JPH04198151A - Production of methacrylic acid - Google Patents

Production of methacrylic acid

Info

Publication number
JPH04198151A
JPH04198151A JP2322463A JP32246390A JPH04198151A JP H04198151 A JPH04198151 A JP H04198151A JP 2322463 A JP2322463 A JP 2322463A JP 32246390 A JP32246390 A JP 32246390A JP H04198151 A JPH04198151 A JP H04198151A
Authority
JP
Japan
Prior art keywords
acid
methyl methacrylate
methacrylic acid
reaction
organic carboxylic
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.)
Pending
Application number
JP2322463A
Other languages
Japanese (ja)
Inventor
Hirobumi Higuchi
博文 樋口
Takafumi Abe
崇文 阿部
Nobuyuki Takara
宝 伸幸
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Gas Chemical Co Inc
Original Assignee
Mitsubishi Gas Chemical Co Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Mitsubishi Gas Chemical Co Inc filed Critical Mitsubishi Gas Chemical Co Inc
Priority to JP2322463A priority Critical patent/JPH04198151A/en
Publication of JPH04198151A publication Critical patent/JPH04198151A/en
Pending legal-status Critical Current

Links

Classifications

    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/52Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

PURPOSE:To easily produce methacrylic acid with a simple apparatus in high quality by carrying out the acid transesterification of methyl methacrylate and an organic carboxylic acid in the presence of an acidic catalyst such as strongly acidic ion exchange resin. CONSTITUTION:Methacrylic acid is produced by reacting methyl methacrylate with an organic carboxylic acid in the presence of an acidic catalyst at 50-120 deg.C for 30min to 24hr. The organic carboxylic acid is preferably the one giving the organic carboxylic acid methyl ester having a boiling point lower than the boiling point of methyl methacrylate used as a raw material and is e.g. formic acid, acetic acid, propionic acid and acrylic acid. Sulfuric acid, benzenesulfonic acid, etc., may be used as the acidic catalyst, however, the use of a strongly acidic ion exchange resin is especially preferable from the viewpoint of the reaction selectivity and the separability of the reaction product.

Description

【発明の詳細な説明】 (産業上の利用分野) 本発明は、メタクリル酸メチルからのメタクリル酸製造
法に関する。 メタクリル酸は、種々のメタクリル酸エ
ステル系ポリマーの原料として大量に使用されており、
工業的に極めて重要な中間原料である。
DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for producing methacrylic acid from methyl methacrylate. Methacrylic acid is used in large quantities as a raw material for various methacrylic acid ester polymers.
It is an extremely important intermediate raw material industrially.

(従来技術およびその問題点) メタクリル酸の工業的製造法としては、青酸トアセトン
を原料としてアセトンシアンヒドリンを経由する所謂A
CH法と、イソブチレンやt−ブタノールを原料とする
所謂C4酸化法とが実用化されているが、何れの方法に
おいてもメタクリル酸メチルが併産されている。  し
かし、画法ともメタクリル酸とメタクリル酸メチルとを
合せて致方トン規模で生産しており、装置も複雑なこと
から数百トン前後の少量規模でのメタクリル酸製造の為
には適した方法とは云えない。
(Prior art and its problems) As an industrial method for producing methacrylic acid, the so-called A method uses toacetone cyanide as a raw material and passes through acetone cyanohydrin.
The CH method and the so-called C4 oxidation method using isobutylene or t-butanol as raw materials have been put into practical use, but methyl methacrylate is co-produced in both methods. However, since the painting method involves producing methacrylic acid and methyl methacrylate together on a ton scale, and the equipment is complicated, it is not suitable for producing methacrylic acid on a small scale of around several hundred tons. I can't say that.

工程数が少なく、比較的簡単な装置を使用してのメタク
リル酸製造法としては、メタクリル酸メチルの加水分解
法が考えられる。
As a method for producing methacrylic acid with a small number of steps and using relatively simple equipment, a method of hydrolyzing methyl methacrylate can be considered.

しかし、この方法では反応原料のメタクリル酸メチルと
水との相溶性が低く、従って反応速度が小さいこと、又
生成するメタノールと原料メタクリル酸メチル、及び水
とが最低共沸混合物を形成し反応系外に留出することか
ら効率的なメタクリル酸製造法であるとは云い難いもの
である。
However, in this method, the compatibility between the reaction raw material methyl methacrylate and water is low, so the reaction rate is low, and the methanol produced, the raw material methyl methacrylate, and water form a minimum azeotrope, resulting in the reaction system Since methacrylic acid is distilled out, it is difficult to say that it is an efficient method for producing methacrylic acid.

(問題点を解決するための手段) 本発明者等は、メタクリル酸メチルから簡単な装置を使
い効率よくメタクリル酸を製造する方法について鋭意研
究を進めた結果、本発明に到達し完成させることができ
た。 即ち、本発明は、メタクリル酸メチルと有機カル
ボン酸とから、酸性触媒存在下でメタクリル酸と有機カ
ルボン酸メチルとを製造することを特徴とするメタクリ
ル酸の製造方法に関するものである。 本発明の方法は
、比較的入手の容易なメタクリル酸メチルと有機カルボ
ン酸とを原料とし、酸エステル交換反応によりメタクリ
ル酸と有機カルボン酸メチルとを製造するものであり、
反応系内にメタクリル酸メチルと共沸する水が存在しな
いことから、効率よく反応を進行させることができ、又
生成するメタクリル酸を容易に分離精製することができ
るものである。
(Means for Solving the Problems) As a result of intensive research into a method for efficiently producing methacrylic acid from methyl methacrylate using a simple device, the present inventors have arrived at and completed the present invention. did it. That is, the present invention relates to a method for producing methacrylic acid, which is characterized in that methacrylic acid and methyl organic carboxylate are produced from methyl methacrylate and an organic carboxylic acid in the presence of an acidic catalyst. The method of the present invention uses relatively easily available methyl methacrylate and organic carboxylic acid as raw materials to produce methacrylic acid and methyl organic carboxylate through an acid transesterification reaction,
Since water that is azeotropic with methyl methacrylate does not exist in the reaction system, the reaction can proceed efficiently, and the methacrylic acid produced can be easily separated and purified.

本発明の方法における酸エステル交換反応は、平衡反応
であり、反応時に生成物だけを反応系外に除くことがで
きれば、反応率を高く維持できる。
The acid transesterification reaction in the method of the present invention is an equilibrium reaction, and if only the product can be removed from the reaction system during the reaction, the reaction rate can be maintained at a high level.

即ち、本発明の方法に用いられる有機カルボン酸は、生
成する有機カルボン酸メチルエステルが原料のメタクリ
ル酸メチルよりも低沸点であることが望ましく、有機カ
ルボン酸としては炭素数1〜3の脂肪族カルボン酸が好
適である。 例えば、ギ酸、酢酸、プロピオン酸、アク
リル酸を挙げることができる。
That is, it is preferable that the organic carboxylic acid used in the method of the present invention has a lower boiling point than the raw material methyl methacrylate, and the organic carboxylic acid is an aliphatic acid having 1 to 3 carbon atoms. Carboxylic acids are preferred. Examples include formic acid, acetic acid, propionic acid, and acrylic acid.

本発明の方法における酸性触媒としては、硫酸、ベンゼ
ンスルホン酸、トルエンスルホン酸、又はスルホン酸基
含有イオン交換樹脂が使用されるが、反応の選択性、及
び触媒と生成物の分離の面から強酸性イオン交換樹脂が
特に好ましく、高選択的に高収率を以て高品質のメタク
リル酸と有機カルボン酸メチルを製造することができる
As the acidic catalyst in the method of the present invention, sulfuric acid, benzenesulfonic acid, toluenesulfonic acid, or an ion exchange resin containing a sulfonic acid group is used. Polymer ion exchange resins are particularly preferred because they can produce high-quality methacrylic acid and methyl organic carboxylate with high selectivity and high yield.

本発明の方法における反応温度は、原料の有機カルボン
酸や触媒の種類によって選択されるが、反応温度20〜
150℃、好ましくは50〜120℃の範囲であり、又
反応時間は10分〜48時間、好ましくは30分〜24
時間の範囲である。
The reaction temperature in the method of the present invention is selected depending on the raw material organic carboxylic acid and the type of catalyst, but the reaction temperature
The temperature is 150°C, preferably 50 to 120°C, and the reaction time is 10 minutes to 48 hours, preferably 30 minutes to 24 hours.
It is a range of time.

本発明の方法におけるメタクリル酸メチルに対する有機
カルボン酸のモル比は、0.2〜5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.
5〜3の範囲が好ましい。
The molar ratio of organic carboxylic acid to methyl methacrylate in the method of the present invention may be from 0.2 to 5, but if the energy cost required for separation after the reaction is taken into account, the molar ratio may be 0.2 to 5.
The range of 5 to 3 is preferable.

本発明における反応方式は、反応原料と触媒が接触する
方法であれば何れの方法でも採 青用することができる
が、酸エステル交換反応は平衡反応である為、反応蒸留
等の方法により副生ずる有機カルボン酸メチルを系外に
留出除去する方法をとることが反応率を高める上で有効
である。
The reaction method used in the present invention can be adopted in any method as long as the reaction raw material and the catalyst come into contact with each other, but since the acid transesterification reaction is an equilibrium reaction, by-products may be produced by methods such as reactive distillation. It is effective to distill and remove organic methyl carboxylate from the system in order to increase the reaction rate.

本発明の方法においては、反応生成液から未反応原料と
触媒を除去するだけで高純度のメタクリル酸を得ること
ができるが、必要に応じて蒸留等の常法により精製すれ
ば゛、更に高品質のメタクリル酸を得ることもできる。
In the method of the present invention, highly pure methacrylic acid can be obtained simply by removing unreacted raw materials and catalyst from the reaction product solution, but if necessary, it can be purified by conventional methods such as distillation. Quality methacrylic acid can also be obtained.

メタクリル酸と同時に副生ずる有機カルボン酸メチルエ
ステルについては、溶剤や化成品の中間原料として活用
される。
Organic carboxylic acid methyl ester, which is produced as a by-product along with methacrylic acid, is used as an intermediate raw material for solvents and chemical products.

(発明の効果) 本発明の方法によれば、メタクリル酸メチルを原料とし
、酸エステル交換反応を利用することにより、簡単な装
置で容易に高品質のメタクリル酸を製造できるものであ
り、通常実施される加水分解法に比べて工業的な価値は
極めて大きい。
(Effects of the Invention) According to the method of the present invention, high-quality methacrylic acid can be easily produced with a simple device by using methyl methacrylate as a raw material and using an acid transesterification reaction, which is not normally carried out. The industrial value is extremely large compared to the conventional hydrolysis method.

(実施例) 以下に、実施例及び比較例を挙げて本発明の方法を更に
詳しく説明するが、本発明はこれらの実施例によりその
範囲を限定されるものではない。
(Examples) The method of the present invention will be explained in more detail below with reference to Examples and Comparative Examples, but the scope of the present invention is not limited by these Examples.

実施例1 留出管、温度計、ガス導入管、撹拌機付きの内容積11
の30フラスコに、メタクリル酸メチル200g、酢酸
132g、ハイドロキノン0.2g、及び強酸性イオン
交換樹脂(アンバーライト200CH)70 gを仕込
み、空気を1 / h rの割合で導入しながら、反応
温度90℃において酢酸メチルを留出させ、12時間反
応を継続した。 酢酸メチルが100g留出した。 反
応生成液を室温まで冷却した後、イオン交換樹脂触媒を
濾別して粗メタクリル酸を210g得た。
Example 1 Internal volume 11 with distillation tube, thermometer, gas introduction tube, and stirrer
200 g of methyl methacrylate, 132 g of acetic acid, 0.2 g of hydroquinone, and 70 g of a strongly acidic ion exchange resin (Amberlite 200CH) were placed in a 30 flask, and while introducing air at a rate of 1/hr, the reaction temperature was increased to 90. Methyl acetate was distilled off at 0.degree. C., and the reaction was continued for 12 hours. 100g of methyl acetate was distilled out. After the reaction product liquid was cooled to room temperature, the ion exchange resin catalyst was filtered off to obtain 210 g of crude methacrylic acid.

ガスクロマド分析の結果、メタクリル酸メチルの反応率
80.6%、メタクリル酸への選択率99%以上であっ
た。
As a result of gas chromad analysis, the reaction rate of methyl methacrylate was 80.6%, and the selectivity to methacrylic acid was 99% or more.

実施例2 酢酸に代えてギ酸100gを使用した他は実施例1と同
様に反応させた。 ギ酸メチルが97g留出した。 ガ
スクロマド分析の結果、メタクリル酸メチルの反応率8
3.5%、メタクリル酸への選択率99%以上であった
Example 2 The reaction was carried out in the same manner as in Example 1, except that 100 g of formic acid was used instead of acetic acid. 97g of methyl formate was distilled out. As a result of gas chromad analysis, the reaction rate of methyl methacrylate was 8.
3.5%, and the selectivity to methacrylic acid was 99% or more.

実施例3 酢酸に代えてアクリル酸160gを使用した他は実施例
1と同様に反応させた。 アクリル酸メチルが102g
留出した。
Example 3 The reaction was carried out in the same manner as in Example 1, except that 160 g of acrylic acid was used instead of acetic acid. 102g of methyl acrylate
Distilled out.

ガスクロマド分析の結果、メタクリル酸メチルの反応率
69.2%、メタクリル酸への選択率99%以上であっ
た。
As a result of gas chromad analysis, the reaction rate of methyl methacrylate was 69.2%, and the selectivity to methacrylic acid was 99% or more.

実施例4 強酸性イオン交換樹脂(アンバーライト200CH)に
代えて濃硫酸3gを使用し、8時間反応させた以外は実
施例1と同様に反応させた。
Example 4 The reaction was carried out in the same manner as in Example 1 except that 3 g of concentrated sulfuric acid was used in place of the strongly acidic ion exchange resin (Amberlite 200CH) and the reaction was carried out for 8 hours.

ガスクロマド分析の結果、メタクリル酸メチルの反応率
95.6%、メタクリル酸への選択率94.3%であっ
た。
As a result of gas chromad analysis, the reaction rate of methyl methacrylate was 95.6% and the selectivity to methacrylic acid was 94.3%.

実施例5 強酸性イオン交換樹脂(アンバーライト200CH)に
代えてパラトルエンスルホン酸5gを使用し、8時間反
応させた以外は実施例1と同様に反応させた。
Example 5 The reaction was carried out in the same manner as in Example 1, except that 5 g of para-toluenesulfonic acid was used in place of the strongly acidic ion exchange resin (Amberlite 200CH) and the reaction was carried out for 8 hours.

ガスクロマド分析の結果、メタクリル酸メチルの反応率
93.3%、メタクリル酸への選択率97.4%であっ
た。
As a result of gas chromad analysis, the reaction rate of methyl methacrylate was 93.3% and the selectivity to methacrylic acid was 97.4%.

比較例 留出管、温度計、ガス導入管、撹拌機付きの内容積Hの
3日フラスコに、メタクリル酸メチル200g、水10
0g、ハイドロキノン0.2 g、及び強酸性イオン交
換樹脂(アンバーライト200CH,ローム・アンド・
ハース社製)70gを仕込み、空気をl / h rの
割合で液中に導入しながら、反応温度100℃において
24時間全還流させた。
Comparative Example In a 3-day flask with an internal volume of H equipped with a distillation tube, thermometer, gas introduction tube, and stirrer, 200 g of methyl methacrylate and 10 g of water were added.
0g, hydroquinone 0.2g, and strongly acidic ion exchange resin (Amberlite 200CH, Rohm & Co., Ltd.)
(manufactured by Haas) was charged, and the mixture was completely refluxed for 24 hours at a reaction temperature of 100° C. while introducing air into the solution at a rate of 1/hr.

反応生成液をガスクロマド分析した結果、メタクリル酸
収率は13.4%であった。
As a result of gas chromatography analysis of the reaction product liquid, the yield of methacrylic acid was 13.4%.

更に、イオン交換樹脂共存下で反応生成液を常圧蒸留し
、留出温度68〜71℃で留出液15gを得た。 ガス
クロマド分析の結果、留出液の重量組成はメタノール5
0%、メタクリル酸メチル45%、水5%であった。
Furthermore, the reaction product liquid was distilled under normal pressure in the presence of an ion exchange resin to obtain 15 g of a distillate at a distillation temperature of 68 to 71°C. As a result of gas chromad analysis, the weight composition of the distillate was methanol 5
0%, methyl methacrylate 45%, and water 5%.

Claims (1)

【特許請求の範囲】 1)酸性触媒の存在下において、メタクリル酸メチルと
有機カルボン酸とから、メタクリル酸と有機カルボン酸
メチルとを製造することを特徴とするメタクリル酸の製
造方法。 2)有機カルボン酸が、炭素数1〜3の脂肪族カルボン
酸である特許請求の範囲第1項記載の方法。 3)酸性触媒が、硫酸、ベンゼンスルホン酸、トルエン
スルホン酸、又はスルホン酸基含有イオン交換樹脂であ
る特許請求の範囲第1項記載の方法。
[Scope of Claims] 1) A method for producing methacrylic acid, which comprises producing methacrylic acid and methyl organic carboxylate from methyl methacrylate and organic carboxylic acid in the presence of an acidic catalyst. 2) The method according to claim 1, wherein the organic carboxylic acid is an aliphatic carboxylic acid having 1 to 3 carbon atoms. 3) The method according to claim 1, wherein the acidic catalyst is sulfuric acid, benzenesulfonic acid, toluenesulfonic acid, or an ion exchange resin containing a sulfonic acid group.
JP2322463A 1990-11-28 1990-11-28 Production of methacrylic acid Pending JPH04198151A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2322463A JPH04198151A (en) 1990-11-28 1990-11-28 Production of methacrylic acid

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2322463A JPH04198151A (en) 1990-11-28 1990-11-28 Production of methacrylic acid

Publications (1)

Publication Number Publication Date
JPH04198151A true JPH04198151A (en) 1992-07-17

Family

ID=18143933

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2322463A Pending JPH04198151A (en) 1990-11-28 1990-11-28 Production of methacrylic acid

Country Status (1)

Country Link
JP (1) JPH04198151A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012531476A (en) * 2009-06-30 2012-12-10 ロディア オペレーションズ Method for producing difluoroacetic acid
CN103588636A (en) * 2013-11-14 2014-02-19 中国科学院过程工程研究所 Method for preparing acrylic acid through hydrolyzation of methyl acrylate under catalysis of acidic resin

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012531476A (en) * 2009-06-30 2012-12-10 ロディア オペレーションズ Method for producing difluoroacetic acid
KR101421332B1 (en) * 2009-06-30 2014-07-18 로디아 오퍼레이션스 Method for preparing difluoroacetic acid
CN103588636A (en) * 2013-11-14 2014-02-19 中国科学院过程工程研究所 Method for preparing acrylic acid through hydrolyzation of methyl acrylate under catalysis of acidic resin

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