WO2003064370A1 - Process for producing (meth)acrylic ester - Google Patents

Process for producing (meth)acrylic ester Download PDF

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Publication number
WO2003064370A1
WO2003064370A1 PCT/JP2003/000594 JP0300594W WO03064370A1 WO 2003064370 A1 WO2003064370 A1 WO 2003064370A1 JP 0300594 W JP0300594 W JP 0300594W WO 03064370 A1 WO03064370 A1 WO 03064370A1
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meth
reactor
reaction
acrylic acid
polymerization inhibitor
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PCT/JP2003/000594
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French (fr)
Japanese (ja)
Inventor
Shuhei Yada
Masayasu Goriki
Mitsuo Nakamura
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Mitsubishi Chemical Corporation
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Publication of WO2003064370A1 publication Critical patent/WO2003064370A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • 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
    • C07C67/62—Use of additives, e.g. for stabilisation

Definitions

  • the present invention relates to a method for producing a (meth) acrylate.
  • (me) acrylic acid means either acrylic acid or methacrylic acid or the rainy way.
  • (meth) acrylic acid ester is a liquid having extremely high polymerizability, and it is known that a polymerization inhibitor such as hydroquinone or phenothiazine is contained in order to prevent the polymerization (for example, see Japanese Patent Application Laid-open No. 0 0 0—3 5 5 5 7 0 public announcement).
  • a polymerization inhibitor such as hydroquinone or phenothiazine
  • the present invention has been made in view of the above circumstances, and has as its object to prevent polymerization of (meth) acrylic acid and (meth) acrylic acid ester in a member existing in a gas phase part of a reactor, and
  • An object of the present invention is to provide a method for producing a (meth) acrylate ester which can be operated continuously over a long period of time.
  • Fig. 1 is a cross section of an example of a reactor and its auxiliary equipment suitably used in the present invention.
  • FIG. Disclosure of the invention is a cross section of an example of a reactor and its auxiliary equipment suitably used in the present invention.
  • the gist of the present invention is that when a (meth) acrylic acid and an alcohol are supplied to a reactor to produce a (meth) acrylic acid ester, a polymerization inhibitor is dissolved in a reaction solution, and the polymerization inhibitor is dissolved.
  • a method for producing a (meth) acrylate ester characterized in that a reaction is carried out while a reaction solution is in contact with a member present in a gas phase part of a reactor.
  • the production of the (meth) acrylic acid ester of the present invention is basically the same as a conventionally known method.
  • Examples of the acrylate ester produced by the present invention include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, and 2-hydroxyethyl acrylate. —Hydroxypropyl, methoxyethyl acrylate and the like.
  • Examples of the methacrylate produced according to the present invention include various methacrylates corresponding to the above acrylate, such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate.
  • the raw material alcohol various alcohols corresponding to the above (meth) acrylic acid ester are used.
  • the reaction between (meth) acrylic acid and alcohol is usually performed in the presence of an acidic catalyst, and para-toluenesulfonic acid or the like is used as the acidic catalyst.
  • the above reaction is industrially performed continuously. That is, (meth) acrylic acid and alcohol are continuously supplied to the reactor, and the generated (meth) acrylic acid ester and water by-produced are continuously withdrawn from the reactor.
  • the supply molar ratio of alcohol to (meth) ataryl acid is usually 0.5 to 2
  • the reaction temperature is usually 80 to 100 t :
  • the reaction pressure is usually 25 to 70 kPa
  • the reaction time (residence) Hours) usually 1-5 Time.
  • phenol compounds examples include hydroquinone, methoquinone (a methoxyhydric quinone), pyrogallol, catechol, resorcinol, and the like.
  • phenothiazine compound examples include phenothiazine, bis- (hy-methylbenzyl) phenothiazine, and bis- (bi-methyl).
  • copper compounds include cupric chloride, copper acetate, copper carbonate, copper acrylate, dimethyldithine copper rubinate and the like. Is mentioned.
  • the polymerization inhibitor is used by dissolving it in an appropriate solvent.
  • a solvent examples include water, acetic acid, (meth) acrylic acid, (meth) acrylic acid ester, and aromatic compound in the case of a phenol compound. , Ketone compounds, alcohols and the like.
  • the concentration of the polymerization inhibitor in the reaction solution is usually 0.01 to 1.5% by weight.
  • a stirred tank reactor as shown in FIG. 1 is preferably used.
  • the stirred tank reactor is configured by adding a stirrer (2) to a cylindrical body (1) having both sides (11) having a substantially hemispherical shape.
  • the ceiling of the cylindrical body (1) is equipped with a vapor pipe (3) for extracting by-product water and a manhole (4) for inspection.
  • the inside of the cylindrical body (1) is divided into compartments of an appropriate volume by a partition plate (5) according to the residence time required for the reaction.
  • each chamber is connected by a connecting pipe (61) with a valve (not shown) installed outside the cylindrical body (1), and a stirrer (2) is installed for each chamber.
  • the raw material (meth) acrylic acid and alcohol are supplied from the top of one end of the reactor by a pump (not shown), and the product (meth) acrylic ester is supplied by a pump (7) to the other end of the reactor. It is pulled out from the bottom. Then, the by-product water is extracted from the vapor pipe (3).
  • the feature of the present invention is that the reaction solution in which the polymerization inhibitor is dissolved
  • the reaction is performed while contacting the material. That is, in the present invention, the polymerization of (meth) acrylic acid ester and the like in the portion existing in the gas phase of the reactor is prevented by wetting the members existing in the gas phase of the reactor with the reaction solution containing the polymerization inhibitor. I do.
  • examples of the members existing in the gas phase of the reactor include a manhole (4) and a top plate of a cylindrical body (1).
  • the means for contacting the reaction solution with the member is not particularly limited, but a means for spraying the reaction solution from a spray nozzle by a pump is preferably employed. For example, the above-mentioned pump for extracting the reaction solution
  • the reaction liquid supply pipe (63) is branched and connected to the discharge pipe (62) (reaction liquid extraction pipe) of (7), and a spray nozzle (8) is provided at the tip of the reaction liquid supply pipe.
  • the reaction liquid supply pipe (63) is arranged so as to discharge from the bottom of the cylindrical body (1) to the upper space, the (meth) acrylic acid ester is exposed to the gas phase of the reactor. This is preferable because the amount of piping in which polymerization occurs is reduced.
  • the type of the spray nozzle (8) is selected as appropriate, for example, a manhole with a small area
  • a conical spray nozzle is preferably used, and for spraying a large-area partition plate (5) or a cylindrical body (1) to a top plate, a wide-angle fan-type spray nozzle is preferably used.
  • a strainer (9) in the middle of the reaction solution supply pipe (63) in order to continuously remove solids accumulated in the reaction solution.
  • two strainers (9) are provided so as to be switchable.
  • the opening of the screen of the strainer (9) is usually 30 mesh or more, preferably 60 to 100 mesh.
  • a flow meter (6 mm) and a pressure gauge (6 ⁇ ) are installed to control the flow rate of the reaction liquid supplied to the spray nozzle (8). It is preferable to manage.
  • the supply amount of the reaction solution is not particularly limited as long as the members existing in the gas phase part of the reactor can always be kept wet by the reaction solution, but is usually 200 L / Hr or more, preferably 200 to 800. L / Hr. BEST MODE FOR CARRYING OUT THE INVENTION
  • the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist.
  • a stainless steel (SUS316L) stirred tank type reactor similar to that shown in Fig. 1 was used.
  • the diameter of the cylinder (1) is 300 Omm and the length is 600 Omm.
  • the diameter of the manhole (4) is 50 Omm and the height of the partition (5) is 280 Omm
  • the reaction liquid was sprayed from the spray nozzle (8) onto the entire surface of the manhole (4), the top plate of the cylindrical body (1), and the space exposed portion of the partition plate (5).
  • the spray volume is 330 L / Hr for the manhole (4), 580 L / Hr for the top of the cylindrical body (1), and 420 for the exposed part of the partition (5). L / Hr.
  • Example 1 a continuous esterification reaction was performed in the same manner as in Example 1 except that the reaction liquid was not sprayed from the spray nozzle (8). About 1 month after the start of the reaction, solids were observed on the strainer (9), and after about 2 months, the reaction stopped because the solids became frequently clogged on the strainer (9). did. As a result of observing the members existing in the gas phase of the reactor from the manhole (4), the manhole (4), the top plate of the cylindrical body (1), and the space exposed part of the partition plate (5) overlapped. Adhesion of the compound was observed, and the total amount was measured after peeling off to be 200 kg. Industrial applicability
  • the method for producing a (meth) acrylic ester according to the present invention described above prevents the polymerization of (meth) acrylic ester and the like in members existing in the gas phase of the reactor, and performs continuous operation for a long period of time. Can be done.

Abstract

A process for producing a (meth)acrylic ester which comprises feeding (meth)acrylic acid and an alcohol to a reactor, wherein a polymerization inhibitor is dissolved in the reaction mixture and the reaction is conducted while keeping the reaction mixture containing the polymerization inhibitor dissolved therein in contact with a member present in the gas-phase part of the reactor. Thus, the (meth)acrylic acid and the (meth)acrylic ester are prevented from polymerizing on the member present in the gas-phase part of the reactor, and a continuous operation can be conducted over long.

Description

明 細 書 (メタ） アクリル酸エステルの製造方法 技術分野  Description (meth) Method for producing acrylic acid ester
本発明は （メタ） アクリル酸エステルの製造方法に関する。 なお、 「 （メ 夕） アクリル酸」 の表記はアクリル酸とメタクリル酸の一方または雨方を意味 する。 背景技術  The present invention relates to a method for producing a (meth) acrylate. The notation “(me) acrylic acid” means either acrylic acid or methacrylic acid or the rainy way. Background art
周知の通り、 （メタ） アクリル酸エステルは重合性が極めて高い液体であ り、 その重合防止のため、 ハイドロキノン、 フエノチアジン等の重合防止剤を 含有させることが知られている （例えば、 特開 2 0 0 0— 3 5 5 5 7 0号公 報） 。  As is well known, (meth) acrylic acid ester is a liquid having extremely high polymerizability, and it is known that a polymerization inhibitor such as hydroquinone or phenothiazine is contained in order to prevent the polymerization (for example, see Japanese Patent Application Laid-open No. 0 0 0—3 5 5 5 7 0 public announcement).
しかしながら、 反応器に （メタ） アクリル酸とアルコールとを供給して （メ タ） アクリル酸エステルを製造する場合、 反応液に重合防止剤を溶解させて も、 反応器の天板 （マンホール） 等の反応器気相部に存在する部材において、 (メタ） アクリル酸および （メタ） アクリル酸エステルの蒸気が凝縮し、 当該 凝縮液中で重合するため、 長期間に亘って連続運転を行なうことが出来ないと いう問題がある。  However, when (meth) acrylic acid and alcohol are supplied to the reactor to produce (meth) acrylic acid ester, even if the polymerization inhibitor is dissolved in the reaction solution, the reactor top plate (manhole) etc. Since the vapors of (meth) acrylic acid and (meth) acrylate ester condense and polymerize in the condensed liquid in the members existing in the gas phase of the reactor, continuous operation can be performed for a long period of time. There is a problem that it cannot be done.
本発明は、 上記実情に鑑みなされたものであり、 その目的は、 反応器気相部 に存在する部材における （メタ） アクリル酸および （メタ） アクリル酸エステ ルの重合を防止し、 長期間に亘つて連続運転を行なうことが出来る様に改良さ れた （メタ） アクリル酸エステルの製造方法を提供することにある。 図面の簡単な説明  The present invention has been made in view of the above circumstances, and has as its object to prevent polymerization of (meth) acrylic acid and (meth) acrylic acid ester in a member existing in a gas phase part of a reactor, and An object of the present invention is to provide a method for producing a (meth) acrylate ester which can be operated continuously over a long period of time. BRIEF DESCRIPTION OF THE FIGURES
図 1 は本発明において好適に使用される反応器とその付帯設備の一例の断面 説明図である。 発明の開示 Fig. 1 is a cross section of an example of a reactor and its auxiliary equipment suitably used in the present invention. FIG. Disclosure of the invention
すなわち、 本発明の要旨は、 反応器に （メタ） アクリル酸とアルコールとを 供給して （メタ） アクリル酸エステルを製造するに際し、 反応液に重合防止剤 を溶解させ、 重合防止剤が溶解した反応液を反応器気相部に存在する部材に接 触させつつ反応を行なうことを特徴とする （メタ） アクリル酸エステルの製造 方法に存する。  That is, the gist of the present invention is that when a (meth) acrylic acid and an alcohol are supplied to a reactor to produce a (meth) acrylic acid ester, a polymerization inhibitor is dissolved in a reaction solution, and the polymerization inhibitor is dissolved. A method for producing a (meth) acrylate ester, characterized in that a reaction is carried out while a reaction solution is in contact with a member present in a gas phase part of a reactor.
以下、 本発明を添付図面に基づいて詳細に説明する。  Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.
本発明の （メタ） アクリル酸エステルの製造は、 基本的には従来公知の方法 と同じである。  The production of the (meth) acrylic acid ester of the present invention is basically the same as a conventionally known method.
本発明によって製造されるアクリル酸エステルとしては、 ァクリル酸メチ ル、 アクリル酸ェチル、 ァクリル酸プ口ピル、 ァクリル酸ブチル、 アタリル酸 2—ェチルへキシル、 アクリル酸 2—ヒドロキシェチル、 アクリル酸 2—ヒド ロキシプロピル、 アクリル酸メトキシェチル等カ s挙げられる。 本発明によって 製造されるメタクリル酸エステルとしては、 上記のアクリル酸エステルに対応 した各種のメタクリル酸エステル、 例えば、 メタクリル酸メチル、 メタクリル 酸ェチル、 メタクリル酸プロピル、 メタクリル酸ブチル等が挙げられる。  Examples of the acrylate ester produced by the present invention include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, and 2-hydroxyethyl acrylate. —Hydroxypropyl, methoxyethyl acrylate and the like. Examples of the methacrylate produced according to the present invention include various methacrylates corresponding to the above acrylate, such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate.
本発明において、 原料アルコールとしては、 上記の （メタ） アクリル酸エス テルに対応する各種のアルコールが使用される。 （メタ） アクリル酸とアル コールとの反応は、 通常、 酸性触媒の存在下に行なわれ、 酸性触媒としては、 パラトルエンスルホン酸などが使用される。  In the present invention, as the raw material alcohol, various alcohols corresponding to the above (meth) acrylic acid ester are used. The reaction between (meth) acrylic acid and alcohol is usually performed in the presence of an acidic catalyst, and para-toluenesulfonic acid or the like is used as the acidic catalyst.
上記の反応は工業的には連続的に行われる。 すなわち、 （メタ） アクリル酸 とアルコールとは反応器に連続的に供給され、 生成した （メタ） アクリル酸ェ ステルと副生した水は反応器から連続的に抜出される。 （メタ） アタリル酸に 対するアルコールの供給モル比は通常 0 . 5〜 2、 反応温度は通常 8 0〜 1 0 0 t：、 反応圧力は通常 2 5〜 7 0 k P a、 反応時間 （滞留時間） は通常 1〜 5 時間である。 The above reaction is industrially performed continuously. That is, (meth) acrylic acid and alcohol are continuously supplied to the reactor, and the generated (meth) acrylic acid ester and water by-produced are continuously withdrawn from the reactor. The supply molar ratio of alcohol to (meth) ataryl acid is usually 0.5 to 2, the reaction temperature is usually 80 to 100 t :, the reaction pressure is usually 25 to 70 kPa, and the reaction time (residence) Hours) usually 1-5 Time.
重合防止剤としては、 各種のフエノール化合物、 フヱノチアジン化合物、 銅 化合物などが使用される。 フエノール化合物としては、 ハイ ドロキノン、 メト キノン （メ トキシハイド口キノン） 、 ピロガロ一ル、 カテコール、 レゾルシン 等が挙げられ、 フエノチアジン化合物としては、 フエノチアジン、 ビス一 （ ひ —メチルベンジル） フエノチアジン、 ビス一 ( ひージメチルベンジル) フエノ チアジン、 3， 7—ジォクチルフエノチアジン等が挙げられ、 銅化合物として は、 塩化第 2銅、 酢酸銅、 炭酸銅、 アクリル酸銅、 ジメチルジチ才力ルバミン 酸銅などが挙げられる。  As the polymerization inhibitor, various phenol compounds, phenothiazine compounds, copper compounds and the like are used. Examples of the phenolic compound include hydroquinone, methoquinone (a methoxyhydric quinone), pyrogallol, catechol, resorcinol, and the like. Examples of the phenothiazine compound include phenothiazine, bis- (hy-methylbenzyl) phenothiazine, and bis- (bi-methyl). -Dimethylbenzyl) phenothiazine, 3,7-dioctyl phenothiazine, etc.Examples of copper compounds include cupric chloride, copper acetate, copper carbonate, copper acrylate, dimethyldithine copper rubinate and the like. Is mentioned.
重合防止剤は適当な溶媒に溶解して使用され、 斯かる溶媒としては、 例え ば、 フヱノール化合物の場合は、 水、 酢酸、 （メタ） アクリル酸、 （メタ） ァ クリル酸エステル、 芳香族化合物、 ケトン化合物、 アルコール等が挙げられ る。 反応液中における重合防止剤の濃度は通常 0. 0 1〜 1. 5重量％であ る  The polymerization inhibitor is used by dissolving it in an appropriate solvent. Examples of such a solvent include water, acetic acid, (meth) acrylic acid, (meth) acrylic acid ester, and aromatic compound in the case of a phenol compound. , Ketone compounds, alcohols and the like. The concentration of the polymerization inhibitor in the reaction solution is usually 0.01 to 1.5% by weight.
本発明においては、 図 1に示す様な撹拌槽型反応器が好適に使用される。 撹 拌槽型反応器は、 両サイド （1 1) が略半球状となされた円筒体 (1) に攪拌 器 （2) を付設して構成される。 円筒体 （1) の天井部には、 副生した水を抜 出すためのベーパー管 （3) と点検用のマンホール （4) が備えられる。 ま た、 円筒体の （1) 内部は、 反応に必要な滞留時間に応じ、 仕切板 （5) に よって適当容量の容室に区切られている。 この場合、 各容室は円筒体 （1) の 外部に設置されたバルブ （図示せず） 付き連絡配管 （61 ) によって連絡さ れ、 各容室毎に攪拌器 （2) 力設置される。  In the present invention, a stirred tank reactor as shown in FIG. 1 is preferably used. The stirred tank reactor is configured by adding a stirrer (2) to a cylindrical body (1) having both sides (11) having a substantially hemispherical shape. The ceiling of the cylindrical body (1) is equipped with a vapor pipe (3) for extracting by-product water and a manhole (4) for inspection. The inside of the cylindrical body (1) is divided into compartments of an appropriate volume by a partition plate (5) according to the residence time required for the reaction. In this case, each chamber is connected by a connecting pipe (61) with a valve (not shown) installed outside the cylindrical body (1), and a stirrer (2) is installed for each chamber.
原料の （メタ） アクリル酸とアルコールは、 ポンプ （図示せず） により反応 器の一端の上部から供給され、 生成物の （メタ） アクリル酸エステルは、 ボン プ （7) により反応器の他端の底部から抜出される。 そして、 副生した水は ベーパー管 (3) から抜出される。  The raw material (meth) acrylic acid and alcohol are supplied from the top of one end of the reactor by a pump (not shown), and the product (meth) acrylic ester is supplied by a pump (7) to the other end of the reactor. It is pulled out from the bottom. Then, the by-product water is extracted from the vapor pipe (3).
本発明の特徴は、 重合防止剤が溶解した反応液を反応器気相部に存在する部 材に接触させつつ反応を行なう点にある。 すなわち、 本発明においては、 重合 防止剤含有反応液で反応器気相部に存在する部材を濡らすことにより、 反応器 気相部に存在する部での （メタ） アクリル酸エステル等の重合を防止する。 反応器気相部に存在する部材としては、 図 1に示した例の場合は、. マンホー ル （4) 、 円筒体 （1) の天板などが挙げられる。 上記の反応液と部材との接 触手段は、 特に制限されないが、 ポンプによってスプレーノズルから反応液を 噴霧する手段が好適に採用される。 例えば、 前記の反応液抜出し用のポンプThe feature of the present invention is that the reaction solution in which the polymerization inhibitor is dissolved The point is that the reaction is performed while contacting the material. That is, in the present invention, the polymerization of (meth) acrylic acid ester and the like in the portion existing in the gas phase of the reactor is prevented by wetting the members existing in the gas phase of the reactor with the reaction solution containing the polymerization inhibitor. I do. In the case of the example shown in Fig. 1, examples of the members existing in the gas phase of the reactor include a manhole (4) and a top plate of a cylindrical body (1). The means for contacting the reaction solution with the member is not particularly limited, but a means for spraying the reaction solution from a spray nozzle by a pump is preferably employed. For example, the above-mentioned pump for extracting the reaction solution
(7) の吐出側配管 （62) (反応液抜出し配管） に反応液供給配管 （63) を分岐させて接続し、 当該反応液供給配管の先端部にスプレーノズル （8) を 設ける。 この場合、 反応液供給配管 （63) は、 円筒体 （1) の底部から上部 の空間部に吐出する様に配置するならば、 反応器気相部に露出して （メタ） ァ クリル酸エステルの重合が起こる配管部分が少なくなるので好ましい。 スプ レーノズル (8) の型式は、 適宜選択され、 例えば、 面積の狭いマンホールThe reaction liquid supply pipe (63) is branched and connected to the discharge pipe (62) (reaction liquid extraction pipe) of (7), and a spray nozzle (8) is provided at the tip of the reaction liquid supply pipe. In this case, if the reaction liquid supply pipe (63) is arranged so as to discharge from the bottom of the cylindrical body (1) to the upper space, the (meth) acrylic acid ester is exposed to the gas phase of the reactor. This is preferable because the amount of piping in which polymerization occurs is reduced. The type of the spray nozzle (8) is selected as appropriate, for example, a manhole with a small area
(4) への噴霧には充円錐型スプレーノズル、 面積の広い仕切板 (5) や円筒 体 （1) の天板への噴霧には広角扇型スプレーノズル力好適に使用される。 本発明においては、 反応液中に蓄積される固形物を連続的に除まするため、 反応液供給管 （63) の途中にストレーナ一 （9) を設けるのが好ましい。 図For spraying to (4), a conical spray nozzle is preferably used, and for spraying a large-area partition plate (5) or a cylindrical body (1) to a top plate, a wide-angle fan-type spray nozzle is preferably used. In the present invention, it is preferable to provide a strainer (9) in the middle of the reaction solution supply pipe (63) in order to continuously remove solids accumulated in the reaction solution. Figure
1に示した例においては、 2個のストレーナ一 （9) が切替え使用可能に設け られている。 ストレーナ一 （9) のスクリーンの目開きは、 通常 30メッシュ 以上、 好ましくは 60〜100メッシュである。 また、 反応液供給管 （63) の途中には、 流量計 （6 ί ) と圧力計 （6 ρ) とを設置し、 これらにより、 ス プレーノズル （8) に供給される反応液の流量を管理するのが好ましい。 反応 液の供給量は、 反応器気相部に存在する部材が常に反応液によって濡れている 状態を維持し得る限り、 特に制限されないが、 通常 200 L/H r以上、 好ま しくは 200〜 800 L/H rである。 発明を実施するための最良の形態 以下、 本発明を実施例により更に詳細に説明するが、 本発明は、 その要旨を 超えない限り、 以下の実施例に限定されるものではない。 In the example shown in 1, two strainers (9) are provided so as to be switchable. The opening of the screen of the strainer (9) is usually 30 mesh or more, preferably 60 to 100 mesh. In the middle of the reaction liquid supply pipe (63), a flow meter (6 mm) and a pressure gauge (6 ρ) are installed to control the flow rate of the reaction liquid supplied to the spray nozzle (8). It is preferable to manage. The supply amount of the reaction solution is not particularly limited as long as the members existing in the gas phase part of the reactor can always be kept wet by the reaction solution, but is usually 200 L / Hr or more, preferably 200 to 800. L / Hr. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist.
実施例 1  Example 1
図 1に示すのと同様のステンレス製 （SUS 3 16 L) 撹拌槽型反応器を使 用した。 円筒体 (1) の直径は 300 Omm、 長さは 600 Ommである。 マ ンホール （4) の直径は 50 Omm、 仕切板 （5) の高さは 280 Ommであ る  A stainless steel (SUS316L) stirred tank type reactor similar to that shown in Fig. 1 was used. The diameter of the cylinder (1) is 300 Omm and the length is 600 Omm. The diameter of the manhole (4) is 50 Omm and the height of the partition (5) is 280 Omm
上記の撹拌槽型反応器にァクリル酸とブチルアルコ^"ルとを供給し、 更に、 反応液中の濃度が 1重量となる量のパラトルエンスルホン酸と 0. 03重量0 /0 となる量のハイドロキノンを供給した。 ハイドロキノンは、 8重量0 /0濃度のブ チルアルコール溶液として供給した。 そして、 反応温度 94°C、 反応圧力 35 k P a、 反応時間 （滞留時間） 3時間の条件で連続的にエステル化反応を行 なった。 Supplying the above stirring tank type reactor Akuriru acid and butyl alcohol ^ "le, further, in the reaction solution concentration is 1 weight become the amount of p-toluenesulfonic acid 0.03 wt 0/0 and becomes the amount of was fed hydroquinone. hydroquinone were supplied as blanking chill alcoholic solution of 8 weight 0/0 concentration. then, the reaction temperature 94 ° C, the reaction pressure 35 k P a, the reaction time (residence time) successively with 3 hours conditions The esterification reaction was carried out.
エステル化反応の間、 マンホール （4) 、 円筒体 （1 ) の天板、 仕切板 （ 5) の空間露出部のそれぞれの全面に対し、 スプレーノズル （8) から反応液 を噴霧した。 噴霧量は、 マンホール （4) に対しては 330 L/H r、 円筒体 (1) の天板に対しては 580 L/H r、 仕切板 （5) の空間露出部に対して は 420 L/H rとした。 約 1年間の連続運転の後、 反応を停止し、 マンホー ル （4) から反応器気相部に存在する部材を観察した結果、 重合物の付着は認 められなかった。  During the esterification reaction, the reaction liquid was sprayed from the spray nozzle (8) onto the entire surface of the manhole (4), the top plate of the cylindrical body (1), and the space exposed portion of the partition plate (5). The spray volume is 330 L / Hr for the manhole (4), 580 L / Hr for the top of the cylindrical body (1), and 420 for the exposed part of the partition (5). L / Hr. After about one year of continuous operation, the reaction was stopped, and observation of the members present in the gas phase of the reactor from the manhole (4) showed no adhesion of polymer.
比較例 1  Comparative Example 1
実施例 1において、 スプレーノズル （8) からの反応液の噴霧を行なわな かった以^ ·は、 実施例 1 と同様に連続エステル化反応を行なった。 反応開始 後、 約 1ヶ月経過した時点でストレーナ一 （9) に固形物が観察され、 約 2ケ 月経過後にはストレーナ一 （9) に固形物が頻繁に詰まる様になつたので反応 を停止した。 マンホール （4) から反応器気相部に存在する部材を観察した結 果、 マンホール （4) 、 円筒体 （1) の天板、 仕切板 （5) の空間露出部に重 合物の付着が認められ、 剥離してその合計量を測定した結果、 2 0 0 K gで あった。 産業上の利用可能性 In Example 1, a continuous esterification reaction was performed in the same manner as in Example 1 except that the reaction liquid was not sprayed from the spray nozzle (8). About 1 month after the start of the reaction, solids were observed on the strainer (9), and after about 2 months, the reaction stopped because the solids became frequently clogged on the strainer (9). did. As a result of observing the members existing in the gas phase of the reactor from the manhole (4), the manhole (4), the top plate of the cylindrical body (1), and the space exposed part of the partition plate (5) overlapped. Adhesion of the compound was observed, and the total amount was measured after peeling off to be 200 kg. Industrial applicability
以上説明した本発明の （メタ） アクリル酸エステルの製造方法は、 反応器気 相部に存在する部材における （メタ） アクリル酸エステル等の重合を防止し、 長期間に亘って連続運転を行なうことが出来る。  The method for producing a (meth) acrylic ester according to the present invention described above prevents the polymerization of (meth) acrylic ester and the like in members existing in the gas phase of the reactor, and performs continuous operation for a long period of time. Can be done.

Claims

請 求 の 範 囲 The scope of the claims
1 . 反応器に （メタ） アクリル酸とアルコールとを供給して （メダ） アクリル 酸エステルを製造するに際し、 反応液に重合防止剤を溶解させ、 重合防止剤が 溶解した反応液を反応器気相部に存在する部材に接触させつつ反応を行なうこ とを特徴とする （メタ） アクリル酸エステルの製造方法。 1. When (meth) acrylic acid and alcohol are supplied to the reactor to produce (meda) acrylate, a polymerization inhibitor is dissolved in the reaction solution, and the reaction solution in which the polymerization inhibitor is dissolved is supplied to the reactor. A method for producing a (meth) acrylic ester, wherein the reaction is carried out while being brought into contact with a member present in a phase portion.
2 . 反応液供給配管の先端にスプレーノズルを設け、 当該スプレーノズルから 反応器気相部に存在する部材に反応液を噴霧する 1に記載の製造方法。  2. The production method according to 1, wherein a spray nozzle is provided at a tip of the reaction liquid supply pipe, and the reaction liquid is sprayed from the spray nozzle onto a member existing in a gas phase part of the reactor.
PCT/JP2003/000594 2002-01-30 2003-01-23 Process for producing (meth)acrylic ester WO2003064370A1 (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5159106A (en) * 1988-12-24 1992-10-27 Henkel Kommanditgesellschaft Auf Aktien Process for the improved production of (meth)acrylic acid esters of polyhydric alcohols (vi)
EP1044957A1 (en) * 1999-04-16 2000-10-18 Nippon Shokubai Co., Ltd. Process for inhibiting the polymerization of easily-polymerizable compounds

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5159106A (en) * 1988-12-24 1992-10-27 Henkel Kommanditgesellschaft Auf Aktien Process for the improved production of (meth)acrylic acid esters of polyhydric alcohols (vi)
EP1044957A1 (en) * 1999-04-16 2000-10-18 Nippon Shokubai Co., Ltd. Process for inhibiting the polymerization of easily-polymerizable compounds

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