JPH0710797B2 - Method for producing methacrylic acid ester - Google Patents
Method for producing methacrylic acid esterInfo
- Publication number
- JPH0710797B2 JPH0710797B2 JP62020591A JP2059187A JPH0710797B2 JP H0710797 B2 JPH0710797 B2 JP H0710797B2 JP 62020591 A JP62020591 A JP 62020591A JP 2059187 A JP2059187 A JP 2059187A JP H0710797 B2 JPH0710797 B2 JP H0710797B2
- Authority
- JP
- Japan
- Prior art keywords
- acid ester
- methacrylic acid
- methoxyisobutyrate
- reaction
- 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 15
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- -1 β-methoxyisobutyric acid ester Chemical class 0.000 claims description 14
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 10
- 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 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 17
- 238000000034 method Methods 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 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
- 239000002994 raw material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- AKWHOGIYEOZALP-UHFFFAOYSA-N methyl 2-methoxy-2-methylpropanoate Chemical compound COC(=O)C(C)(C)OC AKWHOGIYEOZALP-UHFFFAOYSA-N 0.000 description 2
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- JIRULJUIQOAJPM-UHFFFAOYSA-N 3-methoxy-2-methylpropanoic acid Chemical class COCC(C)C(O)=O JIRULJUIQOAJPM-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 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
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003973 paint Substances 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
- 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
て使用される。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。Methacrylic acid ester is used as the main component of acrylic resin products. Methyl methacrylate, which is a typical methacrylic acid ester, is transparent and has good gloss, and is excellent in electrical insulation, chemical resistance, and processability.
また、メタクリル酸エチル、メタクリル酸プロピル、メ
タクリル酸ブチル等は、塗料、接着剤及び繊維処理剤等
として有用な化合物である。In addition, ethyl methacrylate, propyl methacrylate, butyl methacrylate and the like are compounds useful as paints, adhesives, fiber treatment agents and the like.
β‐メトキシイソ酪酸エステルを脱アルコールしてメタ
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、アリールスルホン酸、p-トルエンスルホン酸及
びベンゼンスルホン酸を用いる方法（特開昭48-14617号
公報）が知られている。As a method for dealcoholating β-methoxyisobutyric acid ester to produce a methacrylic acid ester, a method using sulfuric acid, a method using arylsulfonic acid, p-toluenesulfonic acid and benzenesulfonic acid (Japanese Patent Laid-Open No. 48-14617) is disclosed. )It has been known.
しかしながら、硫酸を用いた場合は分解及び副生成物が
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、この時多量の硫酸を必要
とする。またアリールスルホン酸、p-トルエンスルホン
酸及びベンゼンスルホン酸を用いる場合は反応温度が10
0〜170℃と高く、またこの場合も副生成物が生じ易く目
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
ある。However, the use of sulfuric acid has a drawback that decomposition and by-products are likely to occur, resulting in a low yield of the target methacrylic acid ester, and a large amount of sulfuric acid is required at this time. When arylsulfonic acid, p-toluenesulfonic acid and benzenesulfonic acid are used, the reaction temperature is 10
It is as high as 0 to 170 ° C., and also in this case, there is a drawback that the yield of the target methacrylic acid ester is low because a by-product is easily generated.
本発明者らは、前述の方法の欠点を解決するために鋭意
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、副生
成物の生成を抑え高収率かつ容易な操作でメタクリル酸
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。The present inventors have conducted extensive studies in order to solve the drawbacks of the above-mentioned method, and by using sodium methoxide or potassium methoxide as a catalyst, it is possible to suppress the production of by-products and to easily produce a high yield. The inventors have found that a methacrylic acid ester can be produced by an operation, 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、β‐メトキシイソ酪酸エステルを脱アルコール
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) (Wherein R represents an alkyl group having 1 to 4 carbon atoms), the β-methoxyisobutyric acid ester is dealcoholated 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、β‐メト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 solution of β-methoxyisobutyric acid ester and a catalyst to proceed the reaction.
本発明の方法に用いられるβ‐メトキシイソ酪酸エステ
ルとしては、β‐メトキシイソ酪酸メチル、β‐メトキ
シイソ酪酸エチル、β‐メトキシイソ酪酸n-プロピル、
β‐メトキシイソ酪酸iso-プロピル、β‐メトキシイソ
酪酸n-ブチル、β‐メトキシイソ酪酸iso-ブチル及びβ
‐メトキシイソ酪酸t-ブチルがあり、これらのβ‐メト
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-ブチル及びメタクリル酸t-ブチル
を製造することができる。Examples of β-methoxyisobutyric acid ester used in the method of the present invention include methyl β-methoxyisobutyrate, ethyl β-methoxyisobutyrate, and n-propyl β-methoxyisobutyrate.
β-methoxyisobutyrate iso-propyl, β-methoxyisobutyrate n-butyl, β-methoxyisobutyrate iso-butyl and β
-Methoxyisobutyric acid t-butyl is available, and these β-methoxyisobutyric acid esters are used as raw materials for the corresponding methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, isomethacrylate. -Butyl and 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
β‐メトキシイソ酪酸エステルに対して１〜20重量％の
範囲であり、より好ましくは４〜10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 used is in the range of 1 to 20% by weight, more preferably 4 to 10% by weight, based on β-methoxyisobutyric acid ester. Is the range.
本発明の方法において脱アルコール反応は常圧あるいは
減圧下で実施できる。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 dealcoholization 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 material used, temperature, amount of catalyst, etc., but is usually 0.5 to 7 hours.
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β‐メトキシイソ酪酸メチル330g（2.5mol）、ナ
トリウムメトキサイド21.6g（0.4mol）を仕込み、温度7
0〜75℃で撹拌しながら反応を行った。１時間後のβ‐
メトキシイソ酪酸メチルの転化率は78.2％となり、３時
間後の転化率は94.1％となった。Example 1 A flask having an internal volume of 500 ml equipped with a stirrer, a thermometer and a cooling tube was charged with 330 g (2.5 mol) of methyl β-methoxyisobutyrate and 21.6 g (0.4 mol) of sodium methoxide, and the temperature was adjusted to 7
The reaction was carried out with stirring at 0 to 75 ° C. Β-after 1 hour
The conversion rate of methyl methoxyisobutyrate was 78.2%, and the conversion rate after 3 hours was 94.1%.
なお、この時の副生成物濃度は１重量％以下であった。The by-product concentration at this time was 1% by weight or less.
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226.5gを得た。
β‐メトキシイソ酪酸メチル基準の収率は90.5％であっ
た。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 226.5 g of the target methyl methacrylate.
The yield based on methyl β-methoxyisobutyrate was 90.5%.
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β‐メ
ト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 Table 1 shows the results of synthesizing corresponding methacrylic acid esters by using the same apparatus as in Example 1 and changing the type of the raw material β-methoxyisobutyric acid ester in the same manner.
実施例 ５ 実施例１と同じ装置を使用し、β‐メトキシイソ酪酸メ
チル330g（2.5mol）、カリウムメトキサイド28g（0.4mo
l）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β‐メトキシイソ酪酸メチルの転化率は
62.4％となり、３時間後の転化率は81.3％となった。Example 5 Using the same apparatus as in Example 1, 330 g (2.5 mol) of methyl β-methoxyisobutyrate, 28 g of potassium methoxide (0.4 mol) were used.
l) was charged and the reaction was carried out at a temperature of 70 to 75 ° C. with stirring. The conversion rate of methyl β-methoxyisobutyrate after 1 hour is
It was 62.4% and the conversion rate after 3 hours was 81.3%.
なお、この時の副生成物濃度は3.6重量％であった。The by-product concentration at this time was 3.6% 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195.2gを得た。メタクリル酸メチルのβ
‐メトキシイソ酪酸メチル基準の収率は78％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 195.2 g of methyl methacrylate. Β of methyl methacrylate
-The yield based on methyl methoxyisobutyrate was 78%.
Claims (1)
れる、β‐メトキシイソ酪酸エステルを脱アルコール
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. A general formula (1) (Wherein R represents an alkyl group having 1 to 4 carbon atoms), the β-methoxyisobutyric acid ester is dealcoholated 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 |
|---|---|---|---|
| JP62020591A JPH0710797B2 (en) | 1987-02-02 | 1987-02-02 | Method for producing methacrylic acid ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62020591A JPH0710797B2 (en) | 1987-02-02 | 1987-02-02 | Method for producing methacrylic acid ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63188649A JPS63188649A (en) | 1988-08-04 |
| JPH0710797B2 true JPH0710797B2 (en) | 1995-02-08 |
Family
ID=12031486
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62020591A Expired - Lifetime JPH0710797B2 (en) | 1987-02-02 | 1987-02-02 | Method for producing methacrylic acid ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0710797B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19548912A1 (en) * | 1995-12-27 | 1997-07-03 | Basf Ag | Process for the esterification of (meth) acrylic acid with an alkanol |
-
1987
- 1987-02-02 JP JP62020591A patent/JPH0710797B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63188649A (en) | 1988-08-04 |
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