TWI247004B - Purification method of (meth)acrylic acid ester - Google Patents

Purification method of (meth)acrylic acid ester Download PDF

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Publication number
TWI247004B
TWI247004B TW91135277A TW91135277A TWI247004B TW I247004 B TWI247004 B TW I247004B TW 91135277 A TW91135277 A TW 91135277A TW 91135277 A TW91135277 A TW 91135277A TW I247004 B TWI247004 B TW I247004B
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TW
Taiwan
Prior art keywords
meth
acrylate
purifying
acrylic acid
hetero atom
Prior art date
Application number
TW91135277A
Other languages
Chinese (zh)
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TW200301250A (en
Inventor
Shuhei Yada
Kenji Takasaki
Yasushi Ogawa
Yoshiro Suzuki
Original Assignee
Mitsubishi Chem Corp
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Filing date
Publication date
Application filed by Mitsubishi Chem Corp filed Critical Mitsubishi Chem Corp
Publication of TW200301250A publication Critical patent/TW200301250A/en
Application granted granted Critical
Publication of TWI247004B publication Critical patent/TWI247004B/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/48—Separation; Purification; Stabilisation; Use of additives
    • C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
    • C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation

Abstract

In a process for producing a (meth)acrylic ester by esterifying a (meth)acrylic acid and an alcohol in the presence of an acid catalyst, a purification step is conducted which comprises rectifying the reaction mixture in the presence of a heteroatom-containing chelate complex having as the central metal an element in groups 7 to 12 of the long-period Periodic Table to thereby inhibit the (meth)acrylic ester from undergoing transesterification with the hydroxy compound which is a by-product present as an impurity and from yielding an alcohol. Thus, a high-purity (meth)acrylic ester can be produced.

Description

1247004 玖、發明說明 【發明所屬之技術領域】 本發明係關於丙烯酸酯或甲基丙烯酸酯（以下，將丙烯 酸及甲基丙烯酸總稱爲「（甲基）丙烯酸」）之純化方法者， 更詳細言之，本發明係關於：對經過酯化反應步驟及中和、 洗淨及低沸點成分除去步驟得到之（甲基）丙烯酸酯粗純 化物中，經由添加特定的螯合化合物以抑制醇的發生之反 應以製得高純度的（甲基）丙烯酸之工業上有用的純化方 法者。 【先前技術】 向來，（甲基）丙烯酸酯廣泛地被使用作爲用以製造塗覆 劑及接著劑、甚至於隱形眼鏡等之光學材料等之單體成 分。此等中之丙烯酸酯，主要爲藉由使丙烷或丙烯進行接 觸氧化所得之丙烯酸經由酯化而製造；又，甲基丙烯酸酯， 可藉由：丙酮氰醇（acetone cyanhydrin)法、新丙酮氰 醇法、或以異丁烯及特丁醇作爲原料之接觸氧化法直接製 造，將此等方法所獲得之甲基丙烯酸甲酯經由酯化，或使 此等方法中直接得到之甲基丙烯酸甲酯進行酯交換而製 造。其中，尤以在酸觸媒的存在下，使（甲基）丙烯酸與醇 進行酯化反應而製造的方法受到普遍使用。 於該製造法中，須要在反應後將酸觸媒及未反應的（甲 基）丙烯酸從得到之酯化反應液（主成份爲（甲基）丙烯酸 酯）除去的步驟，迄今，普遍使用者爲將酯化反應液以鹼 水溶液處理之方法（日本專利特開昭 6 3 - 9 9 0 3 7、 6 312/發明說明書(補件)/92-03/911352771247004 发明Invention Description: Field of the Invention The present invention relates to a method for purifying acrylate or methacrylate (hereinafter, collectively referred to as "(meth)acrylic acid") The present invention relates to a method for suppressing the occurrence of alcohol by adding a specific chelating compound to a crude (meth) acrylate obtained by an esterification reaction step and a neutralization, washing and low-boiling component removal step. The reaction is carried out to obtain an industrially useful purification method of high purity (meth)acrylic acid. [Prior Art] Conventionally, (meth) acrylate has been widely used as a monomer component for producing a coating agent and an adhesive, an optical material such as a contact lens or the like. The acrylates in these are mainly produced by esterification of acrylic acid obtained by subjecting propane or propylene to contact oxidation; further, methacrylic acid esters can be obtained by: acetone cyanhydrin method, new acetone cyanide The alcohol method or the contact oxidation method using isobutylene and tert-butyl alcohol as a raw material, and the methyl methacrylate obtained by the methods is esterified, or the methyl methacrylate obtained directly in the methods is used. Manufactured by transesterification. Among them, a method in which (meth)acrylic acid is esterified with an alcohol in the presence of an acid catalyst is generally used. In the production method, a step of removing an acid catalyst and unreacted (meth)acrylic acid from the obtained esterification reaction liquid (the main component is (meth) acrylate) after the reaction is required, and so far, a general user A method for treating an esterification reaction solution with an aqueous alkali solution (Japanese Patent Laid-Open Publication No. SHO 63-99 9 3, 6 312/Invention Manual (Supplement)/92-03/91135277

Claims (1)

替换本 1247004 拾、申請專利範掘 工·一種（甲基）丙烯酸酯之純化方法，其特徵在於，係使 含有雜質之（甲基）丙烯酸丁酯或（甲基）丙烯酸2_乙基己 基醋在含有雜原子之螯合錯合物（爲具有以ls族型元素週 期表第族的元素作爲中心金屬者）的存在下進行精 飽’具有低沸點成分分離步驟及高沸點成分分離步驟，且 將上述含有雜原子之螯合錯合物添加至低沸點成分除去後 之塔底殘渣中。A method for purifying a (meth) acrylate, which is characterized in that it is a butyl (meth)acrylate or a (meth)acrylic acid 2-ethylhexyl vinegar. Purifying in the presence of a chelate complex containing a hetero atom (which is an element having a group of elements of the ls group element periodic table as a central metal) having a low boiling component separation step and a high boiling component separation step, and The above-mentioned hetero atom-containing chelate complex is added to the bottom residue after removal of the low boiling component. 2 ·如申請專利範圍第1項之（甲基）丙烯酸酯之純化方 法’其中’（甲基）丙嫌酸酯係（甲基）丙嫌酸與醇類在酸觸 媒的存在下進行酯化反應所製得者，且將上述含有雜原子 之螯合錯合物添加至精餾後之餾出液的回流液中。 3 ·如申請專利範圍第1或2項之（甲基）丙烯酸酯之純化 方法’其中，含有雜質之（甲基）丙烯酸酯，係使（甲基）丙 烯酸與醇類在酸觸媒的存在下進行酯化反應，經中和、洗2 · Purification method of (meth) acrylate according to item 1 of the patent application 'where '(methyl)-propyl acrylate-type (methyl)-acrylic acid and alcohol are esterified in the presence of acid catalyst The chelating complex containing the above hetero atom is added to the reflux of the distillate after rectification. 3. The method for purifying (meth) acrylate according to claim 1 or 2, wherein the (meth) acrylate containing impurities causes the presence of (meth)acrylic acid and an alcohol in the acid catalyst. Esterification reaction, neutralization, washing 淨及低沸點成分除去的各步驟所得之（甲基）丙燦酸酯粗 製物。 4 ·如申請專利範圍第1項之（甲基）丙烯酸酯之純化方 法’其中’含有雑原子之蜜合錯合物’形成其錯合物之有 機配位基的酸解離常數（p Ka )爲4 · 3以上。 5 ·如申請專利範圍第1項之（甲基）丙烯酸酯之純化方 法，其中’含有雜原子之螯合錯合物係以下述通式（i )所 代表之化合物： 15 326\總檔\91\91135277\91135277(替換)-2 1247004 R (1 ) (式中，M表示18族型元素週期表第7〜12族的金屬原 子；R 1、R 2表示可相同或相異、亦可相互鍵結之一價或二 價之脂肪族烴基、芳香族烴基、雜原子基）。 6 .如申請專利範圍第 1項之（甲基）丙烯酸酯之純化方 法，其中，含有雜質之（甲基）丙烯酸酯係含有羥基化合物 與作爲酸觸媒之對甲苯磺酸。 16 326\總檔\91 \9 Π 3527Ά91135277(替換)-2The crude (meth) propionate obtained in each step of removal of the net and low boiling components. 4 · The acid dissociation constant (p Ka ) of the organic ligand of the complex formed by the method for purifying the (meth) acrylate of the first application of the patent range 'the halogenated honey complex' It is 4 · 3 or more. 5. A method for purifying a (meth) acrylate according to claim 1, wherein the 'chelating complex containing a hetero atom is a compound represented by the following formula (i): 15 326\total file\ 91\91135277\91135277(replacement)-2 1247004 R (1 ) (wherein M represents a metal atom of Groups 7 to 12 of the Periodic Table of the Group 18; R 1 and R 2 represent the same or different, One or more divalent aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and hetero atom groups are bonded to each other. 6. A method of purifying a (meth) acrylate according to the first aspect of the invention, wherein the (meth) acrylate containing an impurity contains a hydroxy compound and p-toluenesulfonic acid as an acid catalyst. 16 326\Total file\91 \9 Π 3527Ά91135277 (replace)-2
TW91135277A 2001-12-05 2002-12-05 Purification method of (meth)acrylic acid ester TWI247004B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2001371951 2001-12-05

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TW200301250A TW200301250A (en) 2003-07-01
TWI247004B true TWI247004B (en) 2006-01-11

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CN (1) CN100497290C (en)
AU (1) AU2002349756A1 (en)
TW (1) TWI247004B (en)
WO (1) WO2003048103A1 (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105968002B (en) * 2016-05-06 2019-02-26 中国环境科学研究院 A kind of acrylate production method that pollutant discharge amount is low
WO2018114429A1 (en) * 2016-12-21 2018-06-28 Basf Se Method for obtaining pure 2-ethylhexyl acrylate or pure 2-propylheptyl acrylate from the corresponding raw alkyl acrylate by distillation
MY191922A (en) * 2017-03-31 2022-07-18 Univ Hokkaido Nat Univ Corp Catalyst for producing unsaturated carboxylic acid, method for producing unsaturated carboxylic acid, and method for producing unsaturated carboxylic ester

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* Cited by examiner, † Cited by third party
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EP1043303A1 (en) * 1994-09-09 2000-10-11 Idemitsu Petrochemical Co., Ltd. Method of inhibiting vinyl compound polymerization
JPH10175919A (en) * 1996-12-18 1998-06-30 Daicel Chem Ind Ltd Production of tetrahydrobenzyl (meth)acrylate
JPH10175918A (en) * 1996-12-18 1998-06-30 Daicel Chem Ind Ltd Production of tetrahydrobenzyl (meth)acrylate

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CN1561324A (en) 2005-01-05
AU2002349756A1 (en) 2003-06-17
CN100497290C (en) 2009-06-10
TW200301250A (en) 2003-07-01
WO2003048103A1 (en) 2003-06-12

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