JPS62185051A - Production of acrylic acid or methacrylic acid higher alkyl ester - Google Patents
Production of acrylic acid or methacrylic acid higher alkyl esterInfo
- Publication number
- JPS62185051A JPS62185051A JP61026028A JP2602886A JPS62185051A JP S62185051 A JPS62185051 A JP S62185051A JP 61026028 A JP61026028 A JP 61026028A JP 2602886 A JP2602886 A JP 2602886A JP S62185051 A JPS62185051 A JP S62185051A
- Authority
- JP
- Japan
- Prior art keywords
- acrylic acid
- methacrylic acid
- carbonate
- methyl ester
- ester
- 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
Links
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 title claims abstract description 26
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 26
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 125000005907 alkyl ester group Chemical group 0.000 title claims description 11
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 16
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 8
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims abstract description 5
- 229910000024 caesium carbonate Inorganic materials 0.000 claims abstract description 5
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 claims abstract description 5
- 229910000026 rubidium carbonate Inorganic materials 0.000 claims abstract description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 3
- 150000004702 methyl esters Chemical class 0.000 claims description 10
- 238000005809 transesterification reaction Methods 0.000 claims description 7
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 3
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 27
- 238000006243 chemical reaction Methods 0.000 abstract description 19
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 abstract description 8
- 239000006227 byproduct Substances 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 150000002148 esters Chemical class 0.000 abstract description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 abstract 2
- 239000003513 alkali Substances 0.000 abstract 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 230000007797 corrosion Effects 0.000 abstract 1
- 238000005260 corrosion Methods 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 239000003112 inhibitor Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 3
- 238000005194 fractionation Methods 0.000 description 3
- 229950000688 phenothiazine Drugs 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- ZMVHTLOQSTVDFE-UHFFFAOYSA-N methanol;methyl 2-methylprop-2-enoate Chemical compound OC.COC(=O)C(C)=C ZMVHTLOQSTVDFE-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 150000003476 thallium compounds Chemical class 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 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
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、アクリル酸またはメタクリル酸の高級アルキ
ルエステルの製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for producing higher alkyl esters of acrylic acid or methacrylic acid.
アクリル酸またはメタクリル酸のアルキルエステルは、
重合性のビニル基を有する化合物で重合または共重合し
て、接着剤、繊維処理剤、紙加工剤、塗料、潤滑油添加
剤、可塑剤等の広い分野に使用される有用な化合物であ
る。Alkyl esters of acrylic acid or methacrylic acid are
It is a useful compound that is polymerized or copolymerized with a compound having a polymerizable vinyl group and used in a wide range of fields such as adhesives, fiber processing agents, paper processing agents, paints, lubricating oil additives, and plasticizers.
（従来の技術）
従来から、アクリル酸またはメタクリル酸のメチルエス
テルと高級フルコールとのエステル交換反応を触媒およ
び重合禁止剤の存在下に行い、アクリル酸またはメタク
リル酸の高級アルキルエステルを製造する方法は公知で
あり、種々の酸性または塩基性の触媒が知られている。(Prior Art) Conventionally, there has been a method for producing higher alkyl esters of acrylic acid or methacrylic acid by carrying out a transesterification reaction between methyl esters of acrylic acid or methacrylic acid and higher flucols in the presence of a catalyst and a polymerization inhibitor. Various acidic or basic catalysts are known.
（発明が解決しようとする問題点）
酸性触媒の例としては、硫酸、ｐ−トルエンスルホン酸
等が挙げられる。一方、塩基性触媒の例としては、各種
のアルコラード、アルカリ金属水酸化物、アルカリ土類
金属水酸化物、クリラム化合物等が挙げられる０代表的
酸触媒である硫酸は、副反応も少なく、価格も安価で多
用されているエステル交換触媒であるが、腐食性を有し
、装置の材質として、通常、ガラスライニングの装置が
使用され、最も汎用的なステンレス網は用いることがで
きない、また代表的アルコラードであるナトリウムメチ
ラートを使用した場合、原料のアクリル酸またはメタク
リル酸のメチルエステル及び生成するアクリル酸または
メタクリル酸のアルキルエステルの二重結合部へ原料高
級アルコールまたは副生じたメタノールが付加した副生
物が出来やすいという欠点を有している。またタリウム
化合物は毒性に問題がある。(Problems to be Solved by the Invention) Examples of acidic catalysts include sulfuric acid, p-toluenesulfonic acid, and the like. On the other hand, examples of basic catalysts include various alcolades, alkali metal hydroxides, alkaline earth metal hydroxides, krillam compounds, etc. Sulfuric acid, which is a typical acid catalyst, has few side reactions and is inexpensive. Although it is a cheap and widely used transesterification catalyst, it is corrosive and the equipment is usually lined with glass, and the most general-purpose stainless steel cannot be used. When sodium methylate, which is an alcoholade, is used, the raw material higher alcohol or by-produced methanol is added to the double bond of the raw material acrylic acid or methacrylic acid methyl ester and the generated acrylic acid or methacrylic acid alkyl ester. It has the disadvantage of easily forming organisms. Additionally, thallium compounds have toxicity problems.
（問題点を解決するための手段）
本発明者らは、前述の酸性および塩基性触媒の問題点を
解決するため鋭意検討した結果、触媒として炭酸カリウ
ム、炭酸ルビジウムまたは炭酸セシウムから選ばれるア
ルカリ金属炭酸塩を用いることにより、これらの問題点
が解決できることを見出し、本発明を完成するに至った
。(Means for Solving the Problems) As a result of intensive studies to solve the problems of acidic and basic catalysts described above, the present inventors discovered that an alkali metal selected from potassium carbonate, rubidium carbonate, or cesium carbonate can be used as a catalyst. The inventors have discovered that these problems can be solved by using carbonates, and have completed the present invention.
すなわち、本発明はアクリル酸またはメタクリル酸のメ
チルエステルと一般式（Ｉ）
％式％（）
と式中、Ｒは炭素数２〜２０のアルキル基、シクロアル
キル基を示す）で表される高級アルコールとのエステル
交換反応によりアクリル酸またはメタクリル酸の高級ア
ルキルエステルを製造するに際して、触媒として炭酸カ
リウム、炭酸ルビジウムまたは炭酸セシウムから選ばれ
るアルカリ金属炭酸塩を用いることを特徴とするアクリ
ル酸またはメタクリル酸の高級アルキルエステルの製造
方法である。That is, the present invention relates to a methyl ester of acrylic acid or methacrylic acid and a higher compound represented by the general formula (I) (% formula % ( ) where R represents an alkyl group or cycloalkyl group having 2 to 20 carbon atoms). Acrylic acid or methacrylic acid characterized in that an alkali metal carbonate selected from potassium carbonate, rubidium carbonate, or cesium carbonate is used as a catalyst when producing a higher alkyl ester of acrylic acid or methacrylic acid by transesterification with an alcohol. This is a method for producing higher alkyl esters.
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、アクリル酸またはメタクリル酸のメチ
ルエステルと高級アルコールと触媒の混合液を加熱、攪
拌して反応を進め、目的のアクリル酸またはメタクリル
酸の高級アルキル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 higher alkyl ester of acrylic acid or methacrylic acid by heating and stirring a mixed solution of a methyl ester of acrylic acid or methacrylic acid, a higher alcohol, and a catalyst to advance the reaction.
例えば、メタクリル酸メチルとドブチルアルコールを原
料として使用し、メタクリル酸ｎ−ブチルエステルを製
造する場合、本エステル交換反応は次式で示される。For example, when methacrylic acid n-butyl ester is produced using methyl methacrylate and dobutyl alcohol as raw materials, the transesterification reaction is expressed by the following formula.
ＣＨｇ−Ｃ（ＣＨｓ）ＣＯＯＣＨｓ＋ＣＩｌｉ（Ｃｌ１
ｉ（ＣＨ→ Ｃ１ｈ−Ｃ（ＣＩ装ｓ）Ｃｏｏ（Ｃ１１ｇ
） ５ｃＨｓ＋Ｈｇ。CHg-C(CHs)COOCHs+CIli(Cl1
i(CH→ C1h-C(CI s)Coo(C11g
) 5cHs+Hg.
本発明の方法に用いられる高級アルコールとしては、例
えば、エタノール、ｎ−ブチルアルコール、’１ｓｏ−
ブチルアルコール、【−ブチルアルコール、シクロヘキ
シルアルコール、ラウリルアルコール、ステアリルアル
コールなどを挙げることができる。Examples of the higher alcohol used in the method of the present invention include ethanol, n-butyl alcohol, '1so-
Examples include butyl alcohol, [-butyl alcohol, cyclohexyl alcohol, lauryl alcohol, and stearyl alcohol.
アクリル酸またはメタクリル酸のメチルエステルの使用
量は、高級アルコールに対して、通常、１．２〜１０倍
モル、好ましくは、１．５〜５倍モルである。The amount of methyl ester of acrylic acid or methacrylic acid to be used is usually 1.2 to 10 times the mole, preferably 1.5 to 5 times the mole of the higher alcohol.
本発明の方法に用いられる触媒として、炭酸カリウム、
炭酸ルビジウムまたは炭酸セシウムから選ばれるアルカ
リ金属炭酸塩が用いられるが、特に工業的には、価格の
点から炭酸カリウムが好ましい、これらの品質は、無水
の工業薬品程度の純度で十分使用可能である。Potassium carbonate,
An alkali metal carbonate selected from rubidium carbonate or cesium carbonate is used, but especially for industrial use, potassium carbonate is preferable from a price point of view.The quality of these carbonates is equivalent to that of anhydrous industrial chemicals and they can be used sufficiently. .
これら触媒の使用量は、アクリル酸またはメタクリル酸
のメチルエステルと高級アルコールの総量に対して、０
．０１〜２重量％の範囲であり、より好ましくは、０．
０２〜１．０重量％の範囲である。The amount of these catalysts used is 0 based on the total amount of methyl ester of acrylic acid or methacrylic acid and higher alcohol.
．． 0.01 to 2% by weight, more preferably 0.01 to 2% by weight.
The range is from 0.02 to 1.0% by weight.
本発明の方法に用いられる触媒の活性は、固体状態より
溶解状態で大巾に増加する。しかしながら、これらの触
媒はアクリル酸またはメタクリル酸のメチルエステルと
高級アルコール混合溶媒に難溶性であり、加熱下におい
ても溶解量は依然として小さく、その結果触媒活性は必
ずしも満足でｉるものではない、そこで、これらの触媒
はより溶けやすい高級アルコールに溶解してアクリル酸
またはメタクリル酸のメチルエステルに添加すれば、触
媒活性をより太き（することができる、また触媒をメタ
ノールに溶解して添加する方法も好ましい方法である。The activity of the catalyst used in the process of the invention increases significantly in the dissolved state than in the solid state. However, these catalysts are poorly soluble in a mixed solvent of methyl ester of acrylic acid or methacrylic acid and a higher alcohol, and the amount dissolved is still small even under heating, and as a result, the catalytic activity is not necessarily satisfactory. If these catalysts are dissolved in a higher alcohol, which is more soluble, and added to the methyl ester of acrylic acid or methacrylic acid, the catalytic activity can be increased. is also a preferred method.
このメタノールは、本エステル交換反応の副生物として
生成するメタノールとともに、最終的には反応系から除
去する。This methanol is ultimately removed from the reaction system together with methanol produced as a by-product of the transesterification reaction.
本発明の方法において、エステル交換反応は常圧下でも
実施できるが、通常、反応圧力は重合等の副反応を抑制
するには減圧下、好ましくは、１００〜７６０ｍ５＋Ｈ
ｇの範囲である。In the method of the present invention, the transesterification reaction can be carried out under normal pressure, but the reaction pressure is usually reduced to suppress side reactions such as polymerization, preferably 100 to 760 m5+H.
g range.
反応温度は、その圧力における反応系の沸点により定ま
り、反応速度が十分大きくしかも重合が十分抑制できる
５０〜１２０℃の範囲が好ましい。The reaction temperature is determined by the boiling point of the reaction system at that pressure, and is preferably in the range of 50 to 120°C, where the reaction rate is sufficiently high and polymerization can be sufficiently suppressed.
目的物を高収率に得るためには、副生ずるメタノールを
反応系外へ除去することが望ましい、具体的には未反応
のアクリル酸またはメタクリル酸のメチルエステルとの
共沸蒸留により糸外へ留去することができる。In order to obtain the desired product in high yield, it is desirable to remove the by-product methanol from the reaction system. Specifically, it is desirable to remove the by-product methanol from the reaction system by azeotropic distillation with unreacted methyl ester of acrylic acid or methacrylic acid. It can be distilled off.
反応時間は、使用する原料の量、圧力、温度、触媒量等
により変わるが、通常３．５〜７時間である。 反応に
際しては、通常、重合防止のため重合禁止剤を添加する
。重合禁止剤としては、不飽和エステルに対する重合禁
止剤、例えば、周知のハイドロキノン、ハイドロキノン
モノメチルエーテル、フェノチアジンなどを使用する。The reaction time varies depending on the amount of raw materials used, pressure, temperature, amount of catalyst, etc., but is usually 3.5 to 7 hours. During the reaction, a polymerization inhibitor is usually added to prevent polymerization. As the polymerization inhibitor, a polymerization inhibitor for unsaturated esters such as well-known hydroquinone, hydroquinone monomethyl ether, phenothiazine, etc. is used.
その添加量は好ましくは、反応液に対して０．０５〜２
重量％の範囲である。The amount added is preferably 0.05 to 2
% by weight.
反応終了後、反応液より減圧下にまず未反応のアクリル
酸またはメタクリル酸のメチルエステル留去せしめて、
目的物であるアクリル酸またはメタクリル酸の高級アル
キルエステルを得る。目的物は蒸留等により精製する。After the reaction is completed, unreacted methyl ester of acrylic acid or methacrylic acid is distilled off from the reaction solution under reduced pressure.
The target product, higher alkyl ester of acrylic acid or methacrylic acid, is obtained. The target product is purified by distillation or the like.
（作用）
本発明の方法によれば、反応槽、ポンプ、配管等の材質
としてステンレス網が使用でき、建設費の低減が可能に
なる。また原料のアクリル酸またはメタクリル酸のメチ
ルエステル及び生成するアクリル酸またはメタクリル酸
のアルキルエステルの二重結合部へ原料高級アルコール
または副生じたメタノールが付加も少なく高純度のアク
リル酸またはメタクリル酸の高級アルキルを得ることが
できる。(Function) According to the method of the present invention, stainless steel mesh can be used as the material for the reaction tank, pump, piping, etc., making it possible to reduce construction costs. In addition, the raw material higher alcohol or by-produced methanol is less likely to be added to the double bond of the raw material acrylic acid or methacrylic acid methyl ester and the generated acrylic acid or methacrylic acid alkyl ester. You can get alkyl.
（実施例） 以下、実施例により本発明の方法を具体的に説明する。(Example) Hereinafter, the method of the present invention will be specifically explained with reference to Examples.
実施例−１
攪拌機、温度計及び分留塔を備えた内容積１１のフラス
コにｎ−ブチルアルコール１４８ｇ、メタクリル酸メチ
ル５００ｇ 、触媒として炭酸カリウム１．２ｇ。Example 1 In a flask with an internal volume of 11 equipped with a stirrer, a thermometer, and a fractionator, 148 g of n-butyl alcohol, 500 g of methyl methacrylate, and 1.2 g of potassium carbonate as a catalyst were placed.
重合禁止剤としてフェノチアジン１．５ｇを仕込み、３
００ｖａＨｇで攪拌しながら加熱した０反応に伴い副生
じたメタノールは、分留塔塔頂温度が４０〜４５℃に維
持されるように還元比３〜１０でメタノール−メタクリ
ル酸メチル共沸物として留出させた０反応は５時間で終
了し、次いで圧力を２０ｍｍ１１ｇまで減じ、メタクリ
ル酸メチルを留出せしめ、さらに圧力５＊ｍＨｇ、分留
塔塔頂温度８２〜８３℃でメタクリル酸−ｎ−ブチルエ
ステルを留出させた。得られたメタクリル酸−〇−ブチ
ルエステルは２５２ｇで純度は９９．５％であった。収
率は仕込みｎ−ブチルアルコール基準で８９％であった
。1.5 g of phenothiazine was added as a polymerization inhibitor, and 3
The methanol produced as a by-product during the 0 reaction heated with stirring at 00 vaHg is distilled as a methanol-methyl methacrylate azeotrope at a reduction ratio of 3 to 10 so that the top temperature of the fractionation column is maintained at 40 to 45°C. The resulting reaction was completed in 5 hours, and then the pressure was reduced to 20 mm and 11 g to distill off methyl methacrylate, and then n-butyl methacrylate was distilled out at a pressure of 5*mHg and a fractionation column top temperature of 82-83°C. The ester was distilled out. The obtained methacrylic acid 〇-butyl ester weighed 252 g and had a purity of 99.5%. The yield was 89% based on the charged n-butyl alcohol.
実施例−２〜３
実施例−１と同じ装置を使用し、同様な方法で触媒の種
類を変えて行った結果を表−１に示す。Examples 2 to 3 Table 1 shows the results obtained by using the same apparatus as in Example 1 and changing the type of catalyst in the same manner.
表−１
実施例−４
実施例−１と同じ装置を使用し、フラスコにシクロヘキ
シルアルコール２００ｇ、メタクリル酸メチル５００ｇ
、触媒として炭酸カリウム１．４ｇ、重合禁止剤として
フェノチアジン１．７ｇを仕込み、圧力３００ｍＨｇで
攪拌しながら加熱した０反応に伴い副生ずるメタノール
は分留塔塔頂温度が４０〜４５℃に維持されるように、
還流比３〜ｌＯでメタノール−メタクリル酸メチル共沸
物として留出させた。Table-1 Example-4 Using the same equipment as Example-1, put 200 g of cyclohexyl alcohol and 500 g of methyl methacrylate in a flask.
, 1.4 g of potassium carbonate as a catalyst and 1.7 g of phenothiazine as a polymerization inhibitor were charged and heated under a pressure of 300 mHg with stirring. Methanol was produced as a by-product during the reaction, and the temperature at the top of the fractionating column was maintained at 40 to 45°C. As if
It was distilled out as a methanol-methyl methacrylate azeotrope at a reflux ratio of 3 to 1O.
反応は６時間で終了し、次いで圧力を２０ｍｄｉまで減
じ、メタクリル酸メチルを留出せしめ、さらに圧力を２
ｍｓＨｇｂ分留塔塔頂温度９０〜９２℃でメタクリル酸
シクロヘキシルエステルを留出させた。The reaction was completed in 6 hours, then the pressure was reduced to 20 mdi to distill off methyl methacrylate, and the pressure was further reduced to 20 mdi.
Methacrylic acid cyclohexyl ester was distilled out at an msHgb fractionation column top temperature of 90 to 92°C.
得られたメタクリル酸シクロヘキシルエステルは２９０
ｇで純度９９．６％であった。収率は、仕込みシクロヘ
キシルアルコール基準で８６．５％であった。The obtained methacrylic acid cyclohexyl ester was 290
The purity was 99.6%. The yield was 86.5% based on the charged cyclohexyl alcohol.
（発明の効果）
合成したアクリル酸またはメタクリル酸の高級アルキル
エステルは、接着剤、繊維処理剤、紙加工剤、塗料、潤
滑油添加剤および可塑剤等の用途にに好適な品質のもの
であった。(Effect of the invention) The synthesized higher alkyl ester of acrylic acid or methacrylic acid has a quality suitable for use in adhesives, fiber processing agents, paper processing agents, paints, lubricating oil additives, plasticizers, etc. Ta.
Claims (1)
一般式（ I ） Ｒ−ＯＨ（ I ） （式中、Ｒは炭素数２〜２０のアルキル基、シクロアル
キル基を示す）で表される高級アルコールとのエステル
交換反応によりアクリル酸またはメタクリル酸の高級ア
ルキルエステルを製造するに際して、触媒として炭酸カ
リウム、炭酸ルビジウムまたは炭酸セシウムから選ばれ
るアルカリ金属炭酸塩を用いることを特徴とするアクリ
ル酸またはメタクリル酸の高級アルキルエステルの製造
方法。[Claims] 1) Methyl ester of acrylic acid or methacrylic acid with the general formula (I) R-OH (I) (wherein R represents an alkyl group or cycloalkyl group having 2 to 20 carbon atoms). Acrylic acid characterized by using an alkali metal carbonate selected from potassium carbonate, rubidium carbonate, or cesium carbonate as a catalyst when producing a higher alkyl ester of acrylic acid or methacrylic acid by transesterification with the higher alcohol represented by the formula A method for producing a higher alkyl ester of acid or methacrylic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61026028A JPS62185051A (en) | 1986-02-10 | 1986-02-10 | Production of acrylic acid or methacrylic acid higher alkyl ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61026028A JPS62185051A (en) | 1986-02-10 | 1986-02-10 | Production of acrylic acid or methacrylic acid higher alkyl ester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62185051A true JPS62185051A (en) | 1987-08-13 |
Family
ID=12182247
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61026028A Pending JPS62185051A (en) | 1986-02-10 | 1986-02-10 | Production of acrylic acid or methacrylic acid higher alkyl ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62185051A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002241341A (en) * | 2001-02-13 | 2002-08-28 | Japan U-Pica Co Ltd | Method for producing high purity (meth)acrylic ester |
| GB2396611A (en) * | 2002-12-19 | 2004-06-30 | Procter & Gamble | Preparation of wax esters by transesterifying esters with alcohols below atmospheric pressure |
| JP2007063171A (en) * | 2005-08-30 | 2007-03-15 | Ube Ind Ltd | Manufacturing method of acrylic acid higher alcohol ester and methacrylic acid higher alcohol ester |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5793930A (en) * | 1980-12-03 | 1982-06-11 | Mitsui Toatsu Chem Inc | Preparation of methacrylic ester |
-
1986
- 1986-02-10 JP JP61026028A patent/JPS62185051A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5793930A (en) * | 1980-12-03 | 1982-06-11 | Mitsui Toatsu Chem Inc | Preparation of methacrylic ester |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002241341A (en) * | 2001-02-13 | 2002-08-28 | Japan U-Pica Co Ltd | Method for producing high purity (meth)acrylic ester |
| GB2396611A (en) * | 2002-12-19 | 2004-06-30 | Procter & Gamble | Preparation of wax esters by transesterifying esters with alcohols below atmospheric pressure |
| JP2007063171A (en) * | 2005-08-30 | 2007-03-15 | Ube Ind Ltd | Manufacturing method of acrylic acid higher alcohol ester and methacrylic acid higher alcohol ester |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP7206264B2 (en) | Method for producing dimethylaminoalkyl (meth)acrylate | |
| AU2006314805B2 (en) | Manufacture of esters | |
| KR20030005041A (en) | Process for preparing (meth)acrylic anhydride | |
| JP6006801B2 (en) | Method for producing hydroxyalkyl acrylate | |
| US4285872A (en) | Method for producing glycidyl (metha)acrylate | |
| JPS62185051A (en) | Production of acrylic acid or methacrylic acid higher alkyl ester | |
| JPH02193944A (en) | Production of (meth)acrylic acid ester | |
| JPS635055A (en) | Production of higher alkyl ester of acrylic acid or methacrylic acid | |
| US5744613A (en) | Process for the preparation of alkylimidazolidone (meth)acrylates | |
| JP2702249B2 (en) | Process for producing alkylaminoalkyl ester of acrylic acid or methacrylic acid | |
| JPS635054A (en) | Production of higher alkyl ester of acrylic acid or methacrylic acid | |
| JP3274609B2 (en) | Stabilizer for hydroxyl-containing vinyl compound and method of using the same | |
| WO2014158445A1 (en) | Synthesis of (2-nitro)alkyl (meth)acrylates via transesterification of (meth)acrylate esters | |
| EP1231202A2 (en) | Transesterification of (meth)acrylates in presence of alkali metal cyanate containing mixed catalysts | |
| JPS62175448A (en) | Production of alkylaminoalkyl acrylate or methacrylate | |
| JP2006016339A (en) | Method for producing methyl methacrylate | |
| JPH0747568B2 (en) | Process for producing alkylaminoalkyl ester of acrylic acid or methacrylic acid | |
| JPS62230755A (en) | Production of acrylic acid of methacrylic acid alkylkaminoalkyl ester | |
| JPS62242652A (en) | Production of acrylic acid or methacrylic acid alkylaminoalkyl ester | |
| JPS6152815B2 (en) | ||
| JPS5817455B2 (en) | Method for producing dialkylaminoethyl ester of acrylic acid or methacrylic acid | |
| JPS6320416B2 (en) | ||
| JPS5846047A (en) | Preparation of alkylaminoalkyl acrylate or methacrylate | |
| JPH02160809A (en) | Polymerization inhibitor for dialkylaminoalkyl (meth) acrylate | |
| JPH0222064B2 (en) |