JPH0710796B2 - Method for producing methacrylic acid ester - Google Patents
Method for producing methacrylic acid esterInfo
- Publication number
- JPH0710796B2 JPH0710796B2 JP62020590A JP2059087A JPH0710796B2 JP H0710796 B2 JPH0710796 B2 JP H0710796B2 JP 62020590 A JP62020590 A JP 62020590A JP 2059087 A JP2059087 A JP 2059087A JP H0710796 B2 JPH0710796 B2 JP H0710796B2
- Authority
- JP
- Japan
- Prior art keywords
- acid ester
- methacrylic acid
- reaction
- hydroxyisobutyrate
- methyl
- 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.)
- Expired - Lifetime
Links
- 125000005397 methacrylic acid ester group Chemical group 0.000 title claims description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- -1 α-hydroxyisobutyric acid ester Chemical class 0.000 claims description 11
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 10
- NGEWQZIDQIYUNV-UHFFFAOYSA-N L-valinic acid Natural products CC(C)C(O)C(O)=O NGEWQZIDQIYUNV-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 6
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 20
- 238000000034 method Methods 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- XYVQFUJDGOBPQI-UHFFFAOYSA-N Methyl-2-hydoxyisobutyric acid Chemical compound COC(=O)C(C)(C)O XYVQFUJDGOBPQI-UHFFFAOYSA-N 0.000 description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 5
- BWLBGMIXKSTLSX-UHFFFAOYSA-N 2-hydroxyisobutyric acid Chemical compound CC(C)(O)C(O)=O BWLBGMIXKSTLSX-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 150000002148 esters Chemical class 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
- 239000007788 liquid Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 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
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 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)
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。TECHNICAL FIELD The present invention relates to a method for producing a 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。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 a main component of acrylic resin products, and the polymer obtained by polymerizing these monomers exhibits various different performances depending on the type of alkyl group of the ester. Methyl methacrylate, which is a typical methacrylate ester, is transparent and has good gloss, and is excellent in electrical insulation, chemical resistance, and processability. Building materials,
It has a wide range of applications such as 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60-184047）、アルカリ土類金属塩等の
固体触媒を用いる方法（特公昭44-20611、44-20612、45
-15724）が知られている。Already, as a method for producing a methacrylic acid ester by dehydrating α-hydroxyisobutyric acid ester, a method using sulfuric acid (JP-A-60-184047), a method using a solid catalyst such as an alkaline earth metal salt (Japanese Patent Publication No. 44-20611, 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, decomposition is generally likely to occur, and therefore the yield of the target methacrylic acid ester is low, and in order to increase the yield, it is complicated to adjust the reaction temperature, contact time, etc. Various operations and a large amount of sulfuric acid are required.
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。Further, when a solid catalyst such as an alkaline earth metal salt is used, there is a drawback that the reaction becomes a gas phase reaction at high temperature.
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 conducted various studies, and as a result, by using sodium methoxide or potassium methoxide as a catalyst, a high yield,
Moreover, they have found that a methacrylic acid ester can be produced without performing a complicated operation such as control of reaction temperature and contact time, and have completed the present invention.
すなわち、本発明は 一般式（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 relates to the general formula (1) (In the formula, R represents an alkyl group having 1 to 4 carbon atoms), α-hydroxyisobutyric acid ester is dehydrated to produce a corresponding methacrylic acid ester, and sodium methoxide or potassium methoxide is used as a catalyst. A method for producing a methacrylic acid ester characterized by using a side.
以下、本発明の方法を詳細に説明する。Hereinafter, the method of the present invention will be described in detail.
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 a target methacrylic acid ester by heating and stirring a mixed liquid of α-hydroxyisobutyric acid ester and a catalyst to proceed 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‐ヒドロキシイソ酪酸n-プ
ロピル、α‐ヒドロキシイソ酪酸iso-ピロピル、α‐ヒ
ドロキシイソ酪酸n-ブチル、α‐ヒドロキシイソ酪酸is
o-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
クリル酸n-プロピル、メタクリル酸iso-プロピル、メタ
クリル酸n-ブチル、メタクリル酸iso-ブチル、メタクリ
ル酸t-ブチルを製造することができる。Examples of the α-hydroxyisobutyric acid ester used in the method of the present invention include methyl α-hydroxyisobutyrate, ethyl α-hydroxyisobutyrate, n-propyl α-hydroxyisobutyrate, α-hydroxyisobutyric acid iso-pyropyr, α- N-Butyl hydroxyisobutyrate, α-hydroxyisobutyric acid is
o-Butyl and t-butyl α-hydroxyisobutyrate are available, and these α-hydroxyisobutyric acid esters are used as raw materials for the corresponding methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, and methacrylic acid. n-Butyl, iso-butyl methacrylate, t-butyl methacrylate 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、α‐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 thereof is 0.5 to 10 with respect to α-hydroxyisobutyric acid ester.
It is in the range of wt%, and more preferably in the range of 1 to 7 wt%.
本発明の方法において、脱水反応は常圧あるいは滅圧下
で実施できる。反応温度は50〜150℃の範囲であり、よ
り好ましくは60〜110℃の範囲である。In the method of the present invention, the dehydration reaction can be carried out under normal pressure or reduced pressure. The reaction temperature is in the range of 50 to 150 ° C, more preferably 60 to 110 ° C.
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, the temperature, the 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。The target methacrylic acid ester is purified by an operation such as distillation after the completion of the reaction.
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、温和な条件のもとで短時間の内に反応
を進めることができる。According to the method of the present invention, it is possible to proceed the reaction in a short time under mild conditions without using a complicated operation such as using a large amount of sulfuric acid or controlling the reaction temperature and the contact time. You can
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。Moreover, the production of by-products such as methacrylic acid is small, and the target methacrylic acid 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 described with reference to examples.
実施例１ 撹拌機、温度計及び冷却管を備えた内容積500ml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（0.25mol）を仕込み、温
度70〜75℃で撹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 (2.5 mol) of methyl α-hydroxyisobutyrate was added to a flask having an inner volume of 500 ml equipped with a stirrer, a thermometer and a cooling tube.
13.5 g (0.25 mol) of sodium methoxide was charged and the reaction was carried out at a temperature of 70 to 75 ° C with stirring. Α after 1 hour
-The conversion of methyl hydroxyisobutyrate was 51.5%, the conversion after 3 hours was 81.8%, and remained almost unchanged thereafter.
なお、この時の副生成物濃度は10重量％以下であった。
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170.0g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 concentration at this time was 10% by weight or less.
The reaction was completed in 4 hours, and after completion of the reaction, the reaction solution was distilled under reduced pressure at 300 mmHg to obtain 170.0 g of the objective methyl methacrylate.
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 apparatus as in Example 1 and in the same manner,
Table 1 shows the results of synthesizing corresponding methacrylic acid esters by changing the type of -hydroxyisobutyric acid ester.
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
mol）を仕込み、温度70〜75℃で撹拌しながら反応を行
なった。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 apparatus as in Example 1, 295 g (2.5 mol) of methyl α-hydroxyisobutyrate and 14 g (0.2 g of potassium methoxide) were used.
mol) was charged and the reaction was carried out at a temperature of 70 to 75 ° 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 78.2%.
なお、この時の副生成物濃度は、12重量％であった。The by-product concentration 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155.0g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、62％であ
った。After completion of the reaction, the reaction solution was distilled under reduced pressure in the same manner as in Example 1 to obtain 155.0 g of methyl methacrylate. The yield of methyl methacrylate based on methyl α-hydroxyisobutyrate was 62%.
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。1. The general formula (1) (In the formula, R represents an alkyl group having 1 to 4 carbon atoms), α-hydroxyisobutyric acid ester is dehydrated to produce a corresponding methacrylic acid ester, and sodium methoxide or potassium methoxide is used as a catalyst. A method for producing a methacrylic acid ester, which comprises using a side.
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 JPS63188648A (en) | 1988-08-04 |
| JPH0710796B2 true 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) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6889322B1 (en) | 2020-09-30 | 2021-06-18 | 住友化学株式会社 | Composition |
-
1987
- 1987-02-02 JP JP62020590A patent/JPH0710796B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63188648A (en) | 1988-08-04 |
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