JPH03120263A - Preparation of (meth)acrylate compound - Google Patents
Preparation of (meth)acrylate compoundInfo
- Publication number
- JPH03120263A JPH03120263A JP25694489A JP25694489A JPH03120263A JP H03120263 A JPH03120263 A JP H03120263A JP 25694489 A JP25694489 A JP 25694489A JP 25694489 A JP25694489 A JP 25694489A JP H03120263 A JPH03120263 A JP H03120263A
- Authority
- JP
- Japan
- Prior art keywords
- meth
- reaction
- acrylic acid
- raw material
- amount
- 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.)
- Granted
Links
- -1 acrylate compound Chemical class 0.000 title claims description 17
- 238000002360 preparation method Methods 0.000 title description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 23
- ZIUCSKNITYCKFX-UHFFFAOYSA-N methanol;7-oxabicyclo[4.1.0]heptane Chemical compound OC.C1CCCC2OC21 ZIUCSKNITYCKFX-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 13
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 33
- 239000003054 catalyst Substances 0.000 abstract description 14
- 238000005886 esterification reaction Methods 0.000 abstract description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 7
- 229920005989 resin Polymers 0.000 abstract description 7
- 239000011347 resin Substances 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 238000000465 moulding Methods 0.000 abstract description 2
- 150000002148 esters Chemical class 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 description 17
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 12
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000003112 inhibitor Substances 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 238000005809 transesterification reaction Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 5
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000000976 ink Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- YXAOOTNFFAQIPZ-UHFFFAOYSA-N 1-nitrosonaphthalen-2-ol Chemical compound C1=CC=CC2=C(N=O)C(O)=CC=C21 YXAOOTNFFAQIPZ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- QFSYADJLNBHAKO-UHFFFAOYSA-N 2,5-dihydroxy-1,4-benzoquinone Chemical compound OC1=CC(=O)C(O)=CC1=O QFSYADJLNBHAKO-UHFFFAOYSA-N 0.000 description 2
- DOFIAZGYBIBEGI-UHFFFAOYSA-N 3-sulfanylphenol Chemical compound OC1=CC=CC(S)=C1 DOFIAZGYBIBEGI-UHFFFAOYSA-N 0.000 description 2
- NIJZFHNDUJXJMR-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethanol Chemical compound C1C(CO)CCC2OC21 NIJZFHNDUJXJMR-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- MGPOZFJWYRNWBH-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-6-ylmethanol Chemical compound C1CCCC2OC21CO MGPOZFJWYRNWBH-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-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
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 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
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000011521 glass Substances 0.000 description 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 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- GPKUICFDWYEPTK-UHFFFAOYSA-N methoxycyclohexatriene Chemical group COC1=CC=C=C[CH]1 GPKUICFDWYEPTK-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 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
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は新規な（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 a novel (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でき、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 light, ionizing radiation, or radical polymerization initiators, and are also useful as intermediate raw materials for paint resins. .
（従来の技術） 従来より各種のアクリル酸エステル類が知られている。(Conventional technology) Various acrylic esters have been known so far.
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.
（発明が解決しようとする課題）
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ーの臭気がはな
はだしく問題となる。(Problems to be Solved by the Invention) 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, and therefore have the disadvantage that the properties of the resins are lost.
本発明者らは、鋭意研究の結果、３．４−エポキシシク
ロヘキサンメタノールに（メタ）アクリル酸または（メ
タ）アクリル酸エステルを反応させることにより低粘度
で、かつ、低臭気で広範囲にわたる樹脂への溶解性を有
する新規な三官能（メタ）アクリル酸エステルを得るに
至った。As a result of extensive research, the present inventors have discovered that by reacting 3.4-epoxycyclohexanemethanol with (meth)acrylic acid or (meth)acrylic acid ester, a wide range of resins can be produced with low viscosity and low odor. A novel trifunctional (meth)acrylic acid ester with solubility was obtained.
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。This product is useful as a raw material or modifier for inks, paints, adhesives, coatings, and molding resins.
（発明の構成）
すなわち、本発明は
［３，４−エポキシシクロヘキサンメタノールに（メタ
）アクリル酸または（メタ）アクリル酸エステルを反応
させることを特徴とする下記の一般式（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の製造方法」
である。(Structure of the Invention) That is, the present invention provides the following general formula (I) [wherein R represents a hydrogen atom or a methyl group.
以下に本発明の（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 (meth)acrylate compound of the present invention will be described in detail below.
反応出発原料である３、４−エポキシシクロヘキサンメ
タノールは以下のような構造式で示され、無色透明、蒸
気圧１３０℃／ １０ Ｔ 。3,4-Epoxycyclohexanemethanol, which is a starting material for the reaction, has the following structural formula, is colorless and transparent, and has a vapor pressure of 130°C/10T.
ｒｒの性状を有する環式アルコールであり、エポキシ樹
脂の原料などに用いられている。It is a cyclic alcohol with the properties of rr, and is used as a raw material for epoxy resins.
工業的にはテトラヒドロベンジルアルコールを有機過酸
でエポキシ化させることにより製造されている。Industrially, it is produced by epoxidizing tetrahydrobenzyl alcohol with an organic peracid.
一方、アクリル酸はアクリロニトリルを硫酸で加水分解
するすることにより工業的に大量に製造されている。On the other hand, acrylic acid is industrially produced in large quantities by hydrolyzing acrylonitrile with sulfuric acid.
また、メタクリル酸はメタクリル酸メチルを製造する際
の副生物として得られている。In addition, methacrylic acid is obtained as a by-product during the production of methyl methacrylate.
これらアクリル酸、メタクリル酸は各種樹脂、ポリマー
エマルジョンなどを製造する場合に単独重合または共重
合モノマーとして用いられる凡用モノマーであり、アク
リル酸は無色の酢酸に類似した液体で沸点１４１．７℃
、水に可溶であり、メタクリル酸は無色透明な沸点１５
９〜１６３℃の液体である。これらは共に重合しやすい
。These acrylic acid and methacrylic acid are common monomers used as homopolymerization or copolymerization monomers when manufacturing various resins, polymer emulsions, etc. Acrylic acid is a colorless liquid similar to acetic acid with a boiling point of 141.7°C.
, soluble in water, methacrylic acid is colorless and transparent with a boiling point of 15
It is a liquid with a temperature of 9 to 163°C. Both of these are likely to polymerize.
３．４−エポキシシクロヘキサンメタノールと（メタ）
アクリル酸とのエステル化により（メタ）アクリレート
化合物の製造を行なう場合には触媒を使用し、生成する
水を連続的に系外へ取り出すことにより反応は促進され
る。3.4-Epoxycyclohexane methanol and (meth)
When a (meth)acrylate compound is produced by esterification with acrylic acid, the reaction is accelerated by using a catalyst and continuously removing the produced water from the system.
反応をバッチで行なう場合は先ず、反応容器内に３．４
−エポキシシクロヘキサンメタノールを所定量仕込み、
この中に前記好適量の触媒を溶解させ、この中にアクリ
ル酸またはメタクリル酸を仕込み、行なう。When carrying out the reaction in batches, first add 3.4 ml to the reaction vessel.
-Preparing a predetermined amount of epoxycyclohexane methanol,
The suitable amount of the catalyst is dissolved in this, and acrylic acid or methacrylic acid is charged therein.
３．４−エポキシシクロヘキサンメタノールと（メタ）
アクリル酸とのエステル化反応におけるモル比は理論的
には１／１であるが、本発明などのように実際には１／
１０〜１０／１の範囲、好ましくは１／１〜１／３の範
囲である。3.4-Epoxycyclohexane methanol and (meth)
The molar ratio in the esterification reaction with acrylic acid is theoretically 1/1, but in reality, as in the present invention, it is 1/1.
It is in the range of 10 to 10/1, preferably in the range of 1/1 to 1/3.
エステル化反応のモル比が３，４−エポキシシクロヘキ
サンメタノール／（メタ）アクリル酸−１／１０未満の
場合は３．４−エポキシシクロへ午サンメタノールの選
択率および転化率の点で好ましいが、アクリル酸または
メタクリル酸自身の重合による損失が大きく、また、未
反応のアクリル酸またはメタクリル酸の回収に多大の費
用を要する、などの欠点がある。If the molar ratio of the esterification reaction is less than 1/10 of 3,4-epoxycyclohexane methanol/(meth)acrylic acid, it is preferable in terms of the selectivity and conversion rate of 3,4-epoxycyclohexane methanol. There are drawbacks such as large losses due to polymerization of acrylic acid or methacrylic acid itself, and large costs required to recover unreacted acrylic acid or methacrylic acid.
逆にエステル化反応のモル比が３．４−エポキシシクロ
ヘキサンメタノール／（メタ）アクリル酸−１０／１を
越える場合はアクリル酸またはメタクリル酸の重合によ
るロスは減少するが、３゜４−エポキシシクロヘキサン
メタノールの回収に多大のエネルギーを要するので好ま
しくない。Conversely, when the molar ratio of esterification reaction exceeds 3.4-epoxycyclohexane methanol/(meth)acrylic acid - 10/1, the loss due to polymerization of acrylic acid or methacrylic acid decreases, but 3.4-epoxycyclohexane methanol/(meth)acrylic acid This is not preferred because it requires a large amount of energy to recover methanol.
ここで使用する触媒は硫酸、ｐ−トルエンスルホン酸、
三フッ化ホウ素等の通常用いられているエステル化触媒
として公知のものから任意に選択して使用することがで
きるが、取扱いのし易さ、腐蝕性が小さいなどの点から
ｐ−トルエンスルホン酸が特に好ましい。The catalysts used here are sulfuric acid, p-toluenesulfonic acid,
Any commonly used esterification catalyst such as boron trifluoride can be selected and used, but p-toluenesulfonic acid is preferred due to its ease of handling and low corrosivity. is particularly preferred.
触媒の使用量は出発原料に対して０．００１〜１０重量
％、好ましくは０．０１〜１．０重量％である。The amount of catalyst used is 0.001 to 10% by weight, preferably 0.01 to 1.0% by weight, based on the starting material.
触媒の使用量がｏ、ｏｏｉ重量％より少ない場合は反応
速度が遅かったり、収率が悪いなどの不都合があり、逆
に１０重量％より多くしても反応促進効果は改善される
訳ではないので、無意味である。エステル化反応の進行
とともに必然的に水が生成するので、これを系外に除去
してやる必要がある。反応により生成した水を分離する
にはそのまま蒸留により分離してもよいが、例えばトル
エン、ベンゼン、キシレン、ｎ−へキサン、メチルイソ
ブチルケトンなどの水と共沸混合物をつくり、実質的に
は水と互いに混合しない有機溶媒をエントレーナーとし
て用いるのが有利である。If the amount of catalyst used is less than o or ooi weight%, there will be disadvantages such as slow reaction rate or poor yield, and conversely, if it is more than 10% by weight, the reaction promotion effect will not be improved. Therefore, it is meaningless. As water is inevitably produced as the esterification reaction progresses, it is necessary to remove it from the system. In order to separate the water produced by the reaction, it is possible to separate it directly by distillation, but for example, an azeotrope is created with water such as toluene, benzene, xylene, n-hexane, methyl isobutyl ketone, etc. It is advantageous to use organic solvents as entrainers which are immiscible with each other.
エントレーナーは最初の仕込みの段階で添加しておくの
がよい。It is best to add the entrainer during the initial preparation stage.
エントレーナーの使用量は理論量に対して１〜１０倍で
あり、好ましくは２〜５倍である。The amount of entrainer used is 1 to 10 times the theoretical amount, preferably 2 to 5 times.
水とともに留出したエントレーナーは分液して循環使用
することが出来る。The entrainer distilled together with water can be separated and recycled.
反応温度は、反応時間の短縮と重合防止の点から６５〜
１５０℃、好ましくは７５〜１２０℃で行なわれるのが
有利である。The reaction temperature is set at 65 to 65°C from the viewpoint of shortening the reaction time and preventing polymerization.
Advantageously, it is carried out at 150°C, preferably 75-120°C.
（メタ）アクリル酸の熱重合を防止するために重合禁止
剤を添加する。A polymerization inhibitor is added to prevent thermal polymerization of (meth)acrylic acid.
このような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−ナフトール、Ｐ−ペンゾキノン、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
フェニルが好ましい。Examples of such polymerization inhibitors include hydroquinone, P-methoxyphenol, 2,4-dimethyl-6-t-butylphenol, 3-hydroxythiophenol, α-nitroso-β-naphthol, P-penzoquinone, and 2,5-dihydroxy -P-quinone, copper salt, etc. can be used, but hydroquinone and P-methoxyphenyl are preferred from the viewpoint of stability.
上記のような重合禁止剤の使用量は（メタ）アクリル酸
に対して０．００１〜５．０重量％、好ましくは０．０
１〜１．０重量％である。The amount of the polymerization inhibitor used is 0.001 to 5.0% by weight, preferably 0.0% by weight based on (meth)acrylic acid.
It is 1 to 1.0% by weight.
重合禁止剤の添加量が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 of the polymerization inhibitor 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.
重合禁止剤の添加はエステル化反応を行なう直前に（メ
タ）アクリル酸中に溶解させる。The polymerization inhibitor is added by dissolving it in (meth)acrylic acid immediately before carrying out the esterification reaction.
反応は常圧か又は若干減圧した状態でおこなうのが好適
である。The reaction is preferably carried out at normal pressure or under slightly reduced pressure.
反応の終点の確認は脱水量あるいはガスクロ分析による
のが良い。The end point of the reaction can be confirmed by the amount of dehydration or gas chromatography.
反応終了後の混合液から製品である（メタ）アクリレー
ト化合物を分離するのは薄膜蒸発器などを用いた蒸留に
よるのがよい。The product (meth)acrylate compound is preferably separated from the mixed solution after the reaction is completed by distillation using a thin film evaporator or the like.
反応は常圧か、若干減圧した状態で行なうので、耐圧容
器は必要としないが、ステンレス鋼、グラスライニング
鋼板などの耐蝕性の材料を用いるのがよい。Since the reaction is carried out at normal pressure or under slightly reduced pressure, a pressure-resistant container is not required, but it is preferable to use a corrosion-resistant material such as stainless steel or glass-lined steel plate.
また、以上に述べたようなエステル化反応だけてなく化
合物（１）を３，４−エポキシシクロヘキサンメタノー
ルと（メタ）アクリル酸エステルとからエステル交換反
応によっても製造することが可能である。In addition to the esterification reaction described above, compound (1) can also be produced by transesterification reaction from 3,4-epoxycyclohexane methanol and (meth)acrylic acid ester.
この場合使用する（メタ）アクリル酸エステルとしては
メチル、エチル、ｎ−プロピル、ｉ−プロピル、ブチル
などの公知の（メタ）アクリル酸エステルを使用するこ
とができるが、中でもコスト、入手のし易さおよびエス
テル交換反応に伴って生成してくるアルコールの除去の
し品さなどを考慮するとメタクリル酸メチル、アクリル
酸メチルなどが好ましい。As the (meth)acrylic ester used in this case, known (meth)acrylic esters such as methyl, ethyl, n-propyl, i-propyl, and butyl can be used. Methyl methacrylate, methyl acrylate, and the like are preferred in consideration of the stability and quality of removal of alcohol produced in the transesterification reaction.
３．４−エポキシシクロヘキサンメタノールと（メタ）
アクリル酸エステルとのエステル交換反応のモル比は理
論的には１／１であるが、本発明などのように実際には
１／１ｏ〜１ｏ／１の範囲、好ましくは１／１〜１７３
の範囲である。3.4-Epoxycyclohexane methanol and (meth)
The molar ratio of the transesterification reaction with the acrylic ester is theoretically 1/1, but as in the present invention, it is actually in the range of 1/1 to 1/1, preferably 1/1 to 173.
is within the range of
エステル交換反応のモル比が３，４−エポキシシクロヘ
キサンメタノール／（メタ）アクリル酸エステル−１／
１ｏ未満の場合は３，４−エポキシシクロヘキサンメタ
ノールの選択性、転化率の点では好ましいが、アクリル
酸エステル又はメタクリル酸エステル自身の重合による
ロスが多くなる。また、未反応のアクリル酸エステル又
はメタクリル酸エステルの回収に多大のエネルギーを要
する、などの欠点がある。The molar ratio of the transesterification reaction is 3,4-epoxycyclohexane methanol/(meth)acrylic acid ester-1/
If it is less than 10, it is preferable in terms of the selectivity and conversion rate of 3,4-epoxycyclohexane methanol, but the loss due to polymerization of the acrylic ester or methacrylic ester itself increases. Further, there are drawbacks such as a large amount of energy being required to recover unreacted acrylic ester or methacrylic ester.
逆にエステル交換反応のモル比が３．４−エポキシシク
ロヘキサンメタノール／（メタ）アクリル酸エステル−
１０／１を越える場合はアクリル酸エステル又はメタク
リル酸エステル自身の重合によるロスは減少するが、３
，４−エポキシシクロヘキサンメタノールの回収あるい
は反応粗液の精製に多大のエネルギーを要するので好ま
しくない。反応をバッチで行なう場合は先ず、反応容器
内に３．４−エポキシシクロヘキサンメタノールを所定
量仕込み、この中に前記好適量の触媒を溶解させ、この
中にメタクリル酸メチル、アクリル酸メチルなどを仕込
み、行なう。Conversely, the molar ratio of the transesterification reaction is 3.4-epoxycyclohexane methanol/(meth)acrylic acid ester-
If the ratio exceeds 10/1, the loss due to polymerization of the acrylic ester or methacrylic ester itself will decrease, but 3
, 4-epoxycyclohexane It is not preferable because a large amount of energy is required to recover the methanol or purify the reaction crude liquid. When carrying out the reaction in batches, first, a predetermined amount of 3,4-epoxycyclohexane methanol is charged into the reaction vessel, the appropriate amount of the catalyst is dissolved in this, and methyl methacrylate, methyl acrylate, etc. are charged into this. , do it.
使用する触媒としては前記したようなエステル化反応時
に用いるＰ−）ルエンスルホン酸、硫酸などの他にナト
リウムアルコラード、水酸化リチウム、アルミニウムア
ルコラード、テトラブトキシチタン等のエステル交換触
媒として公知のものから任意に選択して使用することが
できるが、価格、安定性などの点で水酸化リチウム、テ
トラブトキシチタンが好ましい。Catalysts used include P-)luenesulfonic acid, sulfuric acid, etc. used in the esterification reaction as described above, as well as those known as transesterification catalysts such as sodium alcoholade, lithium hydroxide, aluminum alcoholade, and tetrabutoxytitanium. Although it can be arbitrarily selected and used, lithium hydroxide and tetrabutoxytitanium are preferred in terms of cost, stability, and the like.
触媒の使用量は出発原料に対して０．００１〜１０重量
％、好ましくは０．０１〜１重量％である。触媒の使用
量が０．００１重量％をより少ない場合は反応速度が遅
かったり、収率が悪いなどの不都合があり、逆に１０重
量％より多くしても反応促進効果は改善される訳ではな
いので、無意味である。The amount of catalyst used is 0.001 to 10% by weight, preferably 0.01 to 1% by weight, based on the starting material. If the amount of catalyst used is less than 0.001% by weight, there will be disadvantages such as slow reaction rate and poor yield, and conversely, if the amount is more than 10% by weight, the reaction promotion effect will not be improved. Since there is none, it is meaningless.
エステル交換反応の温度は、反応時間の短縮と重合防止
の点から生成するアルコールの１弗点付近の温度で行な
われるのが有利である。The temperature of the transesterification reaction is advantageously carried out at a temperature around the 1 fluoro point of the alcohol produced from the viewpoint of shortening the reaction time and preventing polymerization.
重合禁止剤としては前記エステル化反応と同じハイドロ
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ヒドロキシチオフエノー
ル、α−ニトロソ−βナフトール、Ｐ−ベンゾキノン、
２．５−ジヒドロキ−Ｐ−キノン、銅塩等を使用するこ
とができるが、価格、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特に好ましい。As the polymerization inhibitor, the same hydroquinone, P-methoxyphenol, 2,4-dimethyl-
6-t-butylphenol, 3-hydroxythiophenol, α-nitroso-β-naphthol, P-benzoquinone,
Although 2,5-dihydroxy-P-quinone, copper salts, etc. can be used, hydroquinone and P-methoxyphenol are particularly preferred in terms of cost, stability, and the like.
上記のような重合禁止剤の使用量は（メタ）アクリル酸
エステルに対して０．００１〜５．０重量％、好ましく
は０．０１〜１．０重量％である。The amount of the polymerization inhibitor used as described above is 0.001 to 5.0% by weight, preferably 0.01 to 1.0% by weight based on the (meth)acrylic ester.
重合禁止剤の添加量が０．００１重量％未満の場合は重
合禁止効果か小さく、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 of the polymerization inhibitor added is less than 0.001% by weight, the effect of inhibiting polymerization is small, and conversely, if it is added in an amount of 5.0% by weight or more, the effect will not improve and it will be wasted.
反応は３，４−エポキシシクロヘキサンメタノールと（
メタ）アクリル酸エステルとを重合禁止剤と触媒の存在
下で加熱し、生成する該低級アルコールを系外へ取り出
すことによりエステル交換反応を進行させる。The reaction is between 3,4-epoxycyclohexanemethanol and (
The meth)acrylic acid ester is heated in the presence of a polymerization inhibitor and a catalyst, and the resulting lower alcohol is taken out of the system, thereby allowing the transesterification reaction to proceed.
反応により生成した低級アルコールを分離するにはその
まま蒸留してもよいし、例えばｎ−ヘキサンなどの低級
アルコールと共沸混合物をつくり、実質的には低級アル
コールと互いに混合しない有機溶媒をエントレーナーと
して用いても良い。To separate the lower alcohol produced by the reaction, it may be distilled as it is, or an azeotrope may be created with the lower alcohol such as n-hexane, and an organic solvent that is substantially immiscible with the lower alcohol may be used as an entrainer. May be used.
エントレーナーは最初の仕込みの段階で添加しておくの
がよい。It is best to add the entrainer during the initial preparation stage.
エントレーナーの使用量は理論量に対して１〜１０倍で
あり、好ましくは２〜５倍である。The amount of entrainer used is 1 to 10 times the theoretical amount, preferably 2 to 5 times.
低級アルコールとともに留出したエントレーナーは分液
して再使用することができる。The entrainer distilled together with the lower alcohol can be separated and reused.
反応は常圧か又は若干減圧した状態でおこなうのが好適
である。The reaction is preferably carried out at normal pressure or under slightly reduced pressure.
反応の終点の確認はガスクロ分析によるのが良い。反応
終了後の混合液から製品である（メタ）アクリレート化
合物を分離するのは薄膜式蒸発器などを用いて低沸分を
除去した後、薄膜式蒸発器をリボイラーとする蒸留塔を
用いるのが良い。It is best to confirm the end point of the reaction by gas chromatography. To separate the product (meth)acrylate compound from the mixed solution after the reaction is complete, use a thin film evaporator to remove low boiling components, and then use a distillation column that uses the thin film evaporator as a reboiler. good.
エステル交換反応もエステル化反応と同じように常圧か
、若干減圧した状態で行なうので、耐圧容器は必要とし
ないが、ステンレス鋼、グラスライニング鋼などの耐蝕
性の材料を用いるのがよい。Like the esterification reaction, the transesterification reaction is carried out at normal pressure or under slightly reduced pressure, so a pressure-resistant container is not required, but it is preferable to use a corrosion-resistant material such as stainless steel or glass-lined steel.
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〕
１０段（４０φ）の目皿式ガラス製蒸留塔を備えた５ｇ
丸底フラスコに３．４−エポキシシクロヘキサンメタノ
ール１２００ｇ、メタクリル酸メチル１７４５ｇ、ｎ−
ヘキサン７０７ｇ、水酸化リチウム１０ｇ１ハイドロキ
ノン３．７ｇを加えオイルバスで加熱し１時間全還流さ
せた後ｎ〜ヘキサンをエントレーナーとしメタノールを
留出させた。[Example 1] 5g with a 10-stage (40φ) perforated glass distillation column
In a round bottom flask, 1200 g of 3.4-epoxycyclohexane methanol, 1745 g of methyl methacrylate, n-
707 g of hexane, 10 g of lithium hydroxide, and 3.7 g of hydroquinone were added, heated in an oil bath, and completely refluxed for 1 hour. Then, methanol was distilled off using n-hexane as an entrainer.
３．４−エポキシシクロヘキサンメタノールに対する反
応収率は５６％であった。The reaction yield for 3.4-epoxycyclohexane methanol was 56%.
〔実施例２〕
実施例１と同様の反応装置に３．４−エポキシシクロヘ
キサンメタノール１２７１ｇ、メタクリル酸メチル２１
５９ｇ、テトラブトキシチタン３゜２ｇ、Ｐ−メトキシ
フェノール３．２ｇを加えオイルバスで加熱し１時間全
還流させた後メタツルを留出させた。[Example 2] Into the same reaction apparatus as in Example 1, 1271 g of 3,4-epoxycyclohexane methanol and 21 g of methyl methacrylate were added.
59 g of tetrabutoxytitanium, 3.2 g of tetrabutoxytitanium, and 3.2 g of P-methoxyphenol were added, heated in an oil bath, and completely refluxed for 1 hour, after which the metal sulfur was distilled off.
留出時、塔頂からＰ−メトキシフェノールを滴下した。During distillation, P-methoxyphenol was added dropwise from the top of the column.
３．４−エポキシシクロヘキサンメタノールに対する反
応収率は５９％であった。The reaction yield for 3.4-epoxycyclohexane methanol was 59%.
〔実施例３〕
実施例１と同様の反応装置に３．４−エポキシシクロヘ
キサンメタノール１２００ｇ５ｐ−）ルエンスルホン酸
２ｇ１ハイドロキノン２ｇ、ベンゼン２００ｇを仕込み
、加熱還流させながらアクリル酸７７１ｇを１時間かけ
て滴下した。[Example 3] 1200 g of 3.4-epoxycyclohexane methanol, 2 g of p-)luenesulfonic acid, 2 g of hydroquinone, and 200 g of benzene were placed in the same reaction apparatus as in Example 1, and 771 g of acrylic acid was added dropwise over 1 hour while heating to reflux. .
生成する水をベンゼンとの共沸によって反応系より除い
て反応を進行させた。The reaction was allowed to proceed by removing the produced water from the reaction system by azeotropy with benzene.
留出したベンゼンは分液後反応系に戻し、循環再使用し
た。The distilled benzene was returned to the reaction system after separation and recycled for reuse.
３．４−エポキシシクロヘキサンメタノールに対する反
応収率は５２％であった。The reaction yield for 3.4-epoxycyclohexane methanol was 52%.
Claims (1)
アクリル酸または（メタ）アクリル酸エステルを反応さ
せることを特徴とする下記の一般式（ I ） ▲数式、化学式、表等があります▼（ 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の製造方法。[Claims] 3,4-epoxycyclohexane methanol (meth)
The following general formula (I) characterized by reacting acrylic acid or (meth)acrylic acid ester ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R represents a hydrogen atom or a methyl group] A method for producing a (meth)acrylate compound represented by
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25694489A JP2797000B2 (en) | 1989-10-02 | 1989-10-02 | Method for producing (meth) acrylate compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25694489A JP2797000B2 (en) | 1989-10-02 | 1989-10-02 | Method for producing (meth) acrylate compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03120263A true JPH03120263A (en) | 1991-05-22 |
| JP2797000B2 JP2797000B2 (en) | 1998-09-10 |
Family
ID=17299528
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25694489A Expired - Fee Related JP2797000B2 (en) | 1989-10-02 | 1989-10-02 | Method for producing (meth) acrylate compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2797000B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5382676A (en) * | 1991-08-28 | 1995-01-17 | Daicel Chemical Industries, Ltd. | Purified 3,4-epoxycyclohexyl methyl(meth)acrylate, a process for the preparation thereof and a 3,4-epoxycyclohexyl methyl(meth)acrylate composition |
| US5527927A (en) * | 1994-05-20 | 1996-06-18 | Mitsubishi Gas Chemical Company, Inc. | Process for producing glycidyl acrylate or glycidyl methacrylate |
| JP2002371072A (en) * | 2001-06-12 | 2002-12-26 | Asahi Kasei Corp | Method for manufacturing alicyclic ester including epoxy group |
| JP2002371073A (en) * | 2001-06-12 | 2002-12-26 | Asahi Kasei Corp | Method for manufacturing alicyclic ester including epoxy group |
| CN115028531A (en) * | 2022-07-12 | 2022-09-09 | 湖南艾硅特新材料有限公司 | Epoxy cyclohexane hydroxyethyl methacrylate, epoxy cyclohexane hydroxyethyl acrylate and synthesis method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5711767B2 (en) | 2010-03-09 | 2015-05-07 | ヘンケル ユーエス アイピー エルエルシー | Cationic UV cross-linked acrylic polymer for pressure sensitive adhesives |
-
1989
- 1989-10-02 JP JP25694489A patent/JP2797000B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5382676A (en) * | 1991-08-28 | 1995-01-17 | Daicel Chemical Industries, Ltd. | Purified 3,4-epoxycyclohexyl methyl(meth)acrylate, a process for the preparation thereof and a 3,4-epoxycyclohexyl methyl(meth)acrylate composition |
| US5527927A (en) * | 1994-05-20 | 1996-06-18 | Mitsubishi Gas Chemical Company, Inc. | Process for producing glycidyl acrylate or glycidyl methacrylate |
| JP2002371072A (en) * | 2001-06-12 | 2002-12-26 | Asahi Kasei Corp | Method for manufacturing alicyclic ester including epoxy group |
| JP2002371073A (en) * | 2001-06-12 | 2002-12-26 | Asahi Kasei Corp | Method for manufacturing alicyclic ester including epoxy group |
| CN115028531A (en) * | 2022-07-12 | 2022-09-09 | 湖南艾硅特新材料有限公司 | Epoxy cyclohexane hydroxyethyl methacrylate, epoxy cyclohexane hydroxyethyl acrylate and synthesis method thereof |
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| Publication number | Publication date |
|---|---|
| JP2797000B2 (en) | 1998-09-10 |
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