JP2005132790A - Method for producing 2-methyl-2-hydroxy-1-propyl (meth)acrylate - Google Patents

Method for producing 2-methyl-2-hydroxy-1-propyl (meth)acrylate Download PDF

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JP2005132790A
JP2005132790A JP2003372303A JP2003372303A JP2005132790A JP 2005132790 A JP2005132790 A JP 2005132790A JP 2003372303 A JP2003372303 A JP 2003372303A JP 2003372303 A JP2003372303 A JP 2003372303A JP 2005132790 A JP2005132790 A JP 2005132790A
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JP4336961B2 (en
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Takafumi Abe
崇文 阿部
Hideho Matsuda
秀穂 松田
Yoshikazu Shima
義和 島
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Mitsubishi Gas Chemical Co Inc
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Abstract

<P>PROBLEM TO BE SOLVED: To provide an industrially practicable method capable of simply producing 2-methyl-2-hydroxy-1-propyl (meth)acrylate from a general-purpose raw material in high yield. <P>SOLUTION: The method for producing 2-methyl-2-hydroxy-1-propyl (meth)acrylate comprises reacting a (meth)acrylate with 2-methyl-2-hydroxy-1-propyl alcohol in the presence of a Zn-acetylacetonate catalyst. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

本発明はZn−アセチルアセトナート触媒の存在下、（メタ）アクリル酸エステルと２−メチル−２−ヒドロキシ−１−プロピルアルコールを原料として２−メチル−２−ヒドロキシ−１−プロピル（メタ）アクリレートを効率的に製造する方法に関するものである。２−メチル−２−ヒドロキシ−１−プロピル（メタ）アクリレートは、分子内に３級水酸基を持つ特徴から親水性と耐水性をバランスよく有し、親水性と耐水性を兼ね備える興味深い物性を持つ重合体の原料として有用である。   The present invention provides 2-methyl-2-hydroxy-1-propyl (meth) acrylate using (meth) acrylic acid ester and 2-methyl-2-hydroxy-1-propyl alcohol as raw materials in the presence of a Zn-acetylacetonate catalyst. It is related with the method of manufacturing efficiently. 2-Methyl-2-hydroxy-1-propyl (meth) acrylate has a balance between hydrophilicity and water resistance due to the characteristics of having a tertiary hydroxyl group in the molecule, and has an interesting physical property that combines hydrophilicity and water resistance. Useful as a raw material for coalescence.

２−メチル−２−ヒドロキシ−１−プロピル（メタ）アクリレートの合成法としては、（メタ）アクリル酸と１，１’−ジメチルエチレンオキサイドからの製法が知られているが（例えば、特許文献１参照）、原料となる１，１’−ジメチルエチレンオキサイドは汎用的な原料ではない。   As a synthesis method of 2-methyl-2-hydroxy-1-propyl (meth) acrylate, a production method from (meth) acrylic acid and 1,1′-dimethylethylene oxide is known (for example, Patent Document 1). 1,1′-dimethylethylene oxide as a raw material is not a general-purpose raw material.

その他の製法としてはエステル交換による方法が考えられる。エステル交換触媒としては、一般的にテトライソプロポキシチタネート等のチタンアルコラートやジブチルスズオキサイド等のスズ系触媒の様なものが触媒として用いられることが知られている（例えば、特許文献２参照）。しかしながら、本発明者らがチタンアルコラートやスズ系触媒を用いて２−メチル−２−ヒドロキシ−１−プロピル（メタ）アクリレートの製造を試みたところ機構は不明であるが、反応が途中で停止してしまい好収率で２−メチル−２−ヒドロキシ−１−プロピル（メタ）アクリレートを得ることができなかった。
米国特許第４５２４０９２号明細書 特開平１１−２２２４６１号公報 As another production method, a method by transesterification can be considered. As the transesterification catalyst, it is generally known that a catalyst such as a titanium alcoholate such as tetraisopropoxytitanate or a tin-based catalyst such as dibutyltin oxide is used as the catalyst (see, for example, Patent Document 2). However, when the present inventors tried to produce 2-methyl-2-hydroxy-1-propyl (meth) acrylate using a titanium alcoholate or a tin-based catalyst, the mechanism is unknown, but the reaction stopped midway. As a result, 2-methyl-2-hydroxy-1-propyl (meth) acrylate could not be obtained in good yield.
US Pat. No. 4,524,092 JP-A-11-222461

本発明は従来技術に見られる前記問題を解決し、工業的に有利な２−メチル−２−ヒドロキシ−１−プロピル（メタ）アクリレートの製法を提供することをその課題とする。   The object of the present invention is to solve the above-mentioned problems found in the prior art and to provide an industrially advantageous process for producing 2-methyl-2-hydroxy-1-propyl (meth) acrylate.

本発明者らは、２−メチル−２−ヒドロキシ−１−プロピル（メタ）アクリレートの製造方法に関して工業的に有利な方法を確立すべく鋭意検討した結果、（メタ）アクリル酸エステルと２−メチル−２−ヒドロキシ−１−プロピルアルコールを原料にＺｎ−アセチルアセトナート触媒の存在下エステル交換反応を行うことで、反応が途中で停止することもなく高い収率で２−メチル−２−ヒドロキシ−１−プロピル（メタ）アクリレートが得られることを見いだし、本発明を完成するに至った。即ち本発明は、Ｚｎ−アセチルアセトナートの存在下、（メタ）アクリル酸エステルと２−メチル−２−ヒドロキシ−１−プロピルアルコールとのエステル交換反応を行うことによって２−メチル−２−ヒドロキシ−１−プロピル（メタ）アクリレートを製造する（１）及び（２）に示す方法である。
（１）Zn−アセチルアセトナート触媒の存在下、（メタ）アクリル酸エステルと２−メチル−２−ヒドロキシ−１−プロピルアルコールの反応を行うことを特徴とする、２−メチル−２−ヒドロキシ−１−プロピル（メタ）アクリレートの製造方法。
（２）（メタ）アクリル酸エステルのエステル基が炭素数１〜４の化合物よりなる、請求項１に記載の２−メチル−２−ヒドロキシ−１−プロピル（メタ）アクリレートの製造方法。 As a result of intensive studies to establish an industrially advantageous method for producing 2-methyl-2-hydroxy-1-propyl (meth) acrylate, the present inventors have found that (meth) acrylic acid ester and 2-methyl By performing a transesterification reaction using 2-hydroxy-1-propyl alcohol as a raw material in the presence of a Zn-acetylacetonate catalyst, 2-methyl-2-hydroxy- It was found that 1-propyl (meth) acrylate was obtained, and the present invention was completed. That is, the present invention performs 2-ester-2-hydroxy-transesterification reaction between (meth) acrylic acid ester and 2-methyl-2-hydroxy-1-propyl alcohol in the presence of Zn-acetylacetonate. This is a method shown in (1) and (2) for producing 1-propyl (meth) acrylate.
(1) A reaction between (meth) acrylic acid ester and 2-methyl-2-hydroxy-1-propyl alcohol in the presence of a Zn-acetylacetonate catalyst. A method for producing 1-propyl (meth) acrylate.
(2) The method for producing 2-methyl-2-hydroxy-1-propyl (meth) acrylate according to claim 1, wherein the ester group of (meth) acrylic acid ester is composed of a compound having 1 to 4 carbon atoms.

本発明の方法によれば触媒が失活することなく、簡便な方法で，汎用原料から２−メチル−２−ヒドロキシ−１−プロピル（メタ）アクリレートを高い収率で得ることが可能であり、これにより経済的な工業的プロセスが可能となる。   According to the method of the present invention, 2-methyl-2-hydroxy-1-propyl (meth) acrylate can be obtained in a high yield from a general-purpose raw material by a simple method without deactivating the catalyst. This enables an economical industrial process.

以下、本発明の２−メチル−２−ヒドロキシ−１−プロピル（メタ）アクリレートの製造方法について説明する。本発明における反応温度は通常２０℃〜２００℃、好ましくは５０℃〜１５０℃の範囲である。２０℃未満の場合は反応速度が遅く、２００℃を超える場合は重合問題を引き起こす。   Hereinafter, the manufacturing method of 2-methyl-2-hydroxy-1-propyl (meth) acrylate of this invention is demonstrated. The reaction temperature in this invention is 20 to 200 degreeC normally, Preferably it is the range of 50 to 150 degreeC. When the temperature is lower than 20 ° C., the reaction rate is low, and when it exceeds 200 ° C., a polymerization problem is caused.

反応時間は長くても構わないが長時間では効率的でなくかつ重合が懸念される。好ましい反応時間は５分から４８時間である。   The reaction time may be long, but a long time is not efficient and there is a concern about polymerization. The preferred reaction time is 5 minutes to 48 hours.

本発明に於ける（メタ）アクリル酸エステルに対する２−メチル−２−ヒドロキシ−１−プロピルアルコールのモル比は０．１〜１００であれば良いが、反応後の分離に要するエネルギーコストを考慮すれば０．１〜１０の範囲が好ましい。   In the present invention, the molar ratio of 2-methyl-2-hydroxy-1-propyl alcohol to (meth) acrylic acid ester may be 0.1 to 100, considering the energy cost required for separation after the reaction. A range of 0.1 to 10 is preferable.

反応圧は、減圧，常圧，加圧でもかまわないが、反応物の還流温度が上記の反応温度範囲になるように圧力を設定するのが好ましい。   The reaction pressure may be reduced pressure, normal pressure, or increased pressure, but it is preferable to set the pressure so that the reflux temperature of the reaction product falls within the above reaction temperature range.

本発明における反応方式は、原料と触媒であるZn−アセチルアセトナートが効率的に接触する方法であれば何れの方法でも採用することができる。本発明に於けるエステル交換反応は平衡反応であるため反応蒸留のように、副生するアルコールを系外に留出除去することが反応率を高める上で有効である。副生するアルコールが、原料である（メタ）アクリル酸エステルと共沸してしまう場合、共沸剤としてより低い沸点の共沸混合物を形成する物質を添加することも有効である。また反応を妨害しないものであればどのような溶媒を使用しても良いが、反応後に溶媒を回収する必要が無いこと、及び反応系内の容積あたりの生産性を向上できる点で溶媒を使用しない方が好ましい。   As the reaction method in the present invention, any method can be adopted as long as it is a method in which the raw material and the catalyst, Zn-acetylacetonate, efficiently contact each other. Since the transesterification reaction in the present invention is an equilibrium reaction, it is effective to increase the reaction rate by distilling off the by-produced alcohol out of the system as in the case of reactive distillation. When the by-produced alcohol azeotropes with the raw material (meth) acrylic acid ester, it is also effective to add a substance that forms an azeotropic mixture having a lower boiling point as an azeotropic agent. Any solvent may be used as long as it does not interfere with the reaction, but it is not necessary to recover the solvent after the reaction and the solvent can be used in terms of improving productivity per volume in the reaction system. It is preferable not to.

本反応に用いるZn−アセチルアセトナートは例えばアセチルアセトンと硫酸亜鉛から調整することができる（新実験化学講座８無機化合物の合成（III），丸善，ｐ１５７８，１９７７）。使用するZn−アセチルアセトナート触媒量は２−メチル−２−ヒドロキシ−１−プロピルアルコールに対して重量比で１０−５〜１０、好ましくは１０−３〜１である。１０以上でも構わないが経済的でなく、１０−５より少ない場合は反応速度が低下する。 Zn-acetylacetonate used in this reaction can be prepared from, for example, acetylacetone and zinc sulfate (New Experimental Chemistry Lecture 8, Synthesis of Inorganic Compounds (III), Maruzen, p1578, 1977). The amount of Zn-acetylacetonate catalyst used is 10 −5 to 10 and preferably 10 −3 to 1 by weight with respect to 2-methyl-2-hydroxy-1-propyl alcohol. Although it may be 10 or more, it is not economical, and when it is less than 10 −5 , the reaction rate decreases.

反応終了後、蒸留により２−メチル−２−ヒドロキシ−１−プロピル（メタ）アクリレートを回収精製することができる。蒸留圧力は加圧、常圧、減圧の何れでも良いが重合問題から減圧で蒸留精製することが好ましい。また蒸留後の釜残液は触媒液として再利用することも可能である。   After completion of the reaction, 2-methyl-2-hydroxy-1-propyl (meth) acrylate can be recovered and purified by distillation. The distillation pressure may be any of pressurization, normal pressure, and reduced pressure, but it is preferable to purify by distillation under reduced pressure because of polymerization problems. Further, the kettle residue after distillation can be reused as a catalyst solution.

原料として用いられる（メタ）アクリル酸エステルの炭素数１〜４のエステル基としては、メチル，エチル，ｎ−プロピル等が挙げられる。本エステル基は交換反応によってアルコールとして副生してくるが、反応蒸留を用いることを考慮すると沸点がなるべく低いアルコールである方が好ましい。また、本反応が平衡反応であることからも反応率を高めるためにはアルコールが低沸点であることが好ましく、更に重合問題からも低沸点であることが好ましい。   Examples of the ester group having 1 to 4 carbon atoms of the (meth) acrylic acid ester used as a raw material include methyl, ethyl, n-propyl and the like. Although this ester group is by-produced as an alcohol by an exchange reaction, in view of using reactive distillation, an alcohol having a boiling point as low as possible is preferable. In addition, since this reaction is an equilibrium reaction, the alcohol preferably has a low boiling point in order to increase the reaction rate, and more preferably has a low boiling point from the viewpoint of polymerization.

以下に実施例及び比較例によって本発明の方法を更に具体的に説明するが、本発明は、これらの例に限定されるものではない。
実施例１
撹拌装置、蒸留塔、乾燥空気導入管、温度計を備えた、３L三口フラスコに、２−メチル−２−ヒドロキシ−１−プロピルアルコール５４０ｇ、メチルメタクリレート１５００ｇ、Zn−アセチルアセトナート７ｇと重合禁止剤として４−ヒドロキシテトラメチルピペリジンNオキシル０．７ｇ及びメトキノン０．７ｇを仕込み、少量の空気を吹き込みながら撹拌しつつ、系内を１００〜１２０℃に加熱した。反応の進行につれ生成するメタノールをメチルメタクリレートとの共沸により、蒸留塔 塔頂部より徐々に抜き出し反応を進行させた。４時間後の２−メチル−２−ヒドロキシ−１−プロピルアルコール基準の２−メチル−２−ヒドロキシ−１−プロピルメタクリレート収率は４０％であった。更に反応を継続し、１８時間後の２−メチル−２−ヒドロキシ−１−プロピルアルコール基準の２−メチル−２−ヒドロキシ−１−プロピルメタクリレート収率は、９５％であった。 The method of the present invention will be described more specifically with reference to the following examples and comparative examples, but the present invention is not limited to these examples.
Example 1
In a 3 L three-necked flask equipped with a stirrer, distillation tower, dry air inlet tube and thermometer, 540 g of 2-methyl-2-hydroxy-1-propyl alcohol, 1500 g of methyl methacrylate, 7 g of Zn-acetylacetonate and a polymerization inhibitor As a preparation, 0.7 g of 4-hydroxytetramethylpiperidine N oxyl and 0.7 g of methoquinone were charged, and the system was heated to 100 to 120 ° C. while stirring while blowing a small amount of air. Methanol generated as the reaction progressed was gradually extracted from the top of the distillation column by azeotropy with methyl methacrylate, and the reaction proceeded. The yield of 2-methyl-2-hydroxy-1-propyl methacrylate based on 2-methyl-2-hydroxy-1-propyl alcohol after 4 hours was 40%. The reaction was further continued, and the yield of 2-methyl-2-hydroxy-1-propyl methacrylate based on 2-methyl-2-hydroxy-1-propyl alcohol after 18 hours was 95%.

比較例１
触媒をテトライソプロポキシチタネート７ｇに変更した以外は実施例１同様に反応を行った。４時間後の２−メチル−２−ヒドロキシ−１−プロピルアルコール基準の２−メチル−２−ヒドロキシ−１−プロピルメタクリレートの収率は５０％であった。更に反応を継続したが１８時間後でも２−メチル−２−ヒドロキシ−１−プロピルアルコール基準の２−メチル−２−ヒドロキシ−１−プロピルメタクリレートの収率は５７％であり、触媒が何らかの理由で失活していると考えられた。 Comparative Example 1
The reaction was conducted in the same manner as in Example 1 except that the catalyst was changed to 7 g of tetraisopropoxy titanate. The yield of 2-methyl-2-hydroxy-1-propyl methacrylate based on 2-methyl-2-hydroxy-1-propyl alcohol after 4 hours was 50%. Further, the reaction was continued, but even after 18 hours, the yield of 2-methyl-2-hydroxy-1-propyl methacrylate based on 2-methyl-2-hydroxy-1-propyl alcohol was 57%, and the catalyst was for some reason. It was considered dead.

Claims (2)

Zn−アセチルアセトナート触媒の存在下、（メタ）アクリル酸エステルと２−メチル−２−ヒドロキシ−１−プロピルアルコールの反応を行うことを特徴とする、２−メチル−２−ヒドロキシ−１−プロピル（メタ）アクリレートの製造方法。   2-methyl-2-hydroxy-1-propyl, characterized in that (meth) acrylic acid ester and 2-methyl-2-hydroxy-1-propyl alcohol are reacted in the presence of a Zn-acetylacetonate catalyst A method for producing (meth) acrylate. （メタ）アクリル酸エステルのエステル基が炭素数１〜４の化合物よりなる、請求項１に記載の２−メチル−２−ヒドロキシ−１−プロピル（メタ）アクリレートの製造方法。   The method for producing 2-methyl-2-hydroxy-1-propyl (meth) acrylate according to claim 1, wherein the ester group of the (meth) acrylic acid ester is composed of a compound having 1 to 4 carbon atoms.
JP2003372303A 2003-10-31 2003-10-31 Method for producing 2-methyl-2-hydroxy-1-propyl (meth) acrylate Expired - Fee Related JP4336961B2 (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011157645A2 (en) 2010-06-15 2011-12-22 Ecosynth Bvba Transesterification process using mixed salt acetylacetonates catalysts
CN105330537A (en) * 2015-11-30 2016-02-17 抚顺东联安信化学有限公司 Preparation method of methoxyethyl acrylate
JP2016155997A (en) * 2015-02-24 2016-09-01 株式会社リコー Active energy ray-curable composition, active energy ray-curable ink, composition storage container, apparatus for forming two-dimensional or three-dimensional image, method for forming two-dimensional or three-dimensional image, cured product, decorative body, and active energy ray-polymerizable compound
JP2018104379A (en) * 2016-12-28 2018-07-05 三菱瓦斯化学株式会社 Manufacturing method and composition of 2-methyl-2-hydroxy-1-propyl(meth)acrylate and/or 3-methyl-3-hydroxy-1-butyl(meth)acrylate
JP2018135285A (en) * 2017-02-21 2018-08-30 三菱瓦斯化学株式会社 Method for producing 2-methyl-2-hydroxy-1-propyl (meth)acrylate and/or 3-methyl-3-hydroxy-1-butyl(meth)acrylate and composition comprising the same

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011157645A2 (en) 2010-06-15 2011-12-22 Ecosynth Bvba Transesterification process using mixed salt acetylacetonates catalysts
WO2011157645A3 (en) * 2010-06-15 2012-10-18 Ecosynth Bvba Transesterification process using mixed salt acetylacetonates catalysts
CN103140287A (en) * 2010-06-15 2013-06-05 埃科辛斯私人有限公司 Transesterification process using mixed salt acetylacetonates catalysts
JP2013533861A (en) * 2010-06-15 2013-08-29 エコシンス ベーフェーベーアー Transesterification process using mixed salt acetylacetonate catalyst
US8865931B2 (en) 2010-06-15 2014-10-21 Ecosynth Bvba Transesterification process using mixed salt acetylacetonates catalysts
JP2016155997A (en) * 2015-02-24 2016-09-01 株式会社リコー Active energy ray-curable composition, active energy ray-curable ink, composition storage container, apparatus for forming two-dimensional or three-dimensional image, method for forming two-dimensional or three-dimensional image, cured product, decorative body, and active energy ray-polymerizable compound
CN105330537A (en) * 2015-11-30 2016-02-17 抚顺东联安信化学有限公司 Preparation method of methoxyethyl acrylate
JP2018104379A (en) * 2016-12-28 2018-07-05 三菱瓦斯化学株式会社 Manufacturing method and composition of 2-methyl-2-hydroxy-1-propyl(meth)acrylate and/or 3-methyl-3-hydroxy-1-butyl(meth)acrylate
JP2018135285A (en) * 2017-02-21 2018-08-30 三菱瓦斯化学株式会社 Method for producing 2-methyl-2-hydroxy-1-propyl (meth)acrylate and/or 3-methyl-3-hydroxy-1-butyl(meth)acrylate and composition comprising the same

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