JPH0530822B2 - - Google Patents
Info
- Publication number
- JPH0530822B2 JPH0530822B2 JP55116917A JP11691780A JPH0530822B2 JP H0530822 B2 JPH0530822 B2 JP H0530822B2 JP 55116917 A JP55116917 A JP 55116917A JP 11691780 A JP11691780 A JP 11691780A JP H0530822 B2 JPH0530822 B2 JP H0530822B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- ethylene oxide
- meth
- liquid
- chromium
- 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
- 238000006243 chemical reaction Methods 0.000 claims description 69
- 239000003054 catalyst Substances 0.000 claims description 26
- 125000002947 alkylene group Chemical group 0.000 claims description 24
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 23
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 19
- 150000001845 chromium compounds Chemical class 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 39
- 239000007788 liquid Substances 0.000 description 25
- 238000006116 polymerization reaction Methods 0.000 description 11
- 239000011651 chromium Substances 0.000 description 9
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 8
- 229910052804 chromium Inorganic materials 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 150000001844 chromium Chemical class 0.000 description 7
- 238000004821 distillation Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- FQHYQCXMFZHLAE-UHFFFAOYSA-N 25405-85-0 Chemical compound CC1(C)C2(OC(=O)C=3C=CC=CC=3)C1C1C=C(CO)CC(C(C(C)=C3)=O)(O)C3C1(O)C(C)C2OC(=O)C1=CC=CC=C1 FQHYQCXMFZHLAE-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000001577 simple distillation Methods 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- -1 chromium halides Chemical class 0.000 description 2
- FYDNFZPPZJDFRY-UHFFFAOYSA-K chromium(3+);2-methylprop-2-enoate Chemical compound [Cr+3].CC(=C)C([O-])=O.CC(=C)C([O-])=O.CC(=C)C([O-])=O FYDNFZPPZJDFRY-UHFFFAOYSA-K 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- OLQFXOWPTQTLDP-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCO OLQFXOWPTQTLDP-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- UOUJSJZBMCDAEU-UHFFFAOYSA-N chromium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Cr+3].[Cr+3] UOUJSJZBMCDAEU-UHFFFAOYSA-N 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 231100000676 disease causative agent Toxicity 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 239000012808 vapor phase Substances 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
Description
【発明の詳細な説明】
本発明は、アクリル酸又はメタクリル酸（以
下、（メタ）アクリル酸と称する）と、アルキレ
ンオキサイドとを反応させて２−ヒドロキシアル
キル（メタ）アクリレートを製造する方法に関
し、更に詳しくは、クロムのハロゲン化物、飽和
又は不飽和脂肪酸のクロム化合物およびクロムの
酸化物のうちから選ばれた少なくとも一種の化合
物を触媒として用いて（メタ）アクリル酸とアル
キレンオキサイドとを反応させて２−ヒドロキシ
アルキル（メタ）アクリレートを製造する方法の
改良に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing 2-hydroxyalkyl (meth)acrylate by reacting acrylic acid or methacrylic acid (hereinafter referred to as (meth)acrylic acid) with alkylene oxide. More specifically, (meth)acrylic acid and alkylene oxide are reacted using at least one compound selected from chromium halides, chromium compounds of saturated or unsaturated fatty acids, and chromium oxides as a catalyst. The present invention relates to improvements in methods for producing 2-hydroxyalkyl (meth)acrylates.
（メタ）アクリル酸とアルキレンオキサイドと
から２−ヒドロキシアルキル（メタ）アクリレー
トを合成する際に使用することのできる触媒は数
多く提案されており、クロム化合物を用いること
も知られている。例えば、特公昭46−37805号公
報にはカルボン酸の予め形成されたクロム塩を用
いることが開示され、特公昭45−8970号公報に
は、主触媒として三価の鉄化合物、助触媒として
クロム化合物を用いることが開示されている。ク
ロム化合物は触媒として一般に優れているが反応
速度が早く、活性も高いため、例えば、メタクリ
ル酸とエチレンオキサイドを反応させた場合に
は、主反応（下記反応式(1)参照）と並行してジエ
チレングリコールモノメタクリレート（下記反応
式(2)参照）あるいはエチレングリコールジメタク
リレート（以下、単にジエステルという場合があ
る）（下記反応式(3)参照）を副生する反応が進み、
とくに反応終期において急速にこれらの副反応が
おこる。 Many catalysts have been proposed that can be used to synthesize 2-hydroxyalkyl (meth)acrylate from (meth)acrylic acid and alkylene oxide, and it is also known to use chromium compounds. For example, Japanese Patent Publication No. 46-37805 discloses the use of preformed chromium salts of carboxylic acids, and Japanese Patent Publication No. 45-8970 discloses the use of trivalent iron compounds as the main catalyst and chromium as the co-catalyst. The use of compounds is disclosed. Chromium compounds are generally excellent as catalysts, but their reaction rate is fast and their activity is high. The reaction proceeds to produce diethylene glycol monomethacrylate (see reaction formula (2) below) or ethylene glycol dimethacrylate (hereinafter simply referred to as diester) (see reaction formula (3) below) as a by-product.
These side reactions occur rapidly, especially in the final stage of the reaction.
このため、例えば特公昭46−41524号公報、特
公昭47−14087号公報及び特開昭51−25810号公報
などに種々の提案がなされている。ところがこれ
らの方法においては、第３成分の添加による操作
の複雑化や製品への混入のおそれ、あるいは測定
計器使用による装置上の課題等が残されている。 For this reason, various proposals have been made, for example, in Japanese Patent Publication No. 46-41524, Japanese Patent Publication No. 47-14087, and Japanese Patent Application Laid-Open No. 51-25810. However, in these methods, there remain problems such as complication of operation due to the addition of a third component, fear of contamination with the product, and equipment problems due to the use of measuring instruments.
上記反応式(2)のような反応で特に反応終期に急
速に副生するジアルキレングリコールモノ（メ
タ）クリレートは収率及び製品純度の低下の原因
となり、上記反応式(3)で示されるような反応で副
生するジエステルは反応液またはその後の精製工
程に重合をひきおこす原因物質であるといわれて
いる。 Dialkylene glycol mono(meth)acrylate, which is rapidly produced as a by-product especially at the end of the reaction in the reaction shown in reaction formula (2) above, causes a decrease in yield and product purity, and as shown in reaction formula (3) above, The diester produced as a by-product in this reaction is said to be a substance that causes polymerization in the reaction solution or in the subsequent purification process.
このように（メタ）アクリル酸とアルキレンオ
キサイドから２−ヒドロキシアルキル（メタ）ア
クリレートを合成する工程において最も大きな課
題は、反応終期あるいは蒸留精製時において、重
合による２−ヒドロキシアルキル（メタ）アクリ
レートの損失を防ぐことである。 The biggest problem in the process of synthesizing 2-hydroxyalkyl (meth)acrylate from (meth)acrylic acid and alkylene oxide is the loss of 2-hydroxyalkyl (meth)acrylate due to polymerization at the end of the reaction or during distillation purification. The goal is to prevent
本発明者等はかかる従来技術の問題点を克服す
べく鋭意研究を進めた結果、メタクリル酸とエチ
レンオキサイドとの反応の場合を例にとつて説明
すれば、目的反応生成物を重合させる原因物質が
例えば下記反応式(4)のようにして活性化されたメ
タクリル酸クロムであり、このものが下記反応式
(5)によつて目的とする、例えば２−ヒドロキシエ
チルメタクリレートを生成する反応に寄与すると
共に、生成した２−ヒドロキシエチルメタクリレ
ートを下記反応式(6)によつて重合させる触媒とし
て機能していると思われることを見出しかかる知
見に基づいて、反応中〜反応終了時、特に反応終
期において反応液中に存在するアルキレンオキサ
イドのモル濃度を活性化されたメタクリル酸クロ
ムのモル濃度の３倍より大きくすることによつて
目的反応生成物の重合を実質上完全に防止できる
ことを見出し、本発明をするに至つた。 As a result of intensive research to overcome the problems of the prior art, the present inventors have found that, taking the case of the reaction between methacrylic acid and ethylene oxide as an example, the causative agent that causes the polymerization of the desired reaction product. is, for example, chromium methacrylate activated as shown in the following reaction formula (4), and this product is activated as shown in the following reaction formula (4).
(5) contributes to the desired reaction, for example, to produce 2-hydroxyethyl methacrylate, and also functions as a catalyst to polymerize the produced 2-hydroxyethyl methacrylate according to the following reaction formula (6). Based on this knowledge, we determined that the molar concentration of alkylene oxide present in the reaction solution during the reaction to the end of the reaction, especially in the final stage of the reaction, was set to be more than three times the molar concentration of activated chromium methacrylate. The present inventors have discovered that the polymerization of the desired reaction product can be substantially completely prevented by doing so, leading to the present invention.
即ち、本発明に従えば、酢酸クロムを触媒とし
て、アクリル酸又はメタクリル酸にアルキレンオ
キサイドを添加し乍ら反応させて２−ヒドロキシ
アルキル（メタ）アクリレートを製造するにあた
り、触媒の使用量をアクリル酸又はメタクリル酸
に対して0.1〜0.3重量％とし、かつ、反応中およ
び反応終了時において反応液中に含まれるアルキ
レンオキサイドのモル濃度を前記クロム化合物の
モル濃度の３倍を超えて存在させ乍ら反応を実施
することを特徴とする２−ヒドロキシアルキル
（メタ）アクリレートの製法が提供される。 That is, according to the present invention, when producing 2-hydroxyalkyl (meth)acrylate by adding alkylene oxide to acrylic acid or methacrylic acid and reacting with chromium acetate as a catalyst, the amount of the catalyst used is changed to 2-hydroxyalkyl (meth)acrylate. or 0.1 to 0.3% by weight based on methacrylic acid, and the molar concentration of alkylene oxide contained in the reaction solution during and at the end of the reaction is more than three times the molar concentration of the chromium compound. A method for producing 2-hydroxyalkyl (meth)acrylate is provided, characterized in that the reaction is carried out.
本発明者等の知見によれば、反応物を重合させ
る触媒として活性（メタ）アクリル酸クロムが機
能する条件は、所望反応生成物濃度が十分に高く
かつ反応液中のアルキレンオキサイド濃度が活性
化された（メタ）アクリル酸クロム濃度の３倍を
下回る場合である。 According to the findings of the present inventors, the conditions for active chromium (meth)acrylate to function as a catalyst for polymerizing reactants are such that the concentration of the desired reaction product is sufficiently high and the concentration of alkylene oxide in the reaction solution is activated. This is the case when the concentration of chromium (meth)acrylate is less than three times the concentration of chromium (meth)acrylate.
つまり、アルキレンオキサイドが十分な濃度で
反応液に存在すれば活性（メタ）アクリル酸クロ
ムは所望生成物を重合させる働きをせず、もつぱ
らアルキレンオキサイドと反応し２−ヒドロキシ
アルキル（メタ）アクリレートを生成せしめる。
反応の最終期においては、活性（メタ）アクリル
酸クロムは下記反応式(7)で示すようにアルキレン
オキサイドと反応してしまい、例えば、２−ヒド
ロキシエチルメタクリレート−クロム塩となつて
活性を完全に失ない、もはや反応を進めること
も、２−ヒドロキシアルキル（メタ）アクリレー
トを重合させることもできない。 In other words, if alkylene oxide is present in the reaction solution at a sufficient concentration, activated chromium (meth)acrylate will not act to polymerize the desired product, but will react exclusively with alkylene oxide to form 2-hydroxyalkyl (meth)acrylate. Generate.
In the final stage of the reaction, activated chromium (meth)acrylate reacts with alkylene oxide as shown in reaction formula (7) below, and becomes, for example, 2-hydroxyethyl methacrylate-chromium salt, completely losing its activity. It is no longer possible to proceed with the reaction or polymerize the 2-hydroxyalkyl (meth)acrylate.
したがつて本発明においては、反応中〜反応終
了時において、常にアルキレンオキサイドを活性
化クロム濃度の３倍を上回る濃度に維持すること
が必須の条件である。活性化クロムは反応液中に
おいて濃緑色を呈しているが、本発明の方法に従
つて反応終期に到達し、２−ヒドロキシアルキル
（メタ）アクリレート−クロムとして活性を失つ
たクロムは黒褐色を呈するもので、もはや重合の
おそれのない状態を確認できる。 Therefore, in the present invention, it is essential to maintain alkylene oxide at a concentration of more than three times the activated chromium concentration during the reaction and at the end of the reaction. Activated chromium exhibits a dark green color in the reaction solution, but chromium that has reached the final stage of the reaction according to the method of the present invention and has lost its activity as 2-hydroxyalkyl (meth)acrylate-chromium exhibits a dark brown color. This confirms that there is no longer any risk of polymerization.
本発明者等が得たこのような知見は従来の技術
常識とは大きく異なる画期的なものである。即
ち、本発明に従えば特公昭54−41571号公報に開
示されているように分子状酸素を用いる危険もな
く、特公昭47−51378号公報に記載されているよ
うに蒸留に先立つて重合防止のために触媒塩を除
去する操作を必要とせず、特開昭51−26810号公
報や特公昭47−14087号公報に記載されているよ
うに、過剰のアルキレンオキサイドが反応終期に
存在することによつて副生物が生成することを懸
念することなく、重合のおそれのない所望反応生
成物を製造でき、しかも簡単な蒸留法で製品を収
得することができる。 This kind of knowledge obtained by the present inventors is groundbreaking and differs greatly from conventional technical knowledge. That is, according to the present invention, there is no danger of using molecular oxygen as disclosed in Japanese Patent Publication No. 54-41571, and polymerization can be prevented prior to distillation as described in Japanese Patent Publication No. 47-51378. As described in JP-A-51-26810 and JP-B-47-14087, there is no need for an operation to remove the catalyst salt due to the presence of excess alkylene oxide at the end of the reaction. Therefore, it is possible to produce a desired reaction product without fear of polymerization without worrying about the formation of by-products, and moreover, the product can be obtained by a simple distillation method.
本発明において使用すアルキレンオキサイドな
る語は、エチレンオキサイド、プロピレンオキサ
イドなどの狭義のアルキレンオキサイドのほかに
エピクロルヒドリンなどのオキシラン化合物を含
むものとする。これらのアルキレンオキサイド
は、前述の如く、反応中〜反応終了時において反
応系に存在するクロム化合物のモル濃度の３倍を
超えるモル濃度で存在させなければならない。 The term alkylene oxide used in the present invention includes alkylene oxides in a narrow sense such as ethylene oxide and propylene oxide, as well as oxirane compounds such as epichlorohydrin. As mentioned above, these alkylene oxides must be present at a molar concentration that is more than three times the molar concentration of the chromium compound present in the reaction system during the reaction and at the end of the reaction.
本発明に従つて、酢酸第２クロムを触媒として
メタクリル酸とエチレンオキサイドとを反応させ
て２−ヒドロキシエチルメタクリレート
（2HEMA）を製造した場合に得られた結果を第
１図〜第４図のグラフ図に示す。 The graphs in FIGS. 1 to 4 show the results obtained when 2-hydroxyethyl methacrylate (2HEMA) was produced by reacting methacrylic acid and ethylene oxide using dichromic acetate as a catalyst according to the present invention. As shown in the figure.
第１図は反応器のエチレンオキサイド分圧
（Kg／cm2）と反応速度（mol％／Hr）の関係を示
すグラフ図であり、反応温度90℃、触媒濃度0.1
重量％／MAAの場合の結果である。 Figure 1 is a graph showing the relationship between the ethylene oxide partial pressure (Kg/cm 2 ) in the reactor and the reaction rate (mol%/Hr), at a reaction temperature of 90°C and a catalyst concentration of 0.1.
The results are for weight%/MAA.
第２図は触媒濃度（重量％／MAA）と反応速
度（mol％／Hr）との関係を示すグラフ図で反
応温度は90℃、エチレンオキサイド分圧は１Kg／
cm2である。 Figure 2 is a graph showing the relationship between catalyst concentration (wt%/MAA) and reaction rate (mol%/Hr), where the reaction temperature is 90℃ and the ethylene oxide partial pressure is 1Kg/Hr.
cm2 .
第３図は反応温度（１／Ｔ〓×103）と反応速
度（mol％／Hr）との関係を示すグラフ図で触
媒濃度は0.1重量％／MAA、エチレンオキサイド
分圧は１気圧である。 Figure 3 is a graph showing the relationship between reaction temperature (1/T〓×10 3 ) and reaction rate (mol%/Hr), where the catalyst concentration is 0.1% by weight/MAA and the ethylene oxide partial pressure is 1 atm. .
第４図はエチレンオキサイド分圧1.0Kg／cm2の
場合の液中の２−ヒドロキシエチルメタクリレー
ト（モル率）とエチレンオキサイド溶解度（EO
モル／（MMA＋HEMA）モル）との関係を示
すグラフ図である。 Figure 4 shows 2 -hydroxyethyl methacrylate (molar percentage) and ethylene oxide solubility (EO
It is a graph diagram showing the relationship between mol/(MMA+HEMA) mol).
以下に、本発明に従つて２−ヒドロキシアルキ
ル（メタ）アクリル酸を製造する方法について具
体的に説明する。 Below, a method for producing 2-hydroxyalkyl (meth)acrylic acid according to the present invention will be specifically explained.
原料（メタ）アクリル酸を、加熱及び冷却手段
と撹拌装置を備えた容器に液状で供給し、触媒を
粉末状で、あるいは（メタ）アクリル酸等の適当
な液体に溶解もしくは懸濁させて投入・混合す
る。 The raw material (meth)acrylic acid is supplied in liquid form to a container equipped with heating and cooling means and a stirring device, and the catalyst is added in powder form or dissolved or suspended in a suitable liquid such as (meth)acrylic acid.・Mix.
ついで反応容器内空間を不活性気体で置換し、
液温を60〜120℃、好ましくは80〜100℃に昇温
し、アルキレンオキサイドをガス状もしくは液状
で反応器に送入開始する。反応が始まると液温が
上昇を始めるので冷却を行ない反応温度を上記範
囲に保つ。このとき液の色は活性（メタ）アクリ
ル酸クロムの濃緑色を呈している。アルキレンオ
キサイドの送入速度は、反応温度と触媒濃度と分
圧から求めたアルキレンオキサイド消費速度を上
回る量が液中に存在するに十分な反応器内アルキ
レンオキサイド分圧を保つ速さで送入する。反応
が進み酸濃度が低下し、十分に反応によつて酸消
費が確認されるまで（目安として酸0.1重量％以
下）、アルキレンオキサイド分圧を保ちつづける
と、やがて反応液の色は活性クロムの濃緑色から
２−ヒドロキシアルキル（メタ）アクリレート−
クロムの黒褐色に変化し、活性が失なわれたこと
を示す。このようにして得られた反応終了液は、
そのまま、必要に応じて過して次の精製工程へ
送られるが、この液はもはや重合をひきおこして
プロセスにトラブルをおこすおそれは全くない。 Then, the space inside the reaction vessel is replaced with an inert gas,
The liquid temperature is raised to 60 to 120°C, preferably 80 to 100°C, and alkylene oxide in gas or liquid form is started to be fed into the reactor. When the reaction begins, the liquid temperature begins to rise, so cooling is performed to maintain the reaction temperature within the above range. At this time, the color of the liquid is the dark green color of activated chromium (meth)acrylate. The alkylene oxide is fed at a rate that maintains a sufficient alkylene oxide partial pressure in the reactor so that the amount of alkylene oxide in the liquid exceeds the alkylene oxide consumption rate calculated from the reaction temperature, catalyst concentration, and partial pressure. . As the reaction progresses, the acid concentration decreases, and if the alkylene oxide partial pressure is maintained until sufficient acid consumption is confirmed by the reaction (acid 0.1% by weight or less as a guide), the color of the reaction solution will eventually change to that of activated chromium. From dark green to 2-hydroxyalkyl (meth)acrylate.
The color changes to blackish brown due to chromium, indicating that the activity has been lost. The reaction-completed liquid obtained in this way is
The liquid is passed as is and sent to the next purification step, if necessary, but there is no longer any risk that this liquid will cause trouble in the process by causing polymerization.
以下、実施例をあげて本発明を一層具体的に説
明するが、本発明の技術的範囲をこれらの実施例
に限定するものでないことはいうまでもない。 Hereinafter, the present invention will be explained in more detail with reference to Examples, but it goes without saying that the technical scope of the present invention is not limited to these Examples.
実施例 １
メタクリル酸545ｇｒ、酢酸第２クロム（Cr
（CH3・COO）3・H2O）1.5ｇｒをメタクリル酸50
ｇｒに溶かしたものおよびノンフレツクス−Ｆ
（精工化学社製重合防止剤）1.8ｇｒを１ガラス
反応器に仕込み、反応器内をN2ガス置換して90
℃に昇温し、内圧を1.5気圧とした。次いで液状
エチレンオキサイドを156ｇ／Hrの速さで供給し
た（このときの触媒濃度および反応温度における
エチレンオキサイドの消費速度は分圧0.5気圧の
とき128ｇ／Hrである）。60分後の反応器内圧は
２気圧を示した。したがつてエチレンオキサイド
分圧は0.5気圧である。このときの液に溶解して
いるエチレンオキサイドの濃度は0.0617mol／
液・molであつた（ヘンリー定数Ｅ＝8.10であ
る）。60分経過後、エチレンオキサイドの送入を
消費速度と等しい128ｇ／Ｈで行ない、内圧を２
気圧に保つた。反応液中のエチレンオキサイド濃
度は0.0617mol／molと変らず、触媒濃度は約
0.0009mol／molで、エチレンオキサイド対触媒
モル濃度比は約70であつた。132分後、酸濃度は
0.1重量％になり、反応液色が濃緑色から黒褐色
に変り、エチレンオキサイドの送入を停止した。
反応器内にポリマーの痕跡は見当らず、ついで反
応液を過することなく単蒸留容器に送り、はじ
め減圧下で過剰のエチレンオキサイドを回収した
あと、５mmHg、85℃で蒸留し、留分854ｇｒを得
た。蒸留釜の残液は黒褐色粘性液状であり、重合
物の存在は認められなかつた。Example 1 545gr of methacrylic acid, chromic acetate (Cr
(CH 3・COO) 3・H 2 O) 1.5gr methacrylic acid 50
Dissolved in gr and non-flex-F
(Polymerization inhibitor manufactured by Seiko Kagaku Co., Ltd.) 1.8g was charged into one glass reactor, and the inside of the reactor was replaced with N2 gas.
The temperature was raised to ℃, and the internal pressure was set to 1.5 atm. Next, liquid ethylene oxide was fed at a rate of 156 g/Hr (the consumption rate of ethylene oxide at this catalyst concentration and reaction temperature is 128 g/Hr at a partial pressure of 0.5 atm). The internal pressure of the reactor after 60 minutes was 2 atm. Therefore, the ethylene oxide partial pressure is 0.5 atm. The concentration of ethylene oxide dissolved in the liquid at this time is 0.0617mol/
liquid/mol (Henry's constant E = 8.10). After 60 minutes, ethylene oxide was fed at a rate of 128 g/H, which is equal to the consumption rate, and the internal pressure was reduced to 2.
It was maintained at atmospheric pressure. The ethylene oxide concentration in the reaction solution remained unchanged at 0.0617 mol/mol, and the catalyst concentration was approximately
At 0.0009 mol/mol, the ethylene oxide to catalyst molar concentration ratio was approximately 70. After 132 minutes, the acid concentration is
When the concentration reached 0.1% by weight, the color of the reaction liquid changed from dark green to blackish brown, and the feeding of ethylene oxide was stopped.
No traces of polymer were found in the reactor, so the reaction solution was sent to a simple distillation vessel without passing through, and after first recovering excess ethylene oxide under reduced pressure, it was distilled at 5 mmHg and 85°C to obtain a fraction of 854g. Obtained. The residual liquid in the distillation pot was a blackish brown viscous liquid, and no polymer was observed.
実施例 ２
メタクリル酸371ｇｒ、酢酸第２クロム0.9ｇｒ
およびノンフレツクス−F0.5ｇｒを１ステンレ
ス反応器に仕込み、反応器内をN2ガス置換した
後、90℃に昇温し、内圧を1.5気圧とした。次い
で液状エチレンオキサイドを351ｇ／Ｈで供給し
た（このときの触媒濃度および反応温度における
エチレンオキサイドの消費速度は分圧１気圧のと
き153ｇ／Ｈである）。12分後、反応器内圧は2.5
気圧を示した。エチレンオキサイド分圧は１気圧
であり、液に溶けているエチレンオキサイドの濃
度は0.123mol／mol液であつた。12分経過後、エ
チレンオキサイドの送入を153ｇ／Ｈで行ない、
内圧は2.5気圧に保つた。反応液中のエチレンオ
キサイド対触媒モル濃度比は約147であつた。34
分経過後、反応液150ｇｒを分取し、酸分析した
ところ5.2重量％であつた。直ちにエチレンオキ
サイドの供給を再開した後、13分後に停止して反
応液を採取し、酸分析値は0.15重量％であつた。
反応液の色は黒褐色であり実施例１と同じく単蒸
留で381ｇｒの留分を得た。反応器および蒸留器
のいずれにも重合物の痕跡は認められなかつた。
一方、分取した反応液は濃緑色であり、前記方法
で蒸留を始めたところ、50ｇｒの留分を得た時点
で蒸留釜内液にホツプコーン状の重合が発生し蒸
留継続は不可能となつた。Example 2 Methacrylic acid 371g, chromic acetate 0.9gr
and Nonflex-F0.5gr were charged into a stainless steel reactor, and after replacing the inside of the reactor with N2 gas, the temperature was raised to 90°C and the internal pressure was set to 1.5 atm. Next, liquid ethylene oxide was supplied at 351 g/H (the consumption rate of ethylene oxide at this catalyst concentration and reaction temperature was 153 g/H at a partial pressure of 1 atmosphere). After 12 minutes, the reactor internal pressure is 2.5
It showed atmospheric pressure. The partial pressure of ethylene oxide was 1 atm, and the concentration of ethylene oxide dissolved in the liquid was 0.123 mol/mol liquid. After 12 minutes, ethylene oxide was introduced at a rate of 153 g/H.
The internal pressure was maintained at 2.5 atm. The molar concentration ratio of ethylene oxide to catalyst in the reaction solution was about 147. 34
After a few minutes had elapsed, 150g of the reaction solution was collected and analyzed for acid, and found to be 5.2% by weight. After immediately restarting the supply of ethylene oxide, it was stopped after 13 minutes and the reaction solution was collected, and the acid analysis value was 0.15% by weight.
The color of the reaction liquid was blackish brown, and as in Example 1, a fraction of 381g was obtained by simple distillation. No trace of polymer was observed in either the reactor or the distiller.
On the other hand, the separated reaction liquid was dark green, and when distillation was started using the method described above, hop cone-shaped polymerization occurred in the liquid in the distillation pot and it became impossible to continue distillation. Ta.
比較例 １
メタクリル酸350ｇｒ、酢酸第２クロム0.8ｇｒ
およびノンフレツクス−F1.0ｇｒを１ガラス反
応器に仕込み、実施例１同じ操作のあと液状エチ
レンオキサイドを16ｇｒ／Hrで供給した（この
ときのエチレンオキサイドの消費速度は分圧0.1
気圧のとき14ｇ／Hrである）。60分後、反応器内
圧は1.6気圧を示した。エチレンオキサイド分圧
は0.1気圧であり、液に溶解しているエチレンオ
キサイドの濃度は0.0123mol／mol・液であつた。
60分経過後、エチレンオキサイドの送入を153
ｇ／Ｈで行ない、内圧は1.6気圧に保つた。反応
液中のエチレンオキサイド対触媒モル濃度比は約
15であつた。11時間後エチレンオキサイドの供給
を停止し反応液の酸分析を実施したところ、3.4
重量％であり、液は濃緑色を呈していた。次いで
実施例１と同様にして単蒸留したところ、180ｇ
ｒの留分を得た時点で蒸留器気相壁に半透明黄白
色ポリマーが付着し、留分370ｇｒを得た時、留
出液をガラス棒につけて滴下したところ糸を引き
重合開始が認められた。同時に釜内液は水飴状に
粘性を増したため蒸留を停止した。Comparative example 1 350gr methacrylic acid, 0.8gr chromic acetate
and Nonflex-F1.0gr were charged into a glass reactor, and after the same operation as in Example 1, liquid ethylene oxide was supplied at a rate of 16gr/Hr (the consumption rate of ethylene oxide at this time was a partial pressure of 0.1
14g/Hr at atmospheric pressure). After 60 minutes, the reactor internal pressure showed 1.6 atmospheres. The ethylene oxide partial pressure was 0.1 atm, and the concentration of ethylene oxide dissolved in the liquid was 0.0123 mol/mol·liquid.
After 60 minutes, the supply of ethylene oxide was stopped at 153
g/H, and the internal pressure was maintained at 1.6 atm. The molar concentration ratio of ethylene oxide to catalyst in the reaction solution is approximately
It was 15. After 11 hours, the supply of ethylene oxide was stopped and the acid analysis of the reaction solution was performed, and the result was 3.4.
% by weight, and the liquid had a dark green color. Then, simple distillation was carried out in the same manner as in Example 1, and 180g
When the fraction r was obtained, a translucent yellowish-white polymer adhered to the vapor phase wall of the distiller, and when the distillate 370g was obtained, when the distillate was dipped onto a glass rod and dripped, a string was pulled and polymerization started. It was done. At the same time, the liquid in the pot became viscous like starch syrup, so distillation was stopped.
比較例 ２
メタクリル酸595ｇｒ、酢酸第２クロム4.5ｇｒ
およびノンフレツクス−F1.8ｇｒを１ガラス反
応器に仕込み、容器内をN2ガス置換して90℃に
昇温し、1.5気圧とした。次いで液状エチレンオ
キサイドを23ｇｒ／Ｈで供給した（このときのエ
チレンオキサイドの消費速度はエチレンオキサイ
ド分圧0.02気圧のとき22ｇｒ／Ｈである）。60分
後、反応器内圧は1.52気圧を示した。エチレンオ
キサイド分圧は0.02気圧であり、液に溶解してい
るエチレンオキサイドの濃度は0.00215mol／
mol・液であつた。60分経過後、エチレンオキサ
イドの送入を22ｇｒ／Hrで行ない、内圧は1.52
気圧に保つた。反応液中のエチレンオキサイド対
触媒モル濃度比は約0.8であつた。反応開始後６
時間ごろから液の粘性が増し、12時間後完全に茶
褐色のホップコーン状に重合した。Comparative example 2 595gr methacrylic acid, 4.5gr chromic acetate
and Non-Flex-F1.8gr were charged into a 1-glass reactor, and the inside of the container was replaced with N 2 gas, the temperature was raised to 90°C, and the pressure was set to 1.5 atm. Next, liquid ethylene oxide was supplied at 23 gr/H (the consumption rate of ethylene oxide at this time was 22 gr/H when the partial pressure of ethylene oxide was 0.02 atm). After 60 minutes, the reactor internal pressure showed 1.52 atmospheres. The partial pressure of ethylene oxide is 0.02 atm, and the concentration of ethylene oxide dissolved in the liquid is 0.00215 mol/
It was mol/liquid. After 60 minutes, ethylene oxide was introduced at a rate of 22gr/Hr, and the internal pressure was 1.52.
It was maintained at atmospheric pressure. The molar concentration ratio of ethylene oxide to catalyst in the reaction solution was about 0.8. 6 after the start of the reaction
The viscosity of the liquid increased around that time, and after 12 hours it completely polymerized into a brown hop cone.
第１図は酢酸第２クロムを触媒としてメタクリ
ル酸（MAA）をエチレンオキサイド（EO）と
反応させて２−ヒドロキシエチルメタクリレート
（HEMA）を製造した場合のエチレンオキサイド
分圧と反応速度との関係を示すグラフ図である。
第２図は同じく触媒濃度と反応速度との関係を示
すグラフ図である。第３図は同じく反応温度と反
応速度との関係を示すグラフ図である。第４図は
同じく液中の２−ヒドロキシエチルメタクリレー
ト（HEMA）とエチレンオキサイド（EO）溶解
度との関係を示すグラフ図である。
Figure 1 shows the relationship between ethylene oxide partial pressure and reaction rate when 2-hydroxyethyl methacrylate (HEMA) is produced by reacting methacrylic acid (MAA) with ethylene oxide (EO) using dichromic acetate as a catalyst. FIG.
FIG. 2 is a graph showing the relationship between catalyst concentration and reaction rate. FIG. 3 is a graph showing the relationship between reaction temperature and reaction rate. FIG. 4 is a graph showing the relationship between 2-hydroxyethyl methacrylate (HEMA) and ethylene oxide (EO) solubility in the same liquid.
Claims (1)
タクリル酸にアルキレンオキサイドを添加し乍ら
反応させて２−ヒドロキシアルキル（メタ）アク
リレートを製造するにあたり、触媒の使用量をア
クリル酸又はメタクリル酸に対して0.1〜0.3重量
％とし、かつ、反応中および反応終了時において
反応液中に含まれるアルキレンオキサイドのモル
濃度を前記クロム化合物のモル濃度の３倍を超え
て存在させ乍ら反応を実施することを特徴とする
２−ヒドロキシアルキル（メタ）アクリレートの
製法。1. When producing 2-hydroxyalkyl (meth)acrylate by adding alkylene oxide to acrylic acid or methacrylic acid and reacting with chromium acetate as a catalyst, the amount of catalyst used is 0.1 per acrylic acid or methacrylic acid. ~0.3% by weight, and the reaction is carried out while the molar concentration of alkylene oxide contained in the reaction solution is more than three times the molar concentration of the chromium compound during the reaction and at the end of the reaction. A method for producing 2-hydroxyalkyl (meth)acrylate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55116917A JPS5742657A (en) | 1980-08-27 | 1980-08-27 | Preparation of 2-hydroxyalkyl meth acrylate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55116917A JPS5742657A (en) | 1980-08-27 | 1980-08-27 | Preparation of 2-hydroxyalkyl meth acrylate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5742657A JPS5742657A (en) | 1982-03-10 |
| JPH0530822B2 true JPH0530822B2 (en) | 1993-05-11 |
Family
ID=14698853
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP55116917A Granted JPS5742657A (en) | 1980-08-27 | 1980-08-27 | Preparation of 2-hydroxyalkyl meth acrylate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5742657A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6127944A (en) * | 1984-07-17 | 1986-02-07 | Mitsui Toatsu Chem Inc | Method of distilling 2-hydroxyalkyl (meth)acrylate |
| JPS6127945A (en) * | 1984-07-17 | 1986-02-07 | Mitsui Toatsu Chem Inc | Preparation of 2-hydroxyalkyl (meth)acrylate |
| JP5143325B2 (en) * | 2001-08-17 | 2013-02-13 | 株式会社日本触媒 | Method for producing hydroxyalkyl (meth) acrylate |
| JP4772997B2 (en) * | 2001-07-30 | 2011-09-14 | 株式会社日本触媒 | Method for producing hydroxyalkyl (meth) acrylate |
| CN110922330B (en) * | 2019-11-22 | 2022-08-26 | 广东新华粤石化集团股份公司 | Preparation method of hydroxyethyl acrylate |
| JP7162195B1 (en) | 2022-02-25 | 2022-10-28 | 東レ・オペロンテックス株式会社 | polyurethane elastic fiber |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49124015A (en) * | 1973-03-31 | 1974-11-27 | ||
| US3875211A (en) * | 1973-01-22 | 1975-04-01 | Alcolac Inc | Process for preparing 2-hydroxyalkylacrylates and 2-hydroxyalkylmethacrylates |
-
1980
- 1980-08-27 JP JP55116917A patent/JPS5742657A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3875211A (en) * | 1973-01-22 | 1975-04-01 | Alcolac Inc | Process for preparing 2-hydroxyalkylacrylates and 2-hydroxyalkylmethacrylates |
| JPS49124015A (en) * | 1973-03-31 | 1974-11-27 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5742657A (en) | 1982-03-10 |
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