JPS63188648A - Production of methacrylic acid ester - Google Patents
Production of methacrylic acid esterInfo
- Publication number
- JPS63188648A JPS63188648A JP62020590A JP2059087A JPS63188648A JP S63188648 A JPS63188648 A JP S63188648A JP 62020590 A JP62020590 A JP 62020590A JP 2059087 A JP2059087 A JP 2059087A JP S63188648 A JPS63188648 A JP S63188648A
- Authority
- JP
- Japan
- Prior art keywords
- hydroxyisobutyrate
- acid ester
- alpha
- catalyst
- reaction
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 125000005397 methacrylic acid ester group Chemical group 0.000 title description 5
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 3
- 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 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 12
- -1 alpha-hydroxyisobutyric acid ester Chemical class 0.000 abstract description 9
- XYVQFUJDGOBPQI-UHFFFAOYSA-N Methyl-2-hydoxyisobutyric acid Chemical compound COC(=O)C(C)(C)O XYVQFUJDGOBPQI-UHFFFAOYSA-N 0.000 abstract description 8
- NGEWQZIDQIYUNV-UHFFFAOYSA-N L-valinic acid Natural products CC(C)C(O)C(O)=O NGEWQZIDQIYUNV-UHFFFAOYSA-N 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000004925 Acrylic resin Substances 0.000 abstract description 2
- 229920000178 Acrylic resin Polymers 0.000 abstract description 2
- 239000004566 building material Substances 0.000 abstract description 2
- 238000006297 dehydration reaction Methods 0.000 abstract description 2
- 238000010292 electrical insulation Methods 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 3
- 230000018044 dehydration Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 125000005395 methacrylic acid group Chemical group 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- BWLBGMIXKSTLSX-UHFFFAOYSA-N 2-hydroxyisobutyric acid Chemical class CC(C)(O)C(O)=O BWLBGMIXKSTLSX-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 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
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- GFUIDHWFLMPAGY-UHFFFAOYSA-N ethyl 2-hydroxy-2-methylpropanoate Chemical compound CCOC(=O)C(C)(C)O GFUIDHWFLMPAGY-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明はメタクリル酸エステルの製造方法に関する。[Detailed description of the invention] [Industrial application field] The present invention relates to a method for producing methacrylic acid ester.
メタクリル酸エステルは、アクリル樹脂製品の主成分と
して使用され、これらモノマーを重合して得られるポリ
マーは、エステルのアルキル基の種類によって種々の異
なった性能を示す０代表的なメタクリル酸エステルであ
るメタクリル酸メチルは、透明で光沢が良く、電気絶縁
性、耐薬品性及び加工性に優れているため、建築材料、
照明器具、塗料及び接着剤等幅広い用途がある。Methacrylic acid ester is used as the main component of acrylic resin products, and the polymers obtained by polymerizing these monomers exhibit various different performances depending on the type of alkyl group in the ester. Methyl acid is transparent, has good gloss, and has excellent electrical insulation, chemical resistance, and processability, so it is used as a building material,
It has a wide range of uses including lighting equipment, paints and adhesives.
既に、α−ヒドロキシイソ酪酸エステルを脱水してメタ
クリル酸エステルを製造する方法としては、硫酸を用い
る方法（特開昭６Ｏ−１８４０４７）、アルカリ土類金
属塩等の固体触媒を用いる方法（特公昭４４−２０６１
１．４４−２０６１２．４５−１５７２４）が知られて
いる。Already, methods for producing methacrylic ester by dehydrating α-hydroxyisobutyric acid ester include a method using sulfuric acid (Japanese Patent Publication No. 60-184047) and a method using a solid catalyst such as an alkaline earth metal salt (Japanese Patent Publication No. 60-184047). 44-2061
1.44-20612.45-15724) is known.
しかしながら硫酸を用いた場合は、一般に分解が生じ易
く、そのために目的とするメタクリル酸エステルの収率
が低くなる欠点があり、収率を上げるためには、反応温
度、接触時間等を調節する煩雑な操作及び多量の硫酸を
必要とする。However, when sulfuric acid is used, it generally tends to decompose, resulting in a low yield of the desired methacrylic ester.In order to increase the yield, it is difficult to adjust the reaction temperature, contact time, etc. Requires extensive handling and large amounts of sulfuric acid.
また、アルカリ土類金属塩等の固体触媒を用いる場合は
、反応が高温で気相反応になるという欠点がある。Furthermore, when using a solid catalyst such as an alkaline earth metal salt, there is a drawback that the reaction becomes a gas phase reaction at high temperatures.
本発明者らは、前述の欠点を解決するため、種々検討を
重ねた結果、触媒としてナトリウムメトキサイド、また
はカリウムメトキサイドを用いることにより、高収率、
かつ反応温度、接触時間等の制御といった煩雑な操作を
することなしに、メタクリル酸エステルが製造できるこ
とを見出し、本発明を完成させるに至った。In order to solve the above-mentioned drawbacks, the present inventors have made various studies and found that by using sodium methoxide or potassium methoxide as a catalyst, high yield and
The inventors have also discovered that methacrylic acid esters can be produced without complicated operations such as controlling reaction temperature, contact time, etc., and have completed the present invention.
すなわち、本発明は
一般式（１）
％式％（１）
（式中、Ｒは炭素数１〜４のアルキル基を示す）で表さ
れる、α−ヒドロキシイソ酪酸エステルを脱水し、対応
するメタクリル酸エステルを製造するに際して、触媒と
してナトリウムメトキサイドまたはカリウムメトキサイ
ドを用いることを特徴とするメタクリル酸エステルの製
造方法である。That is, the present invention dehydrates an α-hydroxyisobutyric acid ester represented by the general formula (1) % formula % (1) (wherein R represents an alkyl group having 1 to 4 carbon atoms), and This is a method for producing a methacrylic ester, characterized in that sodium methoxide or potassium methoxide is used as a catalyst in producing the methacrylic ester.
以下、本発明の方法を詳細に説明する。The method of the present invention will be explained in detail below.
本発明の方法は、α−ヒドロキシイソ酪酸エステルと触
媒の混合液を加熱、撹拌して反応を進め、目的のメタク
リル酸エステルを製造する方法である。The method of the present invention is a method for producing the desired methacrylic ester by heating and stirring a mixed solution of α-hydroxyisobutyric acid ester and a catalyst to advance the reaction.
本発明の方法に用いられるα−ヒドロキシイソ酪酸エス
テルとしては、α−ヒドロキシイソ酪酸メチル、α−ヒ
ドロキシイソ酪酸エチル、α−ヒドーロキシイソ酪酸ｎ
−プロピル、α−ヒドロキシイソ酪酸１ｓｏ−プロピル
、α−ヒドロキシイソ酪酸ｎ−ブチル、α−ヒドロキシ
イソ酪酸１ｓｏ−ブチル、α−ヒドロキシイソ酪酸ｔ−
ブチルがあり、これらのα−ヒドロキシイソ酪酸エステ
ルを原料として対応するメタクリル酸メチル、メタクリ
ル酸エチル、メタクリルｆｉｎ−プロピル、メタクリル
＆ｆｉｓｏ−プロピル、メタクリル酸ｎ−ブチル、メタ
クリル酸１ｓｏ−ブチル、メタクリル酸ｔ・ブチルを製
造することができる。The α-hydroxyisobutyric acid esters used in the method of the present invention include methyl α-hydroxyisobutyrate, ethyl α-hydroxyisobutyrate, n-hydroxyisobutyrate
-propyl, 1so-propyl α-hydroxyisobutyrate, n-butyl α-hydroxyisobutyrate, 1so-butyl α-hydroxyisobutyrate, t-hydroxyisobutyrate α-
butyl, and these α-hydroxyisobutyric acid esters are used as raw materials to produce the corresponding methyl methacrylate, ethyl methacrylate, methacrylic fin-propyl, methacrylic & fiso-propyl, n-butyl methacrylate, 1so-butyl methacrylate, and t methacrylate.・Butyl can be produced.
本発明の方法に用いられる触媒は、ナトリウムメトキサ
イド、またはカリウムメトキサイドであり、その使用量
は、ｙ−ヒドロキシイソ酪酸エステルに対して０．５〜
１０重量％の範囲であり、より好ましくは１〜７重量％
の範囲である。The catalyst used in the method of the present invention is sodium methoxide or potassium methoxide, and the amount used is 0.5 to 0.5 to
In the range of 10% by weight, more preferably from 1 to 7% by weight
is within the range of
本発明の方法において、脱水反応は常圧あるいは減圧下
で実施できる０反応塩度は５０〜１５０℃の範囲であり
、より好ましくは６０〜１１０°Ｃの範囲である。In the method of the present invention, the dehydration reaction can be carried out at normal pressure or reduced pressure.
反応時間は、使用する原料の量、温度及び触媒量等によ
って変わるが、通常は０．５〜７時間である。The reaction time varies depending on the amount of raw materials used, temperature, amount of catalyst, etc., but is usually 0.5 to 7 hours.
なお、目的物であるメタクリル酸エステルは、反応終了
後蒸留等の操作によって精製する。Note that the target methacrylic acid ester is purified by operations such as distillation after the reaction is completed.
本発明の方法によれば、多量の硫酸を用いる、または反
応温度、接触時間を制御するといった煩雑な操作を必要
とすることなく、温和な条件のもとて短時間の内に反応
を進めることができる。According to the method of the present invention, the reaction can proceed in a short time under mild conditions without the need for complicated operations such as using a large amount of sulfuric acid or controlling the reaction temperature and contact time. Can be done.
また、メタクリル酸を始めとする副生成物の生成が少な
く、目的とするメタクリル酸エステルを高収率で製造す
ることができる。Furthermore, by-products such as methacrylic acid are less produced, and the desired methacrylic ester can be produced in high yield.
以下、実施例により本発明の方法を具体的に説明する。 Hereinafter, the method of the present invention will be specifically explained with reference to Examples.
′実施例１
攪拌機、温度計及び冷却管を備えた内容積５００−１の
フラスコにα−ヒドロキシイソ酪酸メチル２９５ｇ（２
，５ｍｏｌ）、ナトリウムメトキサイド１３．５ｇ（０
，２５＋５ｏｌ）を仕込み、温度７０〜７５°Ｃで攪拌
しなから反応を行った。１時間後のα−ヒドロキシイソ
酪酸メチルの転化率は５１．５％、３時間後の転化率
゛は８１．８％となり、その後は殆ど変わらなか
った。'Example 1 295 g of methyl α-hydroxyisobutyrate (2
, 5 mol), sodium methoxide 13.5 g (0
, 25+5 ol) and the reaction was carried out at a temperature of 70 to 75°C without stirring. The conversion rate of methyl α-hydroxyisobutyrate after 1 hour was 51.5%, and the conversion rate after 3 hours.
゛ was 81.8% and remained almost unchanged thereafter.
なお、この時の副生酸物濃度は１０重量％以下であった
０反応は４時間で終了し、反応終了後３００ｍｍＨｇで
反応液を減圧蒸留し、目的のメタクリル酸メチルを１７
０．０ｇ得た。α−ヒドロキシイソ酪酸メチル基準の収
率は６８％であった。The by-product acid concentration at this time was 10% by weight or less. The reaction was completed in 4 hours, and after the reaction was completed, the reaction solution was distilled under reduced pressure at 300 mmHg to obtain 17% of the target methyl methacrylate.
0.0g was obtained. The yield based on methyl α-hydroxyisobutyrate was 68%.
実施例２〜４
実施例１と同じ装置を使用し、同様な方法で、原料のα
−ヒドロキシイソ酪酸エステルの種類を変えて対応する
メタクリル酸エステルを合成した結果を表１に示す。Examples 2 to 4 Using the same equipment as in Example 1 and using the same method, α of the raw material was
Table 1 shows the results of synthesizing the corresponding methacrylic esters by changing the types of -hydroxyisobutyric esters.
実施例５
実施例１と同じ装置を使用し、α−ヒドロキシイソ酪酸
メチル２９５ｇ（２，５ｍｏｌ）、カリウムメトキサイ
ド１４ｇ（０，２＋ｇｏ＋）を仕込み、温度７０〜７５
℃で攪拌しながら反応を行った。１時間後のα−ヒドロ
キシイソ酪酸メチルの転化率は４５．２％、３時間後の
転化率は６２．８％となり、５時間後の転化率は７８．
２％となった。Example 5 Using the same equipment as in Example 1, 295 g (2.5 mol) of methyl α-hydroxyisobutyrate and 14 g (0,2+go+) of potassium methoxide were charged, and the temperature was 70-75.
The reaction was carried out at °C with stirring. The conversion rate of methyl α-hydroxyisobutyrate after 1 hour was 45.2%, the conversion rate after 3 hours was 62.8%, and the conversion rate after 5 hours was 78.
It became 2%.
なお、この時の副生酸物濃度は、１２ 重量％であっ
た。Note that the concentration of by-product acid at this time was 12% by weight.
反応終了後、実施例１と同様に反応液を減圧蒸留し、メ
タクリル酸メチル１５５．０．を得た。メタクリル酸メ
チルのα−ヒドロキシイソ酪酸メチル基準の収率は、６
２％であった。After the reaction was completed, the reaction solution was distilled under reduced pressure in the same manner as in Example 1, and 155.0% of methyl methacrylate was obtained. I got it. The yield of methyl methacrylate based on methyl α-hydroxyisobutyrate is 6
It was 2%.
Claims (1)
れる、α−ヒドロキシイソ酪酸エステルを脱水し、対応
するメタクリル酸エステルを製造するに際して、触媒と
してナトリウムメトキサイドまたはカリウムメトキサイ
ドを用いることを特徴とするメタクリル酸エステルの製
造方法。[Claims] 1. General formula (1) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (1) (In the formula, R represents an alkyl group having 1 to 4 carbon atoms), α- 1. A method for producing a methacrylic ester, which comprises using sodium methoxide or potassium methoxide as a catalyst in producing the corresponding methacrylic ester by dehydrating a hydroxyisobutyric ester.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62020590A JPH0710796B2 (en) | 1987-02-02 | 1987-02-02 | Method for producing methacrylic acid ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62020590A JPH0710796B2 (en) | 1987-02-02 | 1987-02-02 | Method for producing methacrylic acid ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63188648A true JPS63188648A (en) | 1988-08-04 |
| JPH0710796B2 JPH0710796B2 (en) | 1995-02-08 |
Family
ID=12031456
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62020590A Expired - Lifetime JPH0710796B2 (en) | 1987-02-02 | 1987-02-02 | Method for producing methacrylic acid ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0710796B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11578160B2 (en) | 2020-09-30 | 2023-02-14 | Sumitomo Chemical Company, Limited | Composition |
-
1987
- 1987-02-02 JP JP62020590A patent/JPH0710796B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11578160B2 (en) | 2020-09-30 | 2023-02-14 | Sumitomo Chemical Company, Limited | Composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0710796B2 (en) | 1995-02-08 |
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