WO2003064370A1 - Procede de production d'ester (meth)acrylique - Google Patents

Procede de production d'ester (meth)acrylique 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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WO
WIPO (PCT)
Prior art keywords
meth
reactor
reaction
acrylic acid
polymerization inhibitor
Prior art date
Application number
PCT/JP2003/000594
Other languages
English (en)
Japanese (ja)
Inventor
Shuhei Yada
Masayasu Goriki
Mitsuo Nakamura
Original Assignee
Mitsubishi Chemical Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Chemical Corporation filed Critical Mitsubishi Chemical Corporation
Publication of WO2003064370A1 publication Critical patent/WO2003064370A1/fr

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Classifications

    • 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.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé de production d'un ester (méth)acrylique qui consiste à envoyer de l'acide (méth)acrylique et un alcool dans un réacteur dans lequel se trouve dissous un inhibiteur de polymérisation dans le mélange de réaction, la réaction étant conduite alors que le mélange de réaction contenant l'inhibiteur de polymérisation est maintenu en contact avec un élément présent dans la partie phase gazeuse du réacteur. De cette manière, l'acide (méth)acrylique et l'ester (méth)acrylique ne peuvent se polymériser sur l'élément présent dans la partie phase gazeuse du réacteur et on peut ainsi effectuer cette opération en continu sur une longue période.
PCT/JP2003/000594 2002-01-30 2003-01-23 Procede de production d'ester (meth)acrylique WO2003064370A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2002-21374 2002-01-30
JP2002021374 2002-01-30

Publications (1)

Publication Number Publication Date
WO2003064370A1 true WO2003064370A1 (fr) 2003-08-07

Family

ID=27654389

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2003/000594 WO2003064370A1 (fr) 2002-01-30 2003-01-23 Procede de production d'ester (meth)acrylique

Country Status (2)

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CN (1) CN1537095A (fr)
WO (1) WO2003064370A1 (fr)

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 (fr) * 1999-04-16 2000-10-18 Nippon Shokubai Co., Ltd. Procédé afin d' inhiber la polymérisation de composants à forte tendance polymérisable

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 (fr) * 1999-04-16 2000-10-18 Nippon Shokubai Co., Ltd. Procédé afin d' inhiber la polymérisation de composants à forte tendance polymérisable

Also Published As

Publication number Publication date
CN1537095A (zh) 2004-10-13

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