JP3850975B2 - Method for producing 2-hydroxyethyl (meth) acrylate - Google Patents
Method for producing 2-hydroxyethyl (meth) acrylate Download PDFInfo
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- JP3850975B2 JP3850975B2 JP04219298A JP4219298A JP3850975B2 JP 3850975 B2 JP3850975 B2 JP 3850975B2 JP 04219298 A JP04219298 A JP 04219298A JP 4219298 A JP4219298 A JP 4219298A JP 3850975 B2 JP3850975 B2 JP 3850975B2
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- meth
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- acrylate
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Description
【０００１】
【発明の属する技術分野】
本発明は、塗料や親水性高分子の原料として有用な（メタ）アクリル酸２−ヒドロキシエチルの製造方法に関し、詳しくはエチレンオキサイド含有量の少ない（メタ）アクリル酸２−ヒドロキシエチルの製造方法に関する。
【０００２】
【従来の技術】
一般に（メタ）アクリル酸２−ヒドロキシエチルは、（メタ）アクリル酸とエチレンオキサイド（以下、ＥＯという）を触媒の存在下に反応させることによって製造される。この製造方法では、反応終了後の反応液中に、目的物質の（メタ）アクリル酸２−ヒドロキシエチル以外に（メタ）アクリル酸、ＥＯ、触媒残渣、高沸点副生成物等が含まれる。従来（メタ）アクリル酸２−ヒドロキシエチル以外の物質を除去するために、蒸留による精製が行われていた。
【０００３】
しかしながら、蒸留によりＥＯ等の不純物を低減するには蒸留温度を高くする必要があるが、温度を上げると（メタ）アクリル酸２−ヒドロキシエチルの重合が起こりやすいため、蒸留温度を無制限に高くすることはできない。このため製品の純度を上げることができないという問題があった。
【０００４】
【発明が解決しようとする課題】
本発明は、このような問題に鑑みてなされたものであり、重合トラブルが生じない温度で効率よくＥＯを除去することにより、ＥＯ含有量の少ない高純度の（メタ）アクリル酸２−ヒドロキシエチルを製造する方法を提供することを目的とする。
【０００５】
【課題を解決するための手段】
本発明は、（メタ）アクリル酸とエチレンオキサイドを反応させて（メタ）アクリル酸２−ヒドロキシエチルを製造する方法において、前記（メタ）アクリル酸とエチレンオキサイドとの反応液を４０〜７０℃に予熱した後脱気塔へ導いて、０．０１〜１．３３ｋＰａの減圧下で該反応液に吸収されにくいキャリアガスと接触させて未反応のエチレンオキサイドを除去した後、薄膜蒸発器にて０．０１〜１．３３ｋＰａの減圧下、６０〜１００℃で（メタ）アクリル酸２−ヒドロキシエチルを分離することを特徴とする（メタ）アクリル酸２−ヒドロキシエチルの製造方法である。
【０００６】
本発明においては、脱気塔内にて反応液と、その反応液に吸収されにくいキャリアガスとを接触させることにより、反応液中の未反応エチレンオキサイドを効率よく除去することができる。
【０００７】
【発明の実施の形態】
以下、図１に基づいて本発明の一例を説明する。本発明の製造方法では、触媒の存在下、（メタ）アクリル酸と（メタ）アクリル酸１モルに対して１．０〜１．２モル、好ましくは１．０３〜１．１０のＥＯを反応釜１にて反応させる。
【０００８】
ここで用いられる触媒としては、公知のものを用いればよく、例えば各種アミン類、四級アンモニウム塩、鉄化合物、または（メタ）アクリル酸金属化合物等を単独で、または組み合わせたものを用いることができる。
【０００９】
反応は、バッチ式または連続式のいずれでもよく、反応温度は、通常５０〜７０℃程度である。
【００１０】
反応終了後の反応液には、目的物質の（メタ）アクリル酸２−ヒドロキシエチル以外に、（メタ）アクリル酸、ＥＯ、触媒残渣、高沸点副生成物等が含まれる。反応液および反応釜に残るＥＯは、脱気等により大部分除去できるが、通常反応液中には３０００ｐｐｍ程度残存する。
【００１１】
次に、残存ＥＯを含む反応終了後の反応液（以下、単に反応液という）を、一旦中間タンク２へ供給する。続いて反応液を、中間タンク２から供給管４を通じて予熱器５へ移液する。予熱器５において、反応液を予熱して脱気塔供給口７を通じて脱気塔６へ導入する。予熱器による予熱温度は、重合のトラブルが生じない程度に高い方がＥＯの除去が効率的に行うことができ、通常３０〜８０℃、好ましくは４０〜７０℃である。
【００１２】
ここで供給管４、脱気塔６および薄膜蒸発器９は、真空発生装置３にて０．０１〜１．３３ｋＰａ、好ましくは０．０７〜０．４ｋＰａの減圧に保たれている。
【００１３】
脱気塔６において、脱気塔供給口７から供給される加熱された反応液とキャリアガス供給口８から供給されるキャリアガスとを接触させることにより、反応液中のＥＯ等の低沸物を除去することができる。脱気塔６は、反応液とキャリアガスが効率的に接触するような構造のものが好ましい。このような構造としては例えば棚段の上から反応液を供給し、一方キャリアガスを下から供給し、向流で気液接触させるシーブトレイ状の構造等を挙げることができる。
【００１４】
キャリアガスとしては、蒸留液に吸収されにくい気体であれば何れも使用できるが、品質，重合防止およびコスト等の面から、乾燥空気を用いることが好ましい。キャリアガスの供給量は目的の純度を達成するために適宜調節されるが、反応液１容量に対して０．３〜２容量供給することが好ましい。
【００１５】
最後に、脱気塔６において低沸物を除去した反応液を、６０〜１００℃、好ましくは６５〜７５℃に加熱した薄膜蒸発器９にて蒸発させ、高純度の（メタ）アクリル酸２−ヒドロキシエチルを蒸発残渣１１から分離して製品１０を得る。
【００１６】
【実施例】
［実施例１］
図１の装置を用いて、メタクリル酸とＥＯを反応釜１で反応させ、脱気操作によりＥＯの大部分除去した。得られた反応液（粗メタクリル酸２−ヒドロキシエチル、液中のＥＯ濃度３０００ｐｐｍ）をポンプにより中間タンク２に移液した。
【００１７】
次に、反応液を中間タンク２から０．１３ｋＰａの減圧下で０．９ｍ3／ｈの流量で予熱器５へ供給した。予熱器５において、液温１５℃の反応液を２９０ｋＰａ蒸気にて５０℃に予熱し、０．９ｍ3／ｈの流量で、５段のシーブトレイで構成されている脱気塔６へ、脱気塔供給口７から供給した。
【００１８】
また、乾燥空気を０．６５ｍ3／ｈの流量でキャリアガス供給口８から供給し、加熱された反応液と脱気塔６内にて０．１３ｋＰａの減圧下で接触させて低沸物を除去した。低沸物を除去した反応液を脱気塔６から移液し、薄膜蒸発器９に供給した。脱気塔から供給された反応液を、薄膜蒸発器９において０．１３ｋＰａ、６８℃で蒸留し、メタクリル酸２−ヒドロキシエチルを得た。得られたメタクリル酸２−ヒドロキシエチルに含まれるＥＯ濃度は１２ｐｐｍであった。
【００１９】
［実施例２〜４］
予熱器５による予熱温度を表１の条件に変えた以外は、実施例１同様の方法でメタクリル酸２−ヒドロキシエチルを製造し、表１に示す結果を得た。
【００２０】
［比較例１］
予熱器５および脱気塔６を使用せず、中間タンク２の１５℃の反応液を薄膜蒸発器９に直接供給した点以外は、実施例１同様の方法でメタクリル酸２−ヒドロキシエチルを製造した。得られたメタクリル酸２−ヒドロキシエチルに含まれるＥＯ濃度は２００ｐｐｍであった。
【００２１】
［参考例１］
予熱器５を使用せず、中間タンク２の１５℃の反応液を脱気塔６に直接供給した点以外は、実施例１同様の方法でメタクリル酸２−ヒドロキシエチルを製造した。得られたメタクリル酸２−ヒドロキシエチルに含まれるＥＯ濃度は６０ｐｐｍであった。
【００２２】
【表１】
【発明の効果】
本発明の方法によれば、重合トラブルが生じない温度で、効率よくＥＯを除去することができるので、ＥＯ含有量の少ない高純度の（メタ）アクリル酸２−ヒドロキシエチルを製造することができる。
【図面の簡単な説明】
【図１】本発明のメタクリル酸２−ヒドロキシエチルの製造方法のプロセスフローおよびそれに用いる装置の概略を示す図である。
【符号の説明】
１ 反応釜
２ 中間タンク
３ 真空発生装置
４ 供給管
５ 予熱器
６ 脱気塔
７ 脱気塔供給口
８ キャリアガス供給口
９ 薄膜蒸発器
１０ 製品
１１ 蒸発残渣[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing 2-hydroxyethyl (meth) acrylate useful as a raw material for paints and hydrophilic polymers, and more particularly to a method for producing 2-hydroxyethyl (meth) acrylate having a low ethylene oxide content. .
[0002]
[Prior art]
In general, 2-hydroxyethyl (meth) acrylate is produced by reacting (meth) acrylic acid and ethylene oxide (hereinafter referred to as EO) in the presence of a catalyst. In this production method, (meth) acrylic acid, EO, catalyst residue, high-boiling by-product, etc. are contained in the reaction solution after completion of the reaction, in addition to the target substance (2-hydroxyethyl) (meth) acrylate. Conventionally, purification by distillation has been performed to remove substances other than 2-hydroxyethyl (meth) acrylate.
[0003]
However, in order to reduce impurities such as EO by distillation, it is necessary to increase the distillation temperature. However, since the polymerization of 2-hydroxyethyl (meth) acrylate tends to occur when the temperature is increased, the distillation temperature is increased without limitation. It is not possible. For this reason, there was a problem that the purity of the product could not be raised.
[0004]
[Problems to be solved by the invention]
The present invention has been made in view of such problems. By efficiently removing EO at a temperature at which polymerization trouble does not occur, high-purity 2-hydroxyethyl (meth) acrylate having a low EO content is obtained. An object of the present invention is to provide a method of producing
[0005]
[Means for Solving the Problems]
In the method of producing 2-hydroxyethyl (meth) acrylate by reacting (meth) acrylic acid and ethylene oxide, the present invention provides a reaction solution of (meth) acrylic acid and ethylene oxide at 40 to 70 ° C. was preheated led to degassing tower, after removing the unreacted ethylene oxide in contact with hard carrier gas is absorbed into the reaction solution under a reduced pressure of 0.01～1.33KPa, in thin-film evaporator 0 This is a method for producing 2-hydroxyethyl (meth) acrylate, wherein 2-hydroxyethyl (meth) acrylate is separated at 60 to 100 ° C. under a reduced pressure of 0.01 to 1.33 kPa .
[0006]
In the present invention, the unreacted ethylene oxide in the reaction solution can be efficiently removed by bringing the reaction solution into contact with the carrier gas that is not easily absorbed by the reaction solution in the deaeration tower.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, an example of the present invention will be described with reference to FIG. In the production method of the present invention, in the presence of a catalyst, 1.0 to 1.2 mol, preferably 1.03 to 1.10 EO is reacted with respect to 1 mol of (meth) acrylic acid and (meth) acrylic acid. React in
[0008]
As the catalyst used here, a known catalyst may be used. For example, various amines, quaternary ammonium salts, iron compounds, or (meth) acrylic acid metal compounds may be used alone or in combination. it can.
[0009]
The reaction may be either a batch type or a continuous type, and the reaction temperature is usually about 50 to 70 ° C.
[0010]
The reaction liquid after completion of the reaction contains (meth) acrylic acid, EO, catalyst residues, high-boiling byproducts, etc., in addition to the target substance, 2-hydroxyethyl (meth) acrylate. Most of the EO remaining in the reaction solution and the reaction kettle can be removed by degassing or the like, but usually about 3000 ppm remains in the reaction solution.
[0011]
Next, a reaction solution (hereinafter simply referred to as reaction solution) containing the remaining EO after completion of the reaction is once supplied to the intermediate tank 2. Subsequently, the reaction solution is transferred from the intermediate tank 2 to the preheater 5 through the supply pipe 4. In the preheater 5, the reaction liquid is preheated and introduced into the degassing tower 6 through the degassing tower supply port 7. The higher the preheating temperature by the preheater is, the higher the extent that polymerization trouble does not occur, the more efficiently EO can be removed, and it is usually 30 to 80 ° C, preferably 40 to 70 ° C.
[0012]
Here, the supply pipe 4, the deaeration tower 6 and the thin film evaporator 9 are maintained at a reduced pressure of 0.01 to 1.33 kPa, preferably 0.07 to 0.4 kPa, in the vacuum generator 3.
[0013]
In the degassing tower 6, by bringing the heated reaction liquid supplied from the degassing tower supply port 7 into contact with the carrier gas supplied from the carrier gas supply port 8, low boiling substances such as EO in the reaction liquid Can be removed. The deaeration tower 6 preferably has a structure in which the reaction liquid and the carrier gas are in efficient contact. Examples of such a structure include a sheave tray-like structure in which the reaction liquid is supplied from the top of the shelf and the carrier gas is supplied from the bottom to make gas-liquid contact in countercurrent.
[0014]
Any gas can be used as the carrier gas as long as it is difficult to be absorbed by the distillate. However, dry air is preferably used from the viewpoints of quality, polymerization prevention and cost. The supply amount of the carrier gas is appropriately adjusted in order to achieve the target purity, but it is preferable to supply 0.3 to 2 volumes with respect to 1 volume of the reaction solution.
[0015]
Finally, the reaction liquid from which low boiling substances have been removed in the deaeration tower 6 is evaporated in a thin film evaporator 9 heated to 60 to 100 ° C., preferably 65 to 75 ° C., and high-purity (meth) acrylic acid 2 -Hydroxyethyl is separated from the evaporation residue 11 to obtain the product 10.
[0016]
【Example】
[Example 1]
Using the apparatus of FIG. 1, methacrylic acid and EO were reacted in the
[0017]
Next, the reaction solution was supplied from the intermediate tank 2 to the preheater 5 at a flow rate of 0.9 m 3 / h under a reduced pressure of 0.13 kPa. In the preheater 5, the reaction liquid having a liquid temperature of 15 ° C. is preheated to 50 ° C. with 290 kPa steam, and degassed to a degassing tower 6 composed of a five-stage sieve tray at a flow rate of 0.9 m 3 / h. It was supplied from the tower supply port 7.
[0018]
In addition, dry air is supplied from the carrier gas supply port 8 at a flow rate of 0.65 m 3 / h, and the heated reaction liquid is brought into contact with the inside of the degassing tower 6 under a reduced pressure of 0.13 kPa to thereby remove low boiling substances. Removed. The reaction solution from which the low boiling point had been removed was transferred from the degassing tower 6 and supplied to the thin film evaporator 9. The reaction liquid supplied from the deaeration tower was distilled at 0.13 kPa and 68 ° C. in the thin film evaporator 9 to obtain 2-hydroxyethyl methacrylate. The EO concentration contained in the obtained 2-hydroxyethyl methacrylate was 12 ppm.
[0019]
[Examples 2 to 4]
Except for changing the preheating temperature by the preheater 5 to the conditions shown in Table 1, 2-hydroxyethyl methacrylate was produced in the same manner as in Example 1, and the results shown in Table 1 were obtained.
[0020]
[Comparative Example 1]
Production of 2-hydroxyethyl methacrylate in the same manner as in Example 1 except that the preheater 5 and the deaeration tower 6 are not used and the reaction liquid at 15 ° C. in the intermediate tank 2 is directly supplied to the thin film evaporator 9. did. The EO concentration contained in the obtained 2-hydroxyethyl methacrylate was 200 ppm.
[0021]
[ Reference Example 1 ]
2-hydroxyethyl methacrylate was produced in the same manner as in Example 1 except that the preheater 5 was not used and the 15 ° C. reaction solution in the intermediate tank 2 was directly supplied to the deaeration tower 6. The EO concentration contained in the obtained 2-hydroxyethyl methacrylate was 60 ppm.
[0022]
[Table 1]
【The invention's effect】
According to the method of the present invention, since EO can be efficiently removed at a temperature at which no polymerization trouble occurs, high-purity 2-hydroxyethyl (meth) acrylate with a low EO content can be produced. .
[Brief description of the drawings]
FIG. 1 is a diagram showing a process flow of a method for producing 2-hydroxyethyl methacrylate of the present invention and an outline of an apparatus used therefor.
[Explanation of symbols]
DESCRIPTION OF
Claims (1)
前記（メタ）アクリル酸とエチレンオキサイドとの反応液を４０〜７０℃に予熱した後脱気塔へ導いて、０．０１〜１．３３ｋＰａの減圧下で該反応液に吸収されにくいキャリアガスと接触させて未反応のエチレンオキサイドを除去した後、薄膜蒸発器にて０．０１〜１．３３ｋＰａの減圧下、６０〜１００℃で（メタ）アクリル酸２−ヒドロキシエチルを分離することを特徴とする（メタ）アクリル酸２−ヒドロキシエチルの製造方法。In the method of producing 2-hydroxyethyl (meth) acrylate by reacting (meth) acrylic acid with ethylene oxide,
A pre-heated reaction solution of (meth) acrylic acid and ethylene oxide at 40 to 70 ° C. and then led to a degassing tower, and a carrier gas that is not easily absorbed by the reaction solution under a reduced pressure of 0.01 to 1.33 kPa After removing unreacted ethylene oxide by contact, 2-hydroxyethyl (meth) acrylate is separated at 60 to 100 ° C. under a reduced pressure of 0.01 to 1.33 kPa in a thin film evaporator. A process for producing 2-hydroxyethyl (meth) acrylate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04219298A JP3850975B2 (en) | 1998-02-24 | 1998-02-24 | Method for producing 2-hydroxyethyl (meth) acrylate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04219298A JP3850975B2 (en) | 1998-02-24 | 1998-02-24 | Method for producing 2-hydroxyethyl (meth) acrylate |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2006098383A Division JP2006213729A (en) | 2006-03-31 | 2006-03-31 | 2-hydroxyethyl (meth)acrylate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11240853A JPH11240853A (en) | 1999-09-07 |
| JP3850975B2 true JP3850975B2 (en) | 2006-11-29 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP04219298A Expired - Lifetime JP3850975B2 (en) | 1998-02-24 | 1998-02-24 | Method for producing 2-hydroxyethyl (meth) acrylate |
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| Country | Link |
|---|---|
| JP (1) | JP3850975B2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1090903A3 (en) * | 1999-10-06 | 2003-04-16 | Nippon Shokubai Co., Ltd. | production process for hydroxyalkyl (meth)acrylate |
| JP3592970B2 (en) | 1999-10-07 | 2004-11-24 | 株式会社日本触媒 | Method for purifying hydroxyalkyl (meth) acrylate |
| JP2002114740A (en) | 2000-09-29 | 2002-04-16 | Nippon Shokubai Co Ltd | Method for producing hydroxyalkyl (meth)acrylate |
| JP4564226B2 (en) * | 2002-09-30 | 2010-10-20 | 株式会社日本触媒 | Method for producing hydroxyalkyl (meth) acrylate |
| JP5577841B2 (en) * | 2009-05-25 | 2014-08-27 | 三菱レイヨン株式会社 | Method for producing hydroxyalkyl (meth) acrylate |
| KR102238298B1 (en) * | 2020-02-27 | 2021-04-12 | 주식회사 삼양사 | Method for purifying diether of anhydrosugar alcohol with high purity |
| CN118416819A (en) * | 2024-07-04 | 2024-08-02 | 吉林市新跃新材料有限公司 | Process and equipment for preparing hydroxyethyl methacrylate |
-
1998
- 1998-02-24 JP JP04219298A patent/JP3850975B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH11240853A (en) | 1999-09-07 |
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