き込みながら昇温した。反応とともに生成する水を除去しながら反応温度を９０℃に保つように圧力を調整した。５時間後、反応理論量の水が流出したため、ガスクロマトグラフィ分析を行ったところ、原料であるトリシクロデカンジオールは検出されず、トリシクロデカンジオールモノアクリレートが６％（面積％）、目的生成物であるトリシクロデカンジオールジアクリレートが９４％（面積％）となったので反応を終了した。反応液を冷却し、４０℃以下になったところで１７重量％食塩水を１００ｇ仕込み３００ｒｐｍで攪拌した。次いで有機層を分液ロートに移し、２５重量％水酸化ナトリウム水溶液５０ｇ、１７重量％食塩水７０ｇを仕込み、中和水洗を行った。このとき、水層のｐＨは１０であったので、水層抜出後、有機層をさらに１７重量％食塩水２００ｇで洗浄して水層のｐＨを７〜８とした。水層抜出後、有機層を１リットルのナス型フラスコにとり、ロータリーエバポレーターを用いてトルエンを減圧下留去して吸引ろ過によりナスフラスコ内液をろ過したところ、淡黄色透明のトリシクロデカンジオールジアクリレートを得た。この時、収量は５１２ｇ（収率８９％）であった。
これをＮＭＲとフーリエ変換赤外線（ＦＴ−ＩＲ）を用いて分析した結果、下記のスペクトルが得られた。
ＮＭＲ（６０ＭＨｚ）：１．６９−２．５８ （１８Ｈ， ｍ），４．７３−５．１５ （２Ｈ， ｍ）， ５．４０ （２Ｈ， ｓ），５．９１ （２Ｈ， ｓ）
ＩＲ（ｆｉｌｍ）： ２９６０， １７１６， １６３７， １４５２， １３２７， １２９８， １１６７， ８７４， ８１６ ｃｍ−１
<Example 2>
350 g (2.08 mol) of tricyclodecanediol, 195 g (2.70 mol) of acrylic acid, 400 g of toluene, 400 g of paratoluene in a 1 liter flask equipped with a stirrer, thermometer, air introduction tube, Dean-Stark trap and condenser tube 35 g of sulfonic acid and 0.17 g of hydroquinone monomethyl ether were charged. The pressure in the system was adjusted to 70.6 KPa, and the temperature was raised while blowing dry air at an introduction rate of 100 ml / min. The pressure was adjusted so as to keep the reaction temperature at 90 ° C. while removing water generated along with the reaction. After 5 hours, since a theoretical amount of water flowed out, gas chromatography analysis was performed. As a result, the starting material tricyclodecanediol was not detected, and tricyclodecanediol monoacrylate was 6% (area%). Since the tricyclodecanediol diacrylate was 94% (area%), the reaction was terminated. The reaction solution was cooled, and when it became 40 ° C. or lower, 100 g of 17 wt% saline was charged and stirred at 300 rpm. Next, the organic layer was transferred to a separatory funnel and charged with 50 g of a 25 wt% aqueous sodium hydroxide solution and 70 g of 17 wt% saline solution and washed with neutralized water. At this time, since the pH of the aqueous layer was 10, after extracting the aqueous layer, the organic layer was further washed with 200 g of 17 wt% saline to adjust the pH of the aqueous layer to 7-8. After extracting the aqueous layer, the organic layer was placed in a 1 liter eggplant-shaped flask, toluene was distilled off under reduced pressure using a rotary evaporator, and the solution in the eggplant flask was filtered by suction filtration. As a result, a pale yellow transparent tricyclodecanediol was obtained. Diacrylate was obtained. At this time, the yield was 512 g (89% yield).
As a result of analyzing this using NMR and Fourier transform infrared (FT-IR), the following spectrum was obtained.
NMR (60 MHz): 1.69-2.58 (18H, m), 4.73-5.15 (2H, m), 5.40 (2H, s), 5.91 (2H, s)
IR (film): 2960, 1716, 1637, 1452, 1327, 1298, 1167, 874, 816 cm −1
Claims (3)
The method for producing tricyclodecanediol di (meth) acrylate according to claim 2, wherein the tricyclodecanediol represented by the formula (II) is reacted with (meth) acrylic acid in the presence of a catalyst.
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| WO2011027618A1 (en) * | 2009-09-03 | 2011-03-10 | 日立化成工業株式会社 | Tricyclodecane monomethanol monocarboxylic acid and derivatives thereof |
| WO2011048851A1 (en) | 2009-10-22 | 2011-04-28 | 日立化成工業株式会社 | Method for manufacturing a tricyclodecane mono-methanol monocarboxylic acid derivative |
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| JP2018511576A (en) * | 2015-02-26 | 2018-04-26 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Process for producing isosorbide di (meth) acrylate |
| US10040967B2 (en) | 2015-11-06 | 2018-08-07 | Hitachi Chemical Company, Ltd. | Photosensitive film, photosensitive element, cured product and touch panel |
| US10717893B2 (en) | 2015-11-06 | 2020-07-21 | Hitachi Chemical Company, Ltd. | Photosensitive film, photosensitive element, cured product and touch panel |
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