JPWO2019193925A1 - Composition containing isobornyl (meth) acrylate and method for producing the same - Google Patents
Composition containing isobornyl (meth) acrylate and method for producing the same Download PDFInfo
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- JPWO2019193925A1 JPWO2019193925A1 JP2020511668A JP2020511668A JPWO2019193925A1 JP WO2019193925 A1 JPWO2019193925 A1 JP WO2019193925A1 JP 2020511668 A JP2020511668 A JP 2020511668A JP 2020511668 A JP2020511668 A JP 2020511668A JP WO2019193925 A1 JPWO2019193925 A1 JP WO2019193925A1
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- JP
- Japan
- Prior art keywords
- meth
- acrylate
- isobornyl
- acrylic acid
- composition containing
- Prior art date
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- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 title claims abstract description 71
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 70
- 239000000203 mixture Substances 0.000 title claims abstract description 67
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 35
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 58
- CRPUJAZIXJMDBK-UHFFFAOYSA-N camphene Chemical compound C1CC2C(=C)C(C)(C)C1C2 CRPUJAZIXJMDBK-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000011541 reaction mixture Substances 0.000 claims abstract description 41
- 238000004817 gas chromatography Methods 0.000 claims abstract description 23
- PXRCIOIWVGAZEP-UHFFFAOYSA-N Primaeres Camphenhydrat Natural products C1CC2C(O)(C)C(C)(C)C1C2 PXRCIOIWVGAZEP-UHFFFAOYSA-N 0.000 claims abstract description 22
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229930006739 camphene Natural products 0.000 claims abstract description 22
- ZYPYEBYNXWUCEA-UHFFFAOYSA-N camphenilone Natural products C1CC2C(=O)C(C)(C)C1C2 ZYPYEBYNXWUCEA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000007787 solid Substances 0.000 claims abstract description 18
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 15
- 239000002585 base Substances 0.000 claims description 18
- -1 alkali metal hydrogen carbonate Chemical class 0.000 claims description 11
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 3
- 150000008041 alkali metal carbonates Chemical group 0.000 claims description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 21
- TZNXGARVNMCICB-UHFFFAOYSA-N Camphen Natural products C1CC2C(C)(C)C(=C)C1C2(C)C TZNXGARVNMCICB-UHFFFAOYSA-N 0.000 abstract description 11
- 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 36
- 238000006243 chemical reaction Methods 0.000 description 24
- 239000003054 catalyst Substances 0.000 description 13
- 238000004821 distillation Methods 0.000 description 13
- 208000012839 conversion disease Diseases 0.000 description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 12
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 11
- 229940119545 isobornyl methacrylate Drugs 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000013329 compounding Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 239000011973 solid acid Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 239000000976 ink Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000004448 titration Methods 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
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000003729 cation exchange resin Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007423 decrease Effects 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
- 230000007613 environmental effect Effects 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 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
- 239000002351 wastewater Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 1
- CSGAUKGQUCHWDP-UHFFFAOYSA-N 1-hydroxy-2,2,6,6-tetramethylpiperidin-4-ol Chemical group CC1(C)CC(O)CC(C)(C)N1O CSGAUKGQUCHWDP-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
- PFEFOYRSMXVNEL-UHFFFAOYSA-N 2,4,6-tritert-butylphenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 PFEFOYRSMXVNEL-UHFFFAOYSA-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
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- UTGQNNCQYDRXCH-UHFFFAOYSA-N N,N'-diphenyl-1,4-phenylenediamine Chemical compound C=1C=C(NC=2C=CC=CC=2)C=CC=1NC1=CC=CC=C1 UTGQNNCQYDRXCH-UHFFFAOYSA-N 0.000 description 1
- BELBBZDIHDAJOR-UHFFFAOYSA-N Phenolsulfonephthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2S(=O)(=O)O1 BELBBZDIHDAJOR-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- PSGCQDPCAWOCSH-OPQQBVKSSA-N [(1s,3r,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] prop-2-enoate Chemical compound C1C[C@]2(C)[C@H](OC(=O)C=C)C[C@H]1C2(C)C PSGCQDPCAWOCSH-OPQQBVKSSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- IXPUJMULXNNEHS-UHFFFAOYSA-L copper;n,n-dibutylcarbamodithioate Chemical compound [Cu+2].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC IXPUJMULXNNEHS-UHFFFAOYSA-L 0.000 description 1
- OBBCYCYCTJQCCK-UHFFFAOYSA-L copper;n,n-diethylcarbamodithioate Chemical compound [Cu+2].CCN(CC)C([S-])=S.CCN(CC)C([S-])=S OBBCYCYCTJQCCK-UHFFFAOYSA-L 0.000 description 1
- ZOUQIAGHKFLHIA-UHFFFAOYSA-L copper;n,n-dimethylcarbamodithioate Chemical compound [Cu+2].CN(C)C([S-])=S.CN(C)C([S-])=S ZOUQIAGHKFLHIA-UHFFFAOYSA-L 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- WGJJZRVGLPOKQT-UHFFFAOYSA-K lanthanum(3+);trifluoromethanesulfonate Chemical compound [La+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F WGJJZRVGLPOKQT-UHFFFAOYSA-K 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 229960003531 phenolsulfonphthalein Drugs 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
- C07C69/54—Acrylic acid esters; Methacrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B61/00—Other general methods
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
イソボルニル（メタ）アクリレートを含む組成物の製造方法であって、（メタ）アクリル酸とカンフェンを反応させることによりイソボルニル（メタ）アクリレートを含む反応混合物を得る工程と、得られた反応混合物を固体塩基で中和する工程および蒸留する工程を含み、イソボルニル（メタ）アクリレートのガスクロマトグラフィーによる純度が９９．５％以上であり、かつ未反応の（メタ）アクリル酸が０.０２重量％以下であるイソボルニル（メタ）アクリレートを含む組成物を得るイソボルニル（メタ）アクリレートを含む組成物の製造方法。当該製造方法によれば、（メタ）アクリル酸とカンフェンを反応させることによって得られるイソボルニル（メタ）アクリレートを含む混合物から、未反応のアクリル酸が低減された高純度のイソボルニル（メタ）アクリレートを含む組成物が得られる。A method for producing a composition containing isobornyl (meth) acrylate, wherein a reaction mixture containing isobornyl (meth) acrylate is obtained by reacting (meth) acrylic acid with camphen, and the obtained reaction mixture is a solid base. Including a step of neutralizing with and a step of distilling, the purity of isobornyl (meth) acrylate by gas chromatography is 99.5% or more, and the unreacted (meth) acrylic acid is 0.02% by weight or less. A method for producing a composition containing isobornyl (meth) acrylate to obtain a composition containing isobornyl (meth) acrylate. According to the production method, a mixture containing isobornyl (meth) acrylate obtained by reacting (meth) acrylic acid with camphene contains high-purity isobornyl (meth) acrylate in which unreacted acrylic acid is reduced. The composition is obtained.
Description
本発明は、イソボルニル（メタ）アクリレートを含む組成物およびその製造方法に関する。 The present invention relates to a composition containing isobornyl (meth) acrylate and a method for producing the same.
イソボルニル（メタ）アクリレートは、例えば、印刷用インク、硬化性塗料用バインダー、接着剤、光硬化反応希釈剤などの製品で使用されている。従来、イソボルニル（メタ）アクリレートの製造方法として、（メタ）アクリル酸とカンフェンを反応させる方法が知られている（特許文献１、２）。このような反応で得られるイソボルニル（メタ）アクリレートを含む反応混合物には、未反応の（メタ）アクリル酸とカンフェンが含まれるため、例えば、特許文献１では、上記反応混合物を減圧蒸留後、アルカリ水で洗浄することにより、ガスクロマトグラフィーによる純度が９９．９％であるイソボルニル（メタ）アクリレートを含む組成物が得られることが開示されている。 Isobornyl (meth) acrylates are used in products such as printing inks, binders for curable paints, adhesives, and photocurable reaction diluents. Conventionally, as a method for producing isobornyl (meth) acrylate, a method of reacting (meth) acrylic acid with camphene has been known (Patent Documents 1 and 2). Since the reaction mixture containing isobornyl (meth) acrylate obtained by such a reaction contains unreacted (meth) acrylic acid and camphen, for example, in Patent Document 1, the reaction mixture is distilled under reduced pressure and then alkaline. It is disclosed that washing with water gives a composition containing isobornyl (meth) acrylate having a purity of 99.9% by gas chromatography.
上記のような製品が高品質化するに伴って、原料のイソボルニル（メタ）アクリレートには、より高純度なものが求められてきている。とくに、（メタ）アクリル酸とカンフェンを反応させて得られるイソボルニル（メタ）アクリレートを含む反応混合物に含まれる未反応の（メタ）アクリル酸は、上記の製品に不具合（例えば、着色、保管安定性の低下等）を起こす要因と考えられ、市場では、未反応の（メタ）アクリル酸が低減されたものが切望されている。 As the quality of the above-mentioned products has improved, the isobornyl (meth) acrylate as a raw material is required to have higher purity. In particular, unreacted (meth) acrylic acid contained in the reaction mixture containing isobornyl (meth) acrylate obtained by reacting (meth) acrylic acid with camphene causes defects (for example, coloring and storage stability) in the above products. It is considered to be a factor that causes a decrease in unreacted (meth) acrylic acid, and the market is eagerly awaiting a product in which unreacted (meth) acrylic acid is reduced.
また、未反応の（メタ）アクリル酸を低減させるためには、上記の特許文献１のように、反応混合物をアルカリ水で洗浄することは有効であると考えられるが、当該製造方法は、アルカリ廃水が多量に発生するため、環境負荷の観点から、問題がある。 Further, in order to reduce unreacted (meth) acrylic acid, it is considered effective to wash the reaction mixture with alkaline water as in Patent Document 1 above, but the production method is alkaline. Since a large amount of wastewater is generated, there is a problem from the viewpoint of environmental load.
本発明は、前記実情に鑑みてなされたものであり、（メタ）アクリル酸とカンフェンを反応させることによって得られるイソボルニル（メタ）アクリレートを含む混合物から、未反応のアクリル酸が低減された高純度のイソボルニル（メタ）アクリレートを含む組成物を得るため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 circumstances, and has a high purity in which unreacted acrylic acid is reduced from a mixture containing isobornyl (meth) acrylate obtained by reacting (meth) acrylic acid with camphene. It is an object of the present invention to provide a production method for obtaining a composition containing isobornyl (meth) acrylate of the above.
また、本発明は、未反応のアクリル酸が低減された高純度のイソボルニル（メタ）アクリレートを含む組成物を提供することを目的とする。 Another object of the present invention is to provide a composition containing high-purity isobornyl (meth) acrylate in which unreacted acrylic acid is reduced.
本発明は、イソボルニル（メタ）アクリレートを含む組成物の製造方法であって、（メタ）アクリル酸とカンフェンを反応させることによりイソボルニル（メタ）アクリレートを含む反応混合物を得る工程と、得られた反応混合物を固体塩基で中和する工程および蒸留する工程を含み、イソボルニル（メタ）アクリレートのガスクロマトグラフィーによる純度が９９．５％以上であり、かつ未反応の（メタ）アクリル酸が０.０２重量％以下であるイソボルニル（メタ）アクリレートを含む組成物を得ることを特徴とするイソボルニル（メタ）アクリレートを含む組成物の製造方法、に関する。 The present invention is a method for producing a composition containing isobornyl (meth) acrylate, which comprises reacting (meth) acrylic acid with camphen to obtain a reaction mixture containing isobornyl (meth) acrylate, and the obtained reaction. Including a step of neutralizing the mixture with a solid base and a step of distilling, the purity of isobornyl (meth) acrylate by gas chromatography is 99.5% or more, and the unreacted (meth) acrylic acid is 0.02 weight. The present invention relates to a method for producing a composition containing isobornyl (meth) acrylate, which comprises obtaining a composition containing isobornyl (meth) acrylate of% or less.
また、本発明は、イソボルニル（メタ）アクリレートのガスクロマトグラフィーによる純度が９９．５％以上であり、かつ（メタ）アクリル酸の割合が０重量％超０.０２重量％以下であることを特徴とするイソボルニル（メタ）アクリレートを含む組成物、に関する。 Further, the present invention is characterized in that the purity of isobornyl (meth) acrylate by gas chromatography is 99.5% or more, and the ratio of (meth) acrylic acid is more than 0% by weight and 0.02% by weight or less. The present invention relates to a composition containing isobornyl (meth) acrylate.
本発明の製造方法によれば、（メタ）アクリル酸とカンフェンを反応させることによって得られるイソボルニル（メタ）アクリレートを含む混合物から、未反応のアクリル酸が低減された高純度のイソボルニル（メタ）アクリレートを含む組成物が得られるため、当該イソボルニル（メタ）アクリレートを含む組成物は、例えば、印刷用インク、硬化性塗料用バインダー、接着剤、光硬化反応希釈剤などの製品に使用する原料として有用である。 According to the production method of the present invention, a high-purity isobornyl (meth) acrylate in which unreacted acrylic acid is reduced from a mixture containing isobornyl (meth) acrylate obtained by reacting (meth) acrylic acid with camphen. Since a composition containing is obtained, the composition containing isobornyl (meth) acrylate is useful as a raw material used in products such as printing inks, binders for curable paints, adhesives, and photocurable reaction diluents. Is.
また、本発明の製造方法によれば、未反応の（メタ）アクリル酸を中和する際に多量のアルカリ水を必要としないため、多量のアルカリ廃水を処理する際の煩雑な後処理工程が不要であり、環境負荷の観点からも有益である。 Further, according to the production method of the present invention, a large amount of alkaline water is not required to neutralize unreacted (meth) acrylic acid, so that a complicated post-treatment step for treating a large amount of alkaline wastewater is required. It is unnecessary and beneficial from the viewpoint of environmental load.
＜イソボルニル（メタ）アクリレートを含む組成物の製造方法＞
本発明のイソボルニル（メタ）アクリレートを含む組成物の製造方法は、（メタ）アクリル酸とカンフェンを反応させることによりイソボルニル（メタ）アクリレートを含む反応混合物を得る工程と、得られた反応混合物を固体塩基で中和する工程および蒸留する工程を含み、イソボルニル（メタ）アクリレートのガスクロマトグラフィーによる純度が９９．５％以上であり、かつ未反応の（メタ）アクリル酸が０.０２重量％以下であるイソボルニル（メタ）アクリレートを含む組成物を得る製造方法である。なお、本発明において、イソボルニル（メタ）アクリレートとは、イソボルニルアクリレートおよび／またはイソボルニルメタクリレートを意味する。また、（メタ）アクリル酸とは、アクリル酸および／またはメタクリル酸を意味する。<Method for producing a composition containing isobornyl (meth) acrylate>
The method for producing a composition containing isobornyl (meth) acrylate of the present invention is a step of obtaining a reaction mixture containing isobornyl (meth) acrylate by reacting (meth) acrylic acid with camphen, and solidifying the obtained reaction mixture. Including a step of neutralizing with a base and a step of distilling, the purity of isobornyl (meth) acrylate by gas chromatography is 99.5% or more, and the unreacted (meth) acrylic acid is 0.02% by weight or less. A production method for obtaining a composition containing a certain isobornyl (meth) acrylate. In the present invention, the isobornyl (meth) acrylate means an isobornyl acrylate and / or an isobornyl methacrylate. Further, (meth) acrylic acid means acrylic acid and / or methacrylic acid.
＜イソボルニル（メタ）アクリレートを含む反応混合物を得る工程＞
前記反応混合物を得る工程において、（メタ）アクリル酸とカンフェンの反応は、（メタ）アクリル酸が、カンフェン１モルに対して０．８〜２．５モルであることが好ましく、０．９〜２モルであることがより好ましい。反応温度は、カンフェンと（メタ）アクリル酸を迅速に混合して生産性を高める観点から、１０〜７５℃であることが好ましく、３５〜６０℃であることがより好ましい。反応時間は、反応温度や、後述する反応転化率などによって異なるので一概には決定できないが、通常、２時間以上２４時間以下程度である。<Step of obtaining a reaction mixture containing isobornyl (meth) acrylate>
In the step of obtaining the reaction mixture, the reaction between (meth) acrylic acid and camphene preferably contains 0.8 to 2.5 mol of (meth) acrylic acid with respect to 1 mol of camphene, and 0.9 to 2.5 mol. More preferably, it is 2 mol. The reaction temperature is preferably 10 to 75 ° C., more preferably 35 to 60 ° C., from the viewpoint of rapidly mixing camphene and (meth) acrylic acid to increase productivity. The reaction time varies depending on the reaction temperature, the reaction conversion rate described later, and the like, and therefore cannot be unconditionally determined, but is usually about 2 hours or more and 24 hours or less.
前記反応混合物を得る工程において、（メタ）アクリル酸とカンフェンの反応は、溶媒を使用してもよい。溶媒は、特に制限されないが、反応系内で不活性な有機溶媒であることが好ましい。有機溶媒としては、例えば、シクロヘキサン、ヘキサン、トルエン、エチルベンゼン、メチルシクロヘキサン、エチルシクロヘキサンなどが挙げられる。前記溶媒の使用量は特に制限されないが、通常、カンフェンと（メタ）アクリル酸の合計量１００重量部に対して、１００重量部以下程度である。 In the step of obtaining the reaction mixture, a solvent may be used for the reaction of (meth) acrylic acid and camphene. The solvent is not particularly limited, but is preferably an organic solvent that is inert in the reaction system. Examples of the organic solvent include cyclohexane, hexane, toluene, ethylbenzene, methylcyclohexane, ethylcyclohexane and the like. The amount of the solvent used is not particularly limited, but is usually about 100 parts by weight or less with respect to 100 parts by weight of the total amount of camphene and (meth) acrylic acid.
（メタ）アクリル酸とカンフェンの反応は、重合防止剤および／または酸化防止剤の存在下で行うことが好ましい。重合防止剤および／または酸化防止剤としては、例えば、ハイドロキノン、ハイドロキノンモノメチルエーテル、ベンゾキノン、ｐ−ｔｅｒｔ−ブチルカテコールなどのキノン系化合物；２，６−ジ−ｔｅｒｔ−ブチルフェノール、２，４−ジ−ｔｅｒｔ−ブチルフェノール、２−ｔｅｒｔ−ブチル−４，６−ジメチルフェノール、２，６−ジ−ｔｅｒｔ−ブチル−４−メチルフェノール、２，４，６−トリ−ｔｅｒｔ−ブチルフェノールなどのアルキルフェノール系化合物；アルキル化ジフェニルアミン、Ｎ，Ｎ’−ジフェニル−ｐ−フェニレンジアミン、フェノチアジンなどのアミン系化合物；４−ヒドロキシ−２，２，６，６−テトラメチルピペリジン−Ｎ−オキシルなどのヒンダートアミン系化合物；金属銅、硫酸銅、塩化第一銅、ジメチルジチオカルバミン酸銅、ジエチルジチオカルバミン酸銅、ジブチルジチオカルバミン酸銅などの銅系化合物、チオエーテル系化合物、リン系化合物などが挙げられる。重合防止剤および／または酸化防止剤は、単独で使用してもよいし、２種以上を併用してもよい。 The reaction of (meth) acrylic acid with camphene is preferably carried out in the presence of a polymerization inhibitor and / or an antioxidant. Antipolymerization agents and / or antioxidants include, for example, quinone compounds such as hydroquinone, hydroquinone monomethyl ether, benzoquinone, p-tert-butylcatechol; 2,6-di-tert-butylphenol, 2,4-di-. Alkylphenol compounds such as tert-butylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol; alkyl Amine compounds such as diphenylamine chemicals, N, N'-diphenyl-p-phenylenediamine, phenothiazine; hindered amine compounds such as 4-hydroxy-2,2,6,6-tetramethylpiperidin-N-oxyl; metals Examples thereof include copper-based compounds such as copper, copper sulfate, cuprous chloride, copper dimethyldithiocarbamate, copper diethyldithiocarbamate, and copper dibutyldithiocarbamate, thioether-based compounds, and phosphorus-based compounds. The polymerization inhibitor and / or the antioxidant may be used alone or in combination of two or more.
重合防止剤および／または酸化防止剤の使用量は、（メタ）アクリル酸１００重量部に対して、０．０００１〜１重量部であることが好ましく、０．００１〜０．１重量部であることがより好ましい。 The amount of the polymerization inhibitor and / or antioxidant used is preferably 0.0001 to 1 part by weight, preferably 0.001 to 0.1 part by weight, based on 100 parts by weight of (meth) acrylic acid. Is more preferable.
（メタ）アクリル酸とカンフェンの反応は、触媒を使用することが好ましい。触媒としては、例えば、ｐ−トルエンスルホン酸、メタンスルホン酸、硫酸などの酸性触媒；固体酸触媒などが挙げられる。 It is preferable to use a catalyst for the reaction between (meth) acrylic acid and camphene. Examples of the catalyst include acidic catalysts such as p-toluenesulfonic acid, methanesulfonic acid, and sulfuric acid; and solid acid catalysts.
固体酸触媒としては、例えば、強酸性陽イオン交換樹脂、硫酸ジルコニアなどの硫酸希土類金属塩、ランタントリフレートなどの希土類金属錯体などが挙げられる。固体酸触媒は、水分とカンフェンおよび（メタ）アクリル酸とが反応するのを抑制する観点から、乾燥されていることが好ましい。 Examples of the solid acid catalyst include a strongly acidic cation exchange resin, a sulfuric acid rare earth metal salt such as zirconia sulfate, and a rare earth metal complex such as lanthanum triflate. The solid acid catalyst is preferably dried from the viewpoint of suppressing the reaction of water with camphene and (meth) acrylic acid.
触媒の使用量は、触媒活性および目的反応率などにより決定されるが、カンフェンと（メタ）アクリル酸の合計量１００重量部に対して、０．１〜１０重量部であることが好ましく、１〜５重量部であることがより好ましい。 The amount of the catalyst used is determined by the catalytic activity, the target reaction rate, etc., but is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the total amount of camphene and (meth) acrylic acid. More preferably, it is ~ 5 parts by weight.
前記反応混合物を得る工程において、（メタ）アクリル酸とカンフェンを反応させる際の反応方式は、単一の反応器内に全ての原料を仕込んで反応を完結させる回分式でもよいし、反応器内に原料を連続的に供給して連続的に反応させる連続式でもよいし、反応器と配合タンクとを備え、反応器と配合タンクとの間で原料を循環させながら反応器で反応させる循環式であってもよい。 In the step of obtaining the reaction mixture, the reaction method for reacting (meth) acrylic acid with camphen may be a batch method in which all the raw materials are charged in a single reactor to complete the reaction, or in the reactor. It may be a continuous type in which the raw materials are continuously supplied to the reactor and continuously reacted, or a circulation type in which a reactor and a compounding tank are provided and the raw materials are circulated between the reactor and the compounding tank and reacted by the reactor. It may be.
循環式での反応に際して使用する反応装置としては、例えば、固体酸触媒などの触媒が充填された反応器と、（メタ）アクリル酸にカンフェンを添加する配合タンクとを備え、反応器と配合タンクとの間で（メタ）アクリル酸とカンフェンとの混合物が循環するように、これらを接続した反応装置を用いることができる。この反応装置では、配合タンク内に仕込んだ（メタ）アクリル酸にカンフェンを滴下し、（メタ）アクリル酸とカンフェンとを含む混合物を、配合タンクと反応器との間で循環させながら、反応器にて反応させる。 As the reactor used for the reaction in the circulation type, for example, a reactor filled with a catalyst such as a solid acid catalyst and a compounding tank for adding camphen to (meth) acrylic acid are provided, and the reactor and the compounding tank are provided. A reactor connecting these can be used so that a mixture of (meth) acrylic acid and camphen circulates between them. In this reactor, camphene is dropped onto the (meth) acrylic acid charged in the compounding tank, and the mixture containing (meth) acrylic acid and camphene is circulated between the compounding tank and the reactor while being circulated in the reactor. React with.
前記反応混合物を得る工程において、（メタ）アクリル酸とカンフェンの反応は、適時、イソボルニル（メタ）アクリレートの反応転化率をガスクロマトグラフィーで調べ、所定の反応転化率に達した時点で、その反応を終了させて、イソボルニル（メタ）アクリレートを含む反応混合物を得ることが好ましい。反応転化率が高くなると、反応速度が低下するため、イソボルニル（メタ）アクリレートの工業的な生産性を考慮した場合、所定の反応転化率は、５０％以上であることが好ましく、８０％以上であることがより好ましい。 In the step of obtaining the reaction mixture, the reaction of (meth) acrylic acid and camphen is timely examined by gas chromatography for the reaction conversion rate of isobornyl (meth) acrylate, and when the reaction conversion rate reaches a predetermined reaction conversion rate, the reaction is performed. Is preferably terminated to obtain a reaction mixture containing isobornyl (meth) acrylate. As the reaction conversion rate increases, the reaction rate decreases. Therefore, when considering the industrial productivity of isobornyl (meth) acrylate, the predetermined reaction conversion rate is preferably 50% or more, preferably 80% or more. More preferably.
＜反応混合物を固体塩基で中和する工程および蒸留する工程＞
（メタ）アクリル酸とカンフェンの反応によって得られたイソボルニル（メタ）アクリレートを含む反応混合物は、固体塩基で中和する工程および蒸留する工程を施すことにより、イソボルニル（メタ）アクリレートのガスクロマトグラフィーによる純度が９９．５％以上であり、かつ未反応の（メタ）アクリル酸が０.０２重量％以下であるイソボルニル（メタ）アクリレートを含む組成物が得られる。<Step of neutralizing the reaction mixture with a solid base and step of distilling>
The reaction mixture containing isobornyl (meth) acrylate obtained by the reaction of (meth) acrylic acid and camphene is subjected to a step of neutralizing with a solid base and a step of distilling, and is subjected to gas chromatography of isobornyl (meth) acrylate. A composition containing isobornyl (meth) acrylate having a purity of 99.5% or more and an unreacted (meth) acrylic acid of 0.02% by weight or less can be obtained.
前記固体塩基で中和する工程、および前記蒸留する工程は、いずれの工程を先に施してもよく、また、各工程を繰り返し施してもよい。（メタ）アクリル酸とカンフェンの反応によって得られたイソボルニル（メタ）アクリレートを含む反応混合物を蒸留する工程を施すことで、未反応の（メタ）アクリル酸を効率よく除去できる観点から、前記蒸留する工程は、前記固体塩基で中和する工程の前に施すことが好ましい。 The step of neutralizing with the solid base and the step of distilling may be performed first, or each step may be repeated. By performing a step of distilling the reaction mixture containing isobornyl (meth) acrylate obtained by the reaction of (meth) acrylic acid and camphen, the unreacted (meth) acrylic acid can be efficiently removed. The step is preferably performed before the step of neutralizing with the solid base.
固体塩基としては、例えば、アルカリ金属炭酸塩、アルカリ金属炭酸水素塩、アルカリ金属水酸化物、アルカリ土類金属炭酸塩、アルカリ土類金属炭酸水素塩、アルカリ土類金属水酸化物、アルカリ土類金属酸化物などが挙げられる。これらの中でも、アルカリ金属炭酸塩、アルカリ土類金属炭酸塩が好ましい。前記アルカリ金属としては、リチウム、ナトリウム、カリウムが好ましい。前記アルカリ土類金属としては、マグネシウム、カルシウム、バリウムが好ましい。固体塩基は、単独で使用してもよいし、２種以上を併用してもよい。 Examples of the solid base include alkali metal carbonate, alkali metal hydrogen carbonate, alkali metal hydroxide, alkaline earth metal carbonate, alkaline earth metal hydrogen carbonate, alkaline earth metal hydroxide, and alkaline earth. Examples include metal oxides. Among these, alkali metal carbonates and alkaline earth metal carbonates are preferable. As the alkali metal, lithium, sodium and potassium are preferable. As the alkaline earth metal, magnesium, calcium and barium are preferable. The solid base may be used alone or in combination of two or more.
前記蒸留する工程を前記固体塩基で中和する工程の前に施す場合、蒸留により未反応の（メタ）アクリル酸の多くが留去できるため、固体塩基の使用量は、（メタ）アクリル酸との接触確率を高め、効率良く中和反応を促進させる観点から、イソボルニル（メタ）アクリレートを含む反応混合物１００重量部に対して、０．０１〜１０重量部であることが好ましく、０．０５〜５重量部であることがより好ましく、０．１〜２重量部であることがさらに好ましい。一方、前記固体塩基で中和する工程を前記蒸留する工程の前に施す場合、上記の反応転化率によって前記反応混合物中の未反応の（メタ）アクリル酸の割合が異なるため一概に言えないが、通常、固体塩基の使用量は、イソボルニル（メタ）アクリレートを含む反応混合物１００重量部に対して、２０〜５０００重量部であることが好ましく、５０〜２０００重量部であることがより好ましく、１００〜１０００重量部であることがさらに好ましい。 When the step of distillation is performed before the step of neutralizing with the solid base, most of the unreacted (meth) acrylic acid can be distilled off by distillation, so that the amount of the solid base used is the same as that of (meth) acrylic acid. From the viewpoint of increasing the contact probability and efficiently promoting the neutralization reaction, the amount is preferably 0.01 to 10 parts by weight, preferably 0.05 to 10 parts by weight, based on 100 parts by weight of the reaction mixture containing isobornyl (meth) acrylate. It is more preferably 5 parts by weight, further preferably 0.1 to 2 parts by weight. On the other hand, when the step of neutralizing with the solid base is performed before the step of distillation, the ratio of unreacted (meth) acrylic acid in the reaction mixture differs depending on the reaction conversion rate, so that it cannot be said unconditionally. Usually, the amount of the solid base used is preferably 20 to 5000 parts by weight, more preferably 50 to 2000 parts by weight, based on 100 parts by weight of the reaction mixture containing isobornyl (meth) acrylate. It is more preferably ~ 1000 parts by weight.
前記固体塩基で中和する工程において、処理温度は、反応混合物の熱安定性を考慮し、中和反応を促進させる観点から、０〜１００℃であることが好ましく、１０〜８０℃であることがより好ましく、２０〜６０℃であることがさらに好ましい。また、処理時間は、処理温度などによって異なるので一概には決定できないが、通常、３０分〜２４時間程度である。 In the step of neutralizing with the solid base, the treatment temperature is preferably 0 to 100 ° C., preferably 10 to 80 ° C., in consideration of the thermal stability of the reaction mixture and from the viewpoint of promoting the neutralization reaction. Is more preferable, and the temperature is even more preferably 20 to 60 ° C. Further, the treatment time varies depending on the treatment temperature and the like and cannot be unconditionally determined, but is usually about 30 minutes to 24 hours.
前記固体塩基で中和する工程において、固体塩基で中和反応させる際の反応方式は、上記の回分式でもよく、連続式でもよく、循環式であってもよい。 In the step of neutralizing with a solid base, the reaction method for neutralizing with a solid base may be the above-mentioned batch method, continuous method, or circulation method.
前記蒸留する工程において、蒸留は、通常、減圧下で加熱することによって行うことが好ましい。（メタ）アクリル酸エステルの重合反応を抑制する観点から、加熱温度は３０〜１５０℃であることが好ましく、５０〜１３０℃であることがより好ましい。また、減圧の程度は、加熱温度によって異なるので一概に決定することはできないが、通常、加熱温度が１５０℃を超えないようにする観点から、１０ｋＰａ以下であることが好ましく、５ｋＰａ以下であることがより好ましい。 In the distillation step, the distillation is usually preferably carried out by heating under reduced pressure. From the viewpoint of suppressing the polymerization reaction of the (meth) acrylic acid ester, the heating temperature is preferably 30 to 150 ° C, more preferably 50 to 130 ° C. Further, the degree of depressurization cannot be unconditionally determined because it depends on the heating temperature, but usually, from the viewpoint of preventing the heating temperature from exceeding 150 ° C., it is preferably 10 kPa or less, and 5 kPa or less. Is more preferable.
また、本発明の製造方法では、上記の前記固体塩基で中和する工程および前記蒸留する工程を設けた後に、目的物（イソボルニル（メタ）アクリレートを含む組成物）の純度をより高めるため、目的物を精留する工程を設けることができる。精留は、通常、減圧下で加熱することによって行うことが好ましい。イソボルニル（メタ）アクリレートの沸点を考慮して、通常、加熱温度は１００〜１３０℃程度であり、減圧の程度は０．５〜３ｋＰａ程度である。 Further, in the production method of the present invention, in order to further increase the purity of the target product (composition containing isobornyl (meth) acrylate) after providing the above-mentioned step of neutralizing with the solid base and the above-mentioned distillation step, the object is A step of rectifying an object can be provided. The rectification is usually preferably carried out by heating under reduced pressure. Considering the boiling point of isobornyl (meth) acrylate, the heating temperature is usually about 100 to 130 ° C., and the degree of depressurization is about 0.5 to 3 kPa.
本発明の製造方法により得られるイソボルニル（メタ）アクリレートを含む組成物において、イソボルニル（メタ）アクリレートのガスクロマトグラフィーによる純度は９９．５％以上である。イソボルニル（メタ）アクリレートのガスクロマトグラフィーによる純度は、９９．８％以上であることが好ましい。 In the composition containing isobornyl (meth) acrylate obtained by the production method of the present invention, the purity of isobornyl (meth) acrylate by gas chromatography is 99.5% or more. The purity of the isobornyl (meth) acrylate by gas chromatography is preferably 99.8% or more.
本発明の製造方法により得られるイソボルニル（メタ）アクリレートを含む組成物において、未反応の（メタ）アクリル酸の割合は０.０２重量％以下である。未反応の（メタ）アクリル酸の割合は、０．０１重量％以下であることが好ましく、０．００５重量％以下であることがより好ましく、０．００３重量％以下であることがさらに好ましい。 In the composition containing isobornyl (meth) acrylate obtained by the production method of the present invention, the proportion of unreacted (meth) acrylic acid is 0.02% by weight or less. The proportion of unreacted (meth) acrylic acid is preferably 0.01% by weight or less, more preferably 0.005% by weight or less, and even more preferably 0.003% by weight or less.
上記の製造方法により得られるイソボルニル（メタ）アクリレートを含む組成物は、未反応のアクリル酸が低減された高純度のイソボルニル（メタ）アクリレートを含むため、例えば、印刷用インク、硬化性塗料用バインダー、接着剤、光硬化反応希釈剤などの製品に使用する原料として有用である。 Since the composition containing isobornyl (meth) acrylate obtained by the above production method contains high-purity isobornyl (meth) acrylate in which unreacted acrylic acid is reduced, for example, a printing ink and a binder for a curable paint. It is useful as a raw material used in products such as adhesives and photocuring reaction diluents.
以下に実施例をあげて本発明を説明するが、本発明はこれら実施例によりなんら限定されるものではない。 The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
＜実施例１＞
＜イソボルニルアクリレートを含む反応混合物の製造＞
攪拌機、冷却器、温度計、サンプリング管、カンフェン４２０ｇ（３．０８ｍｏｌ）を計量した５００ｍｌ滴下ロート備えた１Ｌガラス製反応器に、アクリル酸２７１ｇ（３．７６ｍｏｌ）、重合防止剤としてハイドロキノンを８０ｍｇ、触媒として強酸性陽イオン交換樹脂（Ｄｏｗ Ｃｈｅｍｉｃａｌ社製、商品名「ＡＭＢＥＲＬＹＳＴ １５ ＤＲＹ」）を１６ｇ仕込んだ。反応容器内部の温度が４５〜５５℃となるように温度調節をしながら、滴下ロートからカンフェンを徐々に滴下した。カンフェンの滴下終了後、反応混合液を４５〜５５℃に温度を制御しながら１５時間撹拌混合した。次いで、ガスクロマトグラフィー（Ａｇｉｌｅｎｔ社製６８５０型）を用い、得られた反応混合物におけるイソボルニルアクリレートの反応転化率が８０％を超えていることを確認した後、触媒を濾別した。<Example 1>
<Production of reaction mixture containing isobornyl acrylate>
271 g (3.76 mol) of acrylic acid, 80 mg of hydroquinone as a polymerization inhibitor, in a 1 L glass reactor equipped with a stirrer, cooler, thermometer, sampling tube, and a 500 ml dropping funnel weighing 420 g (3.08 mol) of camphen. As a catalyst, 16 g of a strongly acidic cation exchange resin (manufactured by Dow Chemical Co., Ltd., trade name "AMBERLYST 15 DRY") was charged. Camphene was gradually added dropwise from the dropping funnel while adjusting the temperature so that the temperature inside the reaction vessel was 45 to 55 ° C. After the completion of dropping camphene, the reaction mixture was stirred and mixed at 45 to 55 ° C. for 15 hours while controlling the temperature. Next, gas chromatography (Type 6850 manufactured by Agilent) was used to confirm that the reaction conversion rate of isobornyl acrylate in the obtained reaction mixture exceeded 80%, and then the catalyst was filtered off.
なお、ガスクロマトグラフィーを用いたイソボルニル（メタ）アクリレートの反応転化率の算出方法は以下のとおりである。
［イソボルニル（メタ）アクリレートの反応転化率の算出方法］
イソボルニル（メタ）アクリレートの反応転化率（％）＝イソボルニル（メタ）アクリレートの面積／（イソボルニル（メタ）アクリレートの面積＋カンフェンの面積）×１００
ガスクロマトグラフィー条件は以下のとおりである。注入口は、ヒーター温度２６０℃、検出器は、ＦＩＤを使用し、ヒーター温度２６０℃に設定した。ＧＣカラムは、Ａｇｉｌｅｎｔ社製のＨＰ−１（長さ３０ｍ、内径０．３２ｍｍ、膜厚０．２５μｍ）を使用した。オーブンは、初期温度１００℃から毎分８℃で２６０℃までの昇温に設定した。スプリット比は、５０：１、線速度は、毎分３０ｃｍに設定した。打ち込み量は、０．２μｌとした。The method for calculating the reaction conversion rate of isobornyl (meth) acrylate using gas chromatography is as follows.
[Calculation method of reaction conversion rate of isobornyl (meth) acrylate]
Reaction conversion rate (%) of isobornyl (meth) acrylate = area of isobornyl (meth) acrylate / (area of isobornyl (meth) acrylate + area of camphene) × 100
The gas chromatography conditions are as follows. The inlet was set to a heater temperature of 260 ° C., and the detector was set to a heater temperature of 260 ° C. using FID. As the GC column, HP-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm) manufactured by Agilent was used. The oven was set to raise the temperature from an initial temperature of 100 ° C. to 260 ° C. at 8 ° C. per minute. The split ratio was set to 50: 1 and the linear velocity was set to 30 cm per minute. The driving amount was 0.2 μl.
＜イソボルニルアクリレートを含む組成物の製造＞
上記の触媒を濾別した反応混合物を、減圧下（０．５〜３ｋＰａ）、８５〜１２５℃で、蒸留することにより、未反応のアクリル酸とカンフェンを留去し、イソボルニルアクリレートを含む組成物を４９５ｇ得た。蒸留後のイソボルニルアクリレートを含む組成物において、イソボルニルアクリレートのガスクロマトグラフィーによる純度は９９．８％で、アクリル酸は０．０３重量％であった。続いて、蒸留後のイソボルニルアクリレートを含む組成物に、未反応のアクリル酸を中和するため、炭酸カリウム２．９ｇを加えて５０℃で６時間撹拌した後、炭酸カリウムを濾別してイソボルニルアクリレートを含む組成物を得た。得られたイソボルニルアクリレートを含む組成物において、イソボルニルアクリレートのガスクロマトグラフィーによる純度は９９．８％で、アクリル酸は０．００２重量％であった。<Manufacturing of composition containing isobornyl acrylate>
The reaction mixture obtained by filtering the above catalyst is distilled under reduced pressure (0.5 to 3 kPa) at 85 to 125 ° C. to distill off unreacted acrylic acid and camphene, and contain isobornyl acrylate. 495 g of the composition was obtained. In the composition containing the isobornyl acrylate after distillation, the purity of the isobornyl acrylate by gas chromatography was 99.8%, and the acrylic acid was 0.03% by weight. Subsequently, 2.9 g of potassium carbonate was added to the composition containing the distilled isobornyl acrylate to neutralize the unreacted acrylic acid, and the mixture was stirred at 50 ° C. for 6 hours, and then the potassium carbonate was filtered off and iso. A composition containing Bornyl acrylate was obtained. In the obtained composition containing the isobornyl acrylate, the purity of the isobornyl acrylate by gas chromatography was 99.8%, and the acrylic acid was 0.002% by weight.
なお、イソボルニル（メタ）アクリレートを含む組成物における、イソボルニル（メタ）アクリレートのガスクロマトグラフィーによる純度（％）および（メタ）アクリル酸の割合（重量％）の算出方法は以下のとおりである。
［イソボルニル（メタ）アクリレートのガスクロマトグラフィーによる純度（％）の算出方法］
イソボルニル（メタ）アクリレートの純度（％）は、前記反応転化率の算出で用いた装置条件にて分析を行い、面積百分率から算出した値とした。The method for calculating the purity (%) and the ratio (% by weight) of (meth) acrylic acid of isobornyl (meth) acrylate by gas chromatography in the composition containing isobornyl (meth) acrylate is as follows.
[Method of calculating purity (%) of isobornyl (meth) acrylate by gas chromatography]
The purity (%) of isobornyl (meth) acrylate was analyzed under the equipment conditions used in the calculation of the reaction conversion rate, and was used as a value calculated from the area percentage.
［（メタ）アクリル酸の割合（重量％）の算出方法］
（メタ）アクリル酸の割合（重量％）は、以下の（メタ）アクリル酸換算での遊離酸分（重量％）から算出した。（メタ）アクリル酸換算での遊離酸分（重量％）の測定は、１００ｍＬ三角フラスコにエタノール約５０ｍＬを採り、フェノールレッドを指示薬として、０．１ｍｏｌ／Ｌ水酸化ナトリウム水溶液で中和した後、次いで、当該溶液に、試料（イソボルニル（メタ）アクリレートを含む組成物）約３０ｇを精秤し、均一に溶解撹拌しながら０．１ｍｏｌ／Ｌ水酸化ナトリウム水溶液で滴定を行い、微赤色が約３０秒間消えない点を滴定終点とした。
（メタ）アクリル酸換算の遊離酸分（重量％）＝｛（０．１×ｆ×Ａ×Ｂ）／（Ｃ×１０００）｝×１００
Ａ：滴定量（ｍＬ）
ｆ：０．１ｍｏｌ／Ｌ水酸化ナトリウム水溶液の力価
Ｂ：定量される酸の分子量（アクリル酸の場合７２．０６、メタクリル酸の場合８６．０９）
Ｃ：試料の秤取量（ｇ）[Method of calculating the ratio (% by weight) of (meth) acrylic acid]
The ratio (% by weight) of (meth) acrylic acid was calculated from the following free acid content (% by weight) in terms of (meth) acrylic acid. To measure the free acid content (% by weight) in terms of (meth) acrylic acid, take about 50 mL of ethanol in a 100 mL triangular flask, neutralize with phenol red as an indicator, and then neutralize with 0.1 mol / L sodium hydroxide aqueous solution. Next, about 30 g of a sample (composition containing isobornyl (meth) acrylate) was precisely weighed into the solution, and titration was performed with a 0.1 mol / L sodium hydroxide aqueous solution while uniformly dissolving and stirring, and the slight red color was about 30. The point that did not disappear for a second was defined as the titration end point.
(Meta) Acrylic acid equivalent free acid content (% by weight) = {(0.1 × f × A × B) / (C × 1000)} × 100
A: Titration (mL)
f: Titer of 0.1 mol / L sodium hydroxide aqueous solution B: Molecular weight of acid to be quantified (72.06 for acrylic acid, 86.09 for methacrylic acid)
C: Weighing amount of sample (g)
＜実施例２＞
＜イソボルニルメタクリレートを含む反応混合物、およびイソボルニルメタクリレートを含む組成物の製造＞
上記の実施例１の＜イソボルニルアクリレートを含む反応混合物の製造＞において、アクリル酸２７１ｇ（３．７６ｍｏｌ）の替わりに、メタクリル酸３２４ｇ（３．７６ｍｏｌ）を用いたこと以外は、実施例１と同様の操作を行い、イソボルニルメタクリレートを含む反応混合物を得た。次いで、触媒を濾別した反応混合物を、減圧下（０．５〜３ｋＰａ）、９０〜１３５℃で、蒸留することにより、未反応のメタクリル酸とカンフェンを留去し、イソボルニルメタクリレートを含む組成物を５２１ｇ得た。蒸留後のイソボルニルメタクリレートを含む組成物において、イソボルニルメタクリレートのガスクロマトグラフィーによる純度は９９．９％で、メタクリル酸は０．０４重量％であった。続いて、蒸留後のイソボルニルメタクリレートを含む組成物に、炭酸カリウム３．３ｇを加えて３０℃で１０時間撹拌した後、炭酸カリウムを濾別してイソボルニルメタクリレートを含む組成物を得た。得られたイソボルニルメタクリレートを含む組成物において、イソボルニルメタクリレートのガスクロマトグラフィーによる純度は９９．９％で、アクリル酸は０．００３重量％であった。<Example 2>
<Production of a reaction mixture containing isobornyl methacrylate and a composition containing isobornyl methacrylate>
Example 1 except that 324 g (3.76 mol) of methacrylic acid was used instead of 271 g (3.76 mol) of acrylic acid in <Production of reaction mixture containing isobornyl acrylate> of Example 1 above. The same operation as in the above was carried out to obtain a reaction mixture containing isobornyl methacrylate. The reaction mixture from which the catalyst was filtered off was then distilled under reduced pressure (0.5 to 3 kPa) at 90 to 135 ° C. to distill off unreacted methacrylic acid and camphene and contain isobornyl methacrylate. 521 g of the composition was obtained. In the composition containing isobornyl methacrylate after distillation, the purity of isobornyl methacrylate by gas chromatography was 99.9%, and the methacrylic acid was 0.04% by weight. Subsequently, 3.3 g of potassium carbonate was added to the composition containing isobornyl methacrylate after distillation, and the mixture was stirred at 30 ° C. for 10 hours, and then potassium carbonate was filtered off to obtain a composition containing isobornyl methacrylate. In the obtained composition containing isobornyl methacrylate, the purity of isobornyl methacrylate by gas chromatography was 99.9%, and the acrylic acid was 0.003% by weight.
＜実施例３＞
＜イソボルニルアクリレートを含む反応混合物、およびイソボルニルアクリレートを含む組成物の製造＞
上記の実施例１の＜イソボルニルアクリレートを含む反応混合物の製造＞と同様の操作を行い、イソボルニルアクリレートを含む反応混合物を得た。次いで、実施例１の＜イソボルニルアクリレートを含む組成物の製造＞において、蒸留後のイソボルニルアクリレートを含む組成物に、未反応のアクリル酸を中和するため、炭酸カリウム２．９ｇを加えて５０℃で６時間撹拌した替わりに、炭酸カルシウム２．１ｇを加えて５０℃で２４時間撹拌したこと以外は、実施例１と同様の操作を行い、イソボルニルアクリレートを含む組成物を得た。得られたイソボルニルアクリレートを含む組成物において、イソボルニルアクリレートのガスクロマトグラフィーによる純度は９９．８％で、アクリル酸は０．０１重量％であった。<Example 3>
<Production of a reaction mixture containing isobornyl acrylate and a composition containing isobornyl acrylate>
The same operation as in <Production of reaction mixture containing isobornyl acrylate> in Example 1 above was carried out to obtain a reaction mixture containing isobornyl acrylate. Next, in <Production of a composition containing isobornyl acrylate> of Example 1, 2.9 g of potassium carbonate was added to the composition containing isobornyl acrylate after distillation in order to neutralize unreacted acrylic acid. In addition, instead of stirring at 50 ° C. for 6 hours, 2.1 g of calcium carbonate was added and the mixture was stirred at 50 ° C. for 24 hours. Obtained. In the obtained composition containing the isobornyl acrylate, the purity of the isobornyl acrylate by gas chromatography was 99.8%, and the acrylic acid was 0.01% by weight.
＜実施例４＞
＜イソボルニルアクリレートを含む反応混合物、およびイソボルニルアクリレートを含む組成物の製造＞
上記の実施例１の＜イソボルニルアクリレートを含む反応混合物の製造＞と同様の操作を行い、イソボルニルアクリレートを含む反応混合物を得た。次いで、実施例１の＜イソボルニルアクリレートを含む組成物の製造＞において、蒸留後のイソボルニルアクリレートを含む組成物に、未反応のアクリル酸を中和するため、炭酸カリウム２．９ｇを加えて５０℃で６時間撹拌した替わりに、炭酸ナトリウム２．２ｇを加えて５０℃で２４時間撹拌したこと以外は、実施例１と同様の操作を行い、イソボルニルアクリレートを含む組成物を得た。得られたイソボルニルアクリレートを含む組成物において、イソボルニルアクリレートのガスクロマトグラフィーによる純度は９９．８％で、アクリル酸は０．００３重量％であった。<Example 4>
<Production of a reaction mixture containing isobornyl acrylate and a composition containing isobornyl acrylate>
The same operation as in <Production of reaction mixture containing isobornyl acrylate> in Example 1 above was carried out to obtain a reaction mixture containing isobornyl acrylate. Next, in <Production of a composition containing isobornyl acrylate> of Example 1, 2.9 g of potassium carbonate was added to the composition containing isobornyl acrylate after distillation in order to neutralize unreacted acrylic acid. In addition, the same operation as in Example 1 was carried out except that 2.2 g of sodium carbonate was added and the mixture was stirred at 50 ° C. for 24 hours instead of stirring at 50 ° C. for 6 hours to obtain a composition containing isobornyl acrylate. Obtained. In the obtained composition containing the isobornyl acrylate, the purity of the isobornyl acrylate by gas chromatography was 99.8%, and the acrylic acid was 0.003% by weight.
＜比較例１＞
＜イソボルニルアクリレートを含む反応混合物、およびイソボルニルアクリレートを含む組成物の製造＞
上記の実施例１の＜イソボルニルアクリレートを含む反応混合物の製造＞と同様の操作を行い、イソボルニルアクリレートを含む反応混合物を得た。次いで、実施例１の＜イソボルニル（メタ）アクリレートを含む組成物の製造＞において、蒸留後のイソボルニルアクリレートを含む組成物に、未反応のアクリル酸を中和する工程を施さずに、再度、減圧下（０．５〜３ｋＰａ）、８５〜１２５℃で、蒸留を行ったこと以外は、実施例１と同様の操作を行い、イソボルニルアクリレートを含む組成物を得た。得られたイソボルニルアクリレートを含む組成物において、イソボルニルアクリレートのガスクロマトグラフィーによる純度は９９．８％で、アクリル酸は０．０３重量％であった。<Comparative example 1>
<Production of a reaction mixture containing isobornyl acrylate and a composition containing isobornyl acrylate>
The same operation as in <Production of reaction mixture containing isobornyl acrylate> in Example 1 above was carried out to obtain a reaction mixture containing isobornyl acrylate. Then, in <Production of a composition containing isobornyl (meth) acrylate> of Example 1, the composition containing isobornyl acrylate after distillation was again subjected to the step of neutralizing unreacted acrylic acid. The same operation as in Example 1 was carried out except that distillation was carried out at 85 to 125 ° C. under reduced pressure (0.5 to 3 kPa) to obtain a composition containing isobornyl acrylate. In the obtained composition containing the isobornyl acrylate, the purity of the isobornyl acrylate by gas chromatography was 99.8%, and the acrylic acid was 0.03% by weight.
Claims (3)
（メタ）アクリル酸とカンフェンを反応させることによりイソボルニル（メタ）アクリレートを含む反応混合物を得る工程と、
得られた反応混合物を固体塩基で中和する工程および蒸留する工程を含み、
イソボルニル（メタ）アクリレートのガスクロマトグラフィーによる純度が９９．５％以上であり、かつ未反応の（メタ）アクリル酸が０.０２重量％以下であるイソボルニル（メタ）アクリレートを含む組成物を得ることを特徴とするイソボルニル（メタ）アクリレートを含む組成物の製造方法。A method for producing a composition containing isobornyl (meth) acrylate.
A step of obtaining a reaction mixture containing isobornyl (meth) acrylate by reacting (meth) acrylic acid with camphene, and
The reaction mixture obtained comprises a step of neutralizing with a solid base and a step of distilling.
To obtain a composition containing isobornyl (meth) acrylate having a purity of isobornyl (meth) acrylate by gas chromatography of 99.5% or more and unreacted (meth) acrylic acid of 0.02% by weight or less. A method for producing a composition containing isobornyl (meth) acrylate.
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