JPH01186876A - Production of epoxidized (meth)acrylate - Google Patents
Production of epoxidized (meth)acrylateInfo
- Publication number
- JPH01186876A JPH01186876A JP1008388A JP1008388A JPH01186876A JP H01186876 A JPH01186876 A JP H01186876A JP 1008388 A JP1008388 A JP 1008388A JP 1008388 A JP1008388 A JP 1008388A JP H01186876 A JPH01186876 A JP H01186876A
- Authority
- JP
- Japan
- Prior art keywords
- meth
- acrylate
- oxidizing agent
- reaction
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title abstract description 18
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 27
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000007800 oxidant agent Substances 0.000 claims abstract description 23
- 239000003112 inhibitor Substances 0.000 claims abstract description 15
- -1 methacrylate compound Chemical class 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 4
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 abstract description 14
- 239000007788 liquid Substances 0.000 abstract description 14
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 abstract description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 abstract description 12
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 abstract description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 7
- 239000011347 resin Substances 0.000 abstract description 7
- 229920005989 resin Polymers 0.000 abstract description 7
- 239000002904 solvent Substances 0.000 abstract description 7
- XPCJYQUUKUVAMI-UHFFFAOYSA-N cyclohex-2-ene-1-carbaldehyde Chemical compound O=CC1CCCC=C1 XPCJYQUUKUVAMI-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 239000003822 epoxy resin Substances 0.000 abstract description 2
- 238000000465 moulding Methods 0.000 abstract description 2
- 229920000647 polyepoxide Polymers 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract 2
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 28
- 239000000178 monomer Substances 0.000 description 8
- 238000009835 boiling Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000006735 epoxidation reaction Methods 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- KATROYJQYZJDCU-UHFFFAOYSA-N cyclohexen-1-yl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CCCCC1 KATROYJQYZJDCU-UHFFFAOYSA-N 0.000 description 4
- 230000002401 inhibitory effect Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000976 ink Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 150000002432 hydroperoxides Chemical class 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-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
- 238000005406 washing Methods 0.000 description 2
- 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 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-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
- XYPISWUKQGWYGX-UHFFFAOYSA-N 2,2,2-trifluoroethaneperoxoic acid Chemical compound OOC(=O)C(F)(F)F XYPISWUKQGWYGX-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
- QFSYADJLNBHAKO-UHFFFAOYSA-N 2,5-dihydroxy-1,4-benzoquinone Chemical compound OC1=CC(=O)C(O)=CC1=O QFSYADJLNBHAKO-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- AGIJRRREJXSQJR-UHFFFAOYSA-N 2h-thiazine Chemical compound N1SC=CC=C1 AGIJRRREJXSQJR-UHFFFAOYSA-N 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- YNJSNEKCXVFDKW-UHFFFAOYSA-N 3-(5-amino-1h-indol-3-yl)-2-azaniumylpropanoate Chemical compound C1=C(N)C=C2C(CC(N)C(O)=O)=CNC2=C1 YNJSNEKCXVFDKW-UHFFFAOYSA-N 0.000 description 1
- DOFIAZGYBIBEGI-UHFFFAOYSA-N 3-sulfanylphenol Chemical compound OC1=CC=CC(S)=C1 DOFIAZGYBIBEGI-UHFFFAOYSA-N 0.000 description 1
- FYYIUODUDSPAJQ-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 2-methylprop-2-enoate Chemical compound C1C(COC(=O)C(=C)C)CCC2OC21 FYYIUODUDSPAJQ-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 241000577218 Phenes Species 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 1
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000004967 organic peroxy acids Chemical class 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- CZPZWMPYEINMCF-UHFFFAOYSA-N propaneperoxoic acid Chemical compound CCC(=O)OO CZPZWMPYEINMCF-UHFFFAOYSA-N 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Epoxy Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はエポキシ化された（メタ）アクリレート化合物
の製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for producing an epoxidized (meth)acrylate compound.
（メタ）アクリレート化合物は熱、紫外線、イオン化放
射線、ラジカル重合開始剤の存在下で容易に単独重合ま
たは他の不飽和基含有化合物と共重合することが可能で
、また塗料用樹脂の中間原料としても有用である。(Meth)acrylate compounds can be easily homopolymerized or copolymerized with other unsaturated group-containing compounds in the presence of heat, ultraviolet rays, ionizing radiation, and radical polymerization initiators, and can also be used as intermediate raw materials for paint resins. is also useful.
（従来の技術）
従来より各種のアクリル酸エステル類モノマーが知られ
ている。(Prior Art) Various acrylic acid ester monomers have been known.
例えばアクリル酸メチル、アクリル酸エチル、アクリル
酸２−エチルヘキシル等の単官能モノマーおよびトリメ
チロールプロパントリアクリレート、ペンタエリスリト
ールトリアクリレート等の多官能モノマーが一般的に知
られている。For example, monofunctional monomers such as methyl acrylate, ethyl acrylate, and 2-ethylhexyl acrylate, and polyfunctional monomers such as trimethylolpropane triacrylate and pentaerythritol triacrylate are generally known.
しかしながら、単官能モノマーは印刷インキおよび塗料
に用いた場合には硬化後の未反応モノマ−の臭気がはな
はだしく問題となる。However, when monofunctional monomers are used in printing inks and paints, the odor of unreacted monomers after curing becomes a serious problem.
また多官能モノマーは塗料および印刷インキの希釈剤と
して用いる場合には、樹脂に対して多量に使用する必要
があり、したがって樹脂が有する特性が失われるという
欠点を有している。Furthermore, when polyfunctional monomers are used as diluents for paints and printing inks, they have to be used in large amounts relative to resins, which has the disadvantage that the properties of the resins are lost.
その点
（式中Ｒは水素原子またはメチル基を表わす）で表わさ
れる（メタ）アクリレート化合物を酸化剤でエポキシ化
して得られる
（式中Ｒは水素原子またはメチル基を表わす）は低粘度
で、かつ、低臭気で広範囲に亘る樹脂への溶解性を有し
ており、このものはインキ、塗料、接着剤、被覆剤、成
型用樹脂の原料あるいは改質剤として有用である。In this respect, the (meth)acrylate compound represented by (in the formula, R represents a hydrogen atom or a methyl group) obtained by epoxidizing with an oxidizing agent (in the formula, R represents a hydrogen atom or a methyl group) has a low viscosity, Moreover, it has low odor and solubility in a wide range of resins, and is useful as a raw material or modifier for inks, paints, adhesives, coatings, and molding resins.
しかし、この−紋穴（Ｉｔ）で示されるエポキシ化され
た（メタ）アクリル酸エステルは極めて重合し易く製造
工程、貯蔵及び輸送中に熱、光およびその他の要因によ
ってしばしば重合することが知られている。However, it is known that this epoxidized (meth)acrylic ester represented by the symbol (It) is extremely susceptible to polymerization and is often caused by heat, light, and other factors during the manufacturing process, storage, and transportation. ing.
従来からアクリルモノマー用の一般的な重合禁止剤とし
てアントラキノン、ｐ−キノンなとのキノン類、及びそ
の誘導体、ニトロソ類、パラフェニレンジアミンなどの
アミン類、フェノチアジン。Conventionally, general polymerization inhibitors for acrylic monomers include quinones such as anthraquinone and p-quinone, their derivatives, nitrosos, amines such as paraphenylenediamine, and phenothiazine.
金属銅塩などが知られている。Metallic copper salts are known.
しかしながら−紋穴（ＩＩ）で示されるエポキシ化され
た（メタ）アクリル酸エステルに対しては重合禁止能が
十分でなく製造工程において・重合による収率の低下が
起きるという問題があった。However, the epoxidized (meth)acrylic acid ester represented by Monka (II) does not have sufficient ability to inhibit polymerization, and there is a problem in that a decrease in yield due to polymerization occurs in the manufacturing process.
また、−紋穴（ＩＩ）で示されるエポキシ化された（メ
タ）アクリル酸エステルは未だ、工業的規模で生産され
ていないこととも相代って、今迄該モノマーの重合禁止
剤に関する従来技術は全くないといっても過言ではない
。In addition, the epoxidized (meth)acrylic acid ester represented by Monana (II) has not yet been produced on an industrial scale, and until now there has been no prior art regarding polymerization inhibitors for this monomer. It is no exaggeration to say that there is no such thing at all.
（発明が解決しようとする問題点）
以上のような従来技術の状況に鑑み、本発明者らは前記
の課題を克服すべく、−紋穴（１１）で示されるエポキ
シ化された（メタ）アクリル酸エステルの高温における
有効な重合禁止剤について鋭党検討した結果、アミン類
、特にピペリジンが上記目的に極めて合致することを見
い出し、本発明を完成するに至った。(Problems to be Solved by the Invention) In view of the above-mentioned state of the prior art, the present inventors have attempted to overcome the above-mentioned problems by using an epoxidized (meta) As a result of extensive research into effective polymerization inhibitors for acrylic acid esters at high temperatures, the inventors discovered that amines, particularly piperidine, are highly compatible with the above-mentioned purpose, leading to the completion of the present invention.
（発明の構成）
本発明は
「−紋穴（Ｉ）
（式中Ｒは水素原子またはメチル基を表わす）で表わさ
れる（メタ）アクリレート化合物を酸化剤でエポキシ化
して
一ノ［イヒ式 （ＩＩ）
（式中Ｒは水素原子またはメチル基を表わす）で表わさ
れる化合物を製造する際に重合禁止剤としてピペリジン
を存在させることを特徴とするエポキシ化された（メタ
）アクリレート化合物の製造方法」
である。(Structure of the Invention) The present invention is based on the method of epoxidizing a (meth)acrylate compound represented by -Monken (I) (in the formula, R represents a hydrogen atom or a methyl group) with an oxidizing agent. ) (In the formula, R represents a hydrogen atom or a methyl group) A method for producing an epoxidized (meth)acrylate compound characterized by the presence of piperidine as a polymerization inhibitor when producing the compound. be.
以下に本発明のエポキシされた（メタ）アクリレート化
合物の製造方法について詳述する。The method for producing the epoxidized (meth)acrylate compound of the present invention will be described in detail below.
反応出発原料である一般式（Ｉ）
（式中Ｒは水素原子またはメチル基を表わす）で表わさ
れる（メタ）アクリレート化合物［以下シクロへキセニ
ル（メタ）アクリレートと称する］は無色透明の液体で
あり、エポキシ樹脂の中間原料などに用いられている。The starting material for the reaction, a (meth)acrylate compound represented by the general formula (I) (in which R represents a hydrogen atom or a methyl group) [hereinafter referred to as cyclohexenyl (meth)acrylate], is a colorless and transparent liquid. It is used as an intermediate raw material for epoxy resin.
工業的にはテトラヒドロベンズアルデヒドと（メタ）ア
クリル酸とのエステル化あるいはテトラヒドロベンズア
ルデヒドと（メタ）アクリル酸エステルとのエステ交換
反応により製造されている。この製造方法は特願昭６２
−１０８５６５号に開示されているようにテトラヒドロ
ベンジルアルコール／（メタ）アクリル酸または（メタ
）アクリル酸エステルのモル比１／１０〜１０／１で、
ｐ−トルエンスルホン酸、三フッ化ホウ素などを触媒と
して７５〜１２５℃の反応温度で行うものである。Industrially, it is produced by esterification of tetrahydrobenzaldehyde and (meth)acrylic acid or transesterification reaction of tetrahydrobenzaldehyde and (meth)acrylic acid ester. This manufacturing method was patented in 1986.
-108565 at a molar ratio of tetrahydrobenzyl alcohol/(meth)acrylic acid or (meth)acrylic acid ester from 1/10 to 10/1,
The reaction is carried out at a reaction temperature of 75 to 125° C. using p-toluenesulfonic acid, boron trifluoride, etc. as a catalyst.
また、シクロヘキセニル（メタ）アクリレートをエポキ
シ化して前記化合物（ＩＩ）にする際に用いる酸化剤は
不飽和結合をエポキシ化できるものなら何でもよく過ギ
酸、過酢酸、過プロピオン酸、ｍ−クロロ過安息香酸、
トリフルオロ過酢酸、過安息香酸、ターシャリブチルハ
イドロパーオキサイド、クミルハイドロパーオキサイド
、テトラリルハイドロバーオキサイド、ジイソプロピル
ベンゼンハイドロパーオキサイドなどの各種ハイドロパ
ーオキサイド類、過酸化水素などを例として挙げること
ができる。In addition, the oxidizing agent used when epoxidizing cyclohexenyl (meth)acrylate to form the compound (II) may be any oxidizing agent as long as it can epoxidize unsaturated bonds, such as performic acid, peracetic acid, perpropionic acid, m-chloroperoxylic acid, etc. benzoic acid,
Examples include various hydroperoxides such as trifluoroperacetic acid, perbenzoic acid, tert-butyl hydroperoxide, cumyl hydroperoxide, tetralyl hydroperoxide, diisopropylbenzene hydroperoxide, and hydrogen peroxide. Can be done.
酸化剤は触媒と併用してもよく、例えば、有機過酸を用
いる場合なら炭酸ソーダなどのアルカリや硫酸などの酸
を触媒として併用しうる。The oxidizing agent may be used in combination with a catalyst. For example, when an organic peracid is used, an alkali such as soda carbonate or an acid such as sulfuric acid may be used in combination as a catalyst.
同じく上記各種のハイドロパーオキサイド類を用いる場
合ならモリブデンヘキサカルボニルなど公知の触媒能を
有するものを、また、過酸化水素を用いる場合ならタン
グステン酸と苛性ソーダの混合物を併用することができ
る。Similarly, when using the above-mentioned various hydroperoxides, those having a known catalytic ability such as molybdenum hexacarbonyl can be used, and when using hydrogen peroxide, a mixture of tungstic acid and caustic soda can be used in combination.
反応をバッチで行なう場合は先ず９反応容器内にシレロ
へキセニル（メタ）アクリレートを所定量仕込み、この
中に必要に応じて触媒、安定剤を溶解させ、この中に前
記酸化剤を滴下して行なう。When carrying out the reaction in batches, first charge a predetermined amount of sillerohexenyl (meth)acrylate into a 9 reaction vessel, dissolve the catalyst and stabilizer as necessary in this, and dropwise drop the oxidizing agent into this. Let's do it.
酸化剤とシクロヘキセニル（メタ）アクリレートとの反
応モル比は理論的には１／１であるが、本発明の方法で
は０．１〜１０の範囲、好ましくは、０．５〜１０の範
囲、さらに好ましくは０゜８〜１．２の範囲が良い。The reaction molar ratio between the oxidizing agent and cyclohexenyl (meth)acrylate is theoretically 1/1, but in the method of the present invention, it is in the range of 0.1 to 10, preferably in the range of 0.5 to 10. More preferably, the range is 0°8 to 1.2°.
酸化剤とシクロへキセニル（メタ）アクリレートとのモ
ル比が１０を越える場合はシクロへキセニル（メタ）ア
クリレートの転化率および反応時間短縮、（メタ）アク
リレートの重合によるロスの減少という点で好ましいが
、過剰の酸化剤による副反応や酸化剤の選択率および未
反応の酸化剤を回収回収する場合に多大の費用を要する
。などの欠点がある。When the molar ratio of the oxidizing agent and cyclohexenyl (meth)acrylate exceeds 10, it is preferable in terms of the conversion rate of cyclohexenyl (meth)acrylate, shortening the reaction time, and reducing loss due to polymerization of (meth)acrylate. However, a large amount of cost is required due to side reactions caused by excess oxidizing agent, selectivity of oxidizing agent, and recovery of unreacted oxidizing agent. There are drawbacks such as.
逆に酸化剤とシクロへキセニル（メタ）アクリレートと
の反応のモル比が０．１以下の場合は酸化剤の選択率、
転化率、酸化剤による副反応を抑制するという点で好ま
しいが、（メタ）アクリレートの重合によるロス、未反
応のシクロヘキセニル（メタ）アクリレートを回収する
場合に多大の費用を要する。などの欠点がある。Conversely, if the molar ratio of the reaction between the oxidizing agent and cyclohexenyl (meth)acrylate is 0.1 or less, the selectivity of the oxidizing agent,
Although it is preferable in terms of conversion rate and suppressing side reactions caused by oxidizing agents, it requires loss due to polymerization of (meth)acrylate and a large amount of cost when recovering unreacted cyclohexenyl (meth)acrylate. There are drawbacks such as.
反応温度はエポキシ化反応が酸化剤の分解反応に優先す
るような上限値以下で行ない、たとえば、過酢酸を用い
る場合なら７０℃以下で、ターシャリブチルハイドロパ
ーオキサイドを用いる場合なら１５０℃以下が好ましい
。The reaction temperature is carried out below the upper limit so that the epoxidation reaction has priority over the decomposition reaction of the oxidizing agent. For example, when using peracetic acid, it is 70°C or less, and when using tert-butyl hydroperoxide, it is 150°C or less. preferable.
反応温度が低いと反応の完結までに長時間を要するので
、過酢酸を用いる場合なら０℃、ターシャリブチルハイ
ドロパーオキサイ、ドな用いる場合なら２０℃という下
限値以上で行うことが好ましい。If the reaction temperature is low, it will take a long time to complete the reaction, so it is preferable to carry out the reaction at a temperature higher than the lower limit of 0° C. if peracetic acid is used, and 20° C. if tert-butyl hydroperoxide is used.
また、エポキシ化反応の際、酸化剤からの副生などによ
る有機酸、アルコール、水でエポキシ基が開環してしま
う副反応が生じるので、副反応量が少なくなるような温
度を前記したような温度領域から選定して実施する。In addition, during the epoxidation reaction, a side reaction occurs in which the epoxy group is ring-opened with organic acids, alcohols, and water due to by-products from the oxidizing agent, so the temperature that reduces the amount of side reactions is set as described above. Select and implement from a temperature range.
本発明による方法は種々の圧力下で実施することができ
る。The method according to the invention can be carried out under various pressures.
本発明は一般的には常圧下で操作されるが、加圧または
低圧下でも実施できる。Although the invention generally operates under normal pressure, it can also be practiced under elevated or reduced pressure.
また、本発明の反応は溶媒存在下でも実施できる。溶媒
存在下での反応は反応粗液の粘度低下、酸化剤を希しや
くすることによる安定化などの効果がある。Moreover, the reaction of the present invention can also be carried out in the presence of a solvent. Reaction in the presence of a solvent has effects such as lowering the viscosity of the reaction crude liquid and stabilizing it by making the oxidizing agent more diluted.
使用される溶媒としてはベンゼン、トルエン、キシレン
など芳香族化合物、クロロフォルム、ジメチルクロライ
ド、四塩化炭素、クロルベンゼンなどのハロゲン化物、
酢酸エチル、酢酸ブチル、などのエステル化物、アセト
ン、メチルエチルケトンなどのケトン化合物、１．２−
ジメトキシエタンなどのエーテル化合物などを用いるこ
とができる。Solvents used include aromatic compounds such as benzene, toluene, and xylene; halides such as chloroform, dimethyl chloride, carbon tetrachloride, and chlorobenzene;
Esterified products such as ethyl acetate and butyl acetate, ketone compounds such as acetone and methyl ethyl ketone, 1.2-
Ether compounds such as dimethoxyethane can be used.
溶媒の使用量はシクロへキセニル（メタ）アクリレート
に対して０．５心５倍量が好ましい。The amount of solvent to be used is preferably 0.5 times the amount of cyclohexenyl (meth)acrylate.
０．５倍量より少ない場合は酸化剤を希しゃくすること
による安定化などの効果が少なく、逆に５倍量より多く
しても安定化効果はそれ程アップせず溶媒の回収に多大
の費用を要するので無駄となる。If the amount is less than 0.5 times, there will be little stabilization effect by diluting the oxidizing agent, and conversely, if the amount is more than 5 times, the stabilizing effect will not improve much and it will cost a lot to recover the solvent. It is a waste because it requires .
本発明のポイントは上記のようなエポキシ化反応を行う
際に出発原料であるシクロヘキセニル（メタ）アクリレ
ートが重合するのを防止するためにピペリジンを添加す
ることにある。The key point of the present invention is to add piperidine to prevent the starting material cyclohexenyl (meth)acrylate from polymerizing during the epoxidation reaction as described above.
なお、ピペリジンは出発原料であるシクロヘキセニル（
メタ）アクリレートおよび反応生成物であるエポキシ化
物の両方に対して重合禁止効果を有している。Note that piperidine is the starting material cyclohexenyl (
It has a polymerization inhibiting effect on both meth)acrylate and the epoxide product which is the reaction product.
なお、ピペリジンは従来から使用されていた重合禁止剤
と併用してもよい。Note that piperidine may be used in combination with a conventionally used polymerization inhibitor.
併用される重合禁止剤としてはハイドロキノン、Ｐ−メ
トキシフェノール、２．４−ジメチル−６−ｔ−ブチル
フェノール、３−ヒドロキシチオフェノール、α−ニト
ロソ−β−ナフ）−／１／、Ｐ−ベンゾキノン、フェネ
、チアジン、２．５−ジヒドロキシ−Ｐ−キノン、銅塩
等を使用することができるが、安定性などの点でハイド
ロキノン、Ｐ−メトキシフェノールが好ましい。Polymerization inhibitors used in combination include hydroquinone, P-methoxyphenol, 2,4-dimethyl-6-t-butylphenol, 3-hydroxythiophenol, α-nitroso-β-naph)-/1/, P-benzoquinone, Phene, thiazine, 2,5-dihydroxy-P-quinone, copper salt, etc. can be used, but hydroquinone and P-methoxyphenol are preferred from the viewpoint of stability.
ピペリジンを主とする重合禁止剤の使用量は出発原料で
あるシクロヘキセニル（メタ）アクリレートに対して０
．００１〜５．０重量％、好ましくは０．０１〜１．０
重量％である。The amount of polymerization inhibitor, mainly piperidine, used is 0 relative to the starting material cyclohexenyl (meth)acrylate.
．． 001-5.0% by weight, preferably 0.01-1.0
Weight%.
添加量が０．００１重量％未満の場合は重合禁止効果が
小さく、逆に５．０重量％以上添加しても効果は向上し
ないので無駄となる。If the amount added is less than 0.001% by weight, the effect of inhibiting polymerization will be small, and conversely, if the amount added is 5.0% by weight or more, the effect will not improve and it will be wasted.
ピペリジンを主とする重合禁止剤の添加はエポキシ化反
応を行なう直前にシクロへキセニル（メタ）アクリレー
トに溶解させて行う。A polymerization inhibitor mainly consisting of piperidine is added by dissolving it in cyclohexenyl (meth)acrylate immediately before carrying out the epoxidation reaction.
また、反応粗液を精製する際にさらに重合禁止剤を添加
することは重合禁止に有効である。Furthermore, adding a polymerization inhibitor when purifying the reaction crude liquid is effective for inhibiting polymerization.
反応の終点の確認は残存する酸化剤濃度の測定およびガ
スクロマトグラフィーによるのが良い。The end point of the reaction is preferably confirmed by measuring the concentration of the remaining oxidizing agent and by gas chromatography.
反応終了後のエポキシ化反応粗液は溶媒、低沸点物質、
未反応原料、触媒などの除去、中和、吸着剤やイオン交
換樹脂処理などによって精製することができる。After the reaction is completed, the epoxidation reaction crude liquid contains a solvent, a low boiling point substance,
It can be purified by removing unreacted raw materials, catalysts, etc., neutralizing it, and treating it with an adsorbent or ion exchange resin.
必要があれば、さらにフラッシュ蒸溜、精密蒸溜などに
よって精製しても良い。If necessary, it may be further purified by flash distillation, precision distillation, etc.
精製処理は最終製品の品質要求に応じて選択することが
できる。Purification treatments can be selected depending on the quality requirements of the final product.
精製処理しなくても使用に耐える品質の最終製品が得ら
れる場合は省略することもできる。If a final product of usable quality can be obtained without purification, it may be omitted.
特に酸化剤として有機酸を用いる場合、反応粗液を中和
せずに低沸点成分を除去すると（メタ）アクリレートの
重合によるロスが大であるので、低沸点成分を除去する
前に中和する方が好ましい。Particularly when using an organic acid as an oxidizing agent, removing low-boiling components without neutralizing the crude reaction solution will result in large losses due to polymerization of (meth)acrylate, so neutralize the low-boiling components before removing them. is preferable.
中和に用いるアルカリ水溶液としては例えば、ＮａＯＨ
％ＫＯＨ，Ｋ Ｃｏ 、Ｎａ２ Ｃ０、Ｎａ
ＨＣＯ、ＫＨＣＯ、ＮＨ３
などのようなアルカリ性物質の水溶液を使用することが
できる。Examples of alkaline aqueous solutions used for neutralization include NaOH
%KOH, K Co , Na2 C0, Na
Aqueous solutions of alkaline substances such as HCO, KHCO, NH3, etc. can be used.
使用する際の濃度はひろい範囲で自由に選択することが
できる。The concentration used can be freely selected from a wide range.
分液性の点からＮ ａ ＣＯ３水溶液、ＮａＨＣＯ
３水溶液を用いるのが好ましい。From the viewpoint of liquid separation, NaCO3 aqueous solution, NaHCO
3. Preferably, an aqueous solution is used.
中和後、水洗せずに低沸点成分を除去し、塔底液を製品
にすると製品中に中和塩が残存することになるので中和
後水洗することが好ましい。After neutralization, if low-boiling components are removed without washing with water and the bottom liquid is made into a product, neutralized salts will remain in the product, so it is preferable to wash with water after neutralization.
中和および水洗は１０〜９０℃、好ましくは１０〜５０
℃の温度範囲で行うのが良い。Neutralization and water washing at 10-90°C, preferably 10-50°C
It is best to perform this in the temperature range of ℃.
中和あるいは水洗を行った反応粗液から低沸点成分を除
去するには重合禁止剤を添加した後薄膜式蒸発器などを
用いるのが良い。In order to remove low-boiling components from the reaction crude liquid that has been neutralized or washed with water, it is preferable to use a thin film evaporator or the like after adding a polymerization inhibitor.
本発明の方法を適用することができる装置の材質はステ
ンレス、グラスライニング鋼などが望ましいが、普通の
鉄材などでも構わない。The material of the apparatus to which the method of the present invention can be applied is preferably stainless steel, glass-lined steel, etc., but ordinary iron materials may also be used.
以下に実施例を示し本発明の効果を具体的に説明するが
、本発明はこれらの実施例によって限定されるものでは
ない。EXAMPLES The effects of the present invention will be specifically explained below with reference to Examples, but the present invention is not limited to these Examples.
〔実施例１〕および〔比較例１〜６〕
シクロヘキセニルメタクリレート４０％、これをエポキ
シ化した３、４工ポキシシクロヘキシルメチルメタクリ
レート６０％の混合溶液に対する重合禁止能を比較した
結果を第−表に示す。[Example 1] and [Comparative Examples 1 to 6] Table 1 shows the results of comparing the polymerization inhibition ability of a mixed solution of 40% cyclohexenyl methacrylate and 60% tertiary and quaternary polycyclohexyl methyl methacrylate obtained by epoxidizing this. show.
なお、温度はいずれも１３０℃、雰囲気は比較例１が窒
素である以外はいずれも空気である。The temperature was 130° C. in all cases, and the atmosphere was air in all cases except for Comparative Example 1, in which nitrogen was used.
また、この組成は薄膜蒸発器で反応粗液を漏出させる際
の液組成に近い。Moreover, this composition is close to the liquid composition when the reaction crude liquid is leaked from a thin film evaporator.
第−表
第一表から明らかなようにピペリジンは顕著な重合禁止
効果を有している。As is clear from Table 1, piperidine has a remarkable polymerization inhibiting effect.
なお、第−表の値は温度１３０℃で１１０００ｐｐの重
合禁止剤を添加した時のものである。The values in Table 1 are those obtained when 11,000 pp of polymerization inhibitor was added at a temperature of 130°C.
〔実施例２〕および〔比較例７〕
温度１６０℃における３、４エポキシシクロヘキシルメ
チルメタクリレートに対する重合禁止能を重合禁止剤を
添加した時と添加しない時について比較した結果を第二
表に示す。[Example 2] and [Comparative Example 7] Table 2 shows the results of comparing the polymerization inhibition ability for 3,4 epoxycyclohexylmethyl methacrylate at a temperature of 160° C. with and without the addition of a polymerization inhibitor.
第二表
（以下余白）
〔実施例３〕
冷却用のジャケット付きの内容量２．５ｊの反応器にシ
クロへキセニルメタクリレート３００ｇ。Table 2 (blank below) [Example 3] 300 g of cyclohexenyl methacrylate was placed in a reactor with an internal capacity of 2.5 j and equipped with a cooling jacket.
酢酸エチル６００ｇ、ピペリジン２．８ｇを加えた後過
酢酸の３０％酢酸エチル溶液４７８ｇを２時間かけて滴
下した。After adding 600 g of ethyl acetate and 2.8 g of piperidine, 478 g of a 30% solution of peracetic acid in ethyl acetate was added dropwise over 2 hours.
滴下中は反応温度が４０℃になるようにジャケットに流
す温水の温度を４０℃よりやや高めに調節した。During the dropping, the temperature of the hot water flowing through the jacket was adjusted to be slightly higher than 40°C so that the reaction temperature was 40°C.
滴下終了後も反応温度を４０℃に５時間保ち、反応を終
了させた。After the dropwise addition was completed, the reaction temperature was maintained at 40° C. for 5 hours to complete the reaction.
この時の反応粗液中の過酢酸の濃度は１％以下であった
。At this time, the concentration of peracetic acid in the reaction crude liquid was 1% or less.
反応粗液１３７８ｇを６％Ｎ ａ １（ＣＯ３水溶液３
５８３ｇで洗浄した。1378 g of the reaction crude liquid was mixed with 6% Na 1 (CO3 aqueous solution 3
Washed with 583g.
分液後、上層を水１３７８ｇで洗浄し、分液した後上層
液の低沸点成分の除去を行った。After liquid separation, the upper layer was washed with 1378 g of water, and after separation, low-boiling components of the upper layer liquid were removed.
低沸点成分の除去は薄膜蒸発器を用い、ピペリジンの添
加量は５００ｐｐｍ、圧力２０Ｔｏｒｒ。A thin film evaporator was used to remove low boiling point components, the amount of piperidine added was 500 ppm, and the pressure was 20 Torr.
温度９０〜９５℃の条件で行った。The test was carried out at a temperature of 90 to 95°C.
製品化は薄膜蒸発器を用い、圧力５Ｔｏｒｒ。Commercialization uses a thin film evaporator at a pressure of 5 Torr.
温度９０〜９５℃の条件で行ない、未反応原料であるシ
クロへキセニルメタクリレートを除去した。The reaction was carried out at a temperature of 90 to 95°C to remove cyclohexenyl methacrylate, which is an unreacted raw material.
収率はシクロヘキセニルメタクリレート基準で９３％で
あった。The yield was 93% based on cyclohexenyl methacrylate.
Claims (1)
剤でエポキシ化して 一般式（II） ▲数式、化学式、表等があります▼（II） （式中Ｒは水素原子またはメチル基を表 わす）で表わされる化合物を製造する際に重合禁止剤と
してピペリジンを存在させることを特徴とするエポキシ
化された（メタ）アクリレート化合物の製造方法。[Claims] General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R represents a hydrogen atom or a methyl group) A (meth)acrylate compound is epoxied with an oxidizing agent. The general formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R represents a hydrogen atom or a methyl group) When producing a compound represented by the following, piperidine is present as a polymerization inhibitor. A method for producing an epoxidized (meth)acrylate compound, characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1008388A JPH01186876A (en) | 1988-01-20 | 1988-01-20 | Production of epoxidized (meth)acrylate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1008388A JPH01186876A (en) | 1988-01-20 | 1988-01-20 | Production of epoxidized (meth)acrylate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01186876A true JPH01186876A (en) | 1989-07-26 |
Family
ID=11740454
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1008388A Pending JPH01186876A (en) | 1988-01-20 | 1988-01-20 | Production of epoxidized (meth)acrylate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01186876A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997002311A1 (en) * | 1995-06-30 | 1997-01-23 | Origin Electric Company, Limited | Surface-coated molded plastic articles having good durability |
| WO2011112643A2 (en) | 2010-03-09 | 2011-09-15 | Henkel Corporation | Cationic uv-crosslinkable acrylic polymers for pressure sensitive adhesives |
-
1988
- 1988-01-20 JP JP1008388A patent/JPH01186876A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997002311A1 (en) * | 1995-06-30 | 1997-01-23 | Origin Electric Company, Limited | Surface-coated molded plastic articles having good durability |
| US6048617A (en) * | 1995-06-30 | 2000-04-11 | Origin Electric Company, Limited | Surface-coated molded plastic articles having good durability |
| WO2011112643A2 (en) | 2010-03-09 | 2011-09-15 | Henkel Corporation | Cationic uv-crosslinkable acrylic polymers for pressure sensitive adhesives |
| US8796350B2 (en) | 2010-03-09 | 2014-08-05 | Henkel US IP LLC | Cationic UV-crosslinkable acrylic polymers for pressure sensitive adhesives |
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