WO2006126479A1 - Procede pour produire un ester acrylique - Google Patents

Procede pour produire un ester acrylique Download PDF

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Publication number
WO2006126479A1
WO2006126479A1 PCT/JP2006/310133 JP2006310133W WO2006126479A1 WO 2006126479 A1 WO2006126479 A1 WO 2006126479A1 JP 2006310133 W JP2006310133 W JP 2006310133W WO 2006126479 A1 WO2006126479 A1 WO 2006126479A1
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WO
WIPO (PCT)
Prior art keywords
acrylic acid
less
producing
high boiling
ppm
Prior art date
Application number
PCT/JP2006/310133
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English (en)
Japanese (ja)
Inventor
Masanobu Koyama
Original Assignee
Toagosei Co., Ltd.
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 Toagosei Co., Ltd. filed Critical Toagosei Co., Ltd.
Publication of WO2006126479A1 publication Critical patent/WO2006126479A1/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

Definitions

  • the present invention relates to a method for producing a high-boiling acrylate ester without purification by distillation, represented by an acrylate ester, in particular, an acrylate ester of pentaerythritol or polyalkyleneoxide-modified phenol. .
  • acrylic acid is produced by a gas phase oxidation reaction of propylene, and therefore contains aldehydes as impurities.
  • acrylates such as furfural and benzaldehyde, maleic anhydride, j8- are used in the production of acrylate esters by esterification reaction of acrylic acid and alcohol obtained by propylene gas-phase acid-acid reaction. It is described that the use of acrylic acid containing a specific amount of ataloxypropionic acid, etc. causes blockage of equipment such as piping due to the polymer, a decrease in the main raw material unit, and a change in the polymerization behavior of the product.
  • Patent Document 1 specifically exemplified in Patent Document 1 is an acrylic acid ester of a low-boiling alcohol that can be distilled as a purification process, and a specific description of an acrylate ester of a high-boiling alcohol. Flower ,.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2003-171347
  • the present invention seeks to provide a high-boiling acrylate ester having low coloration and excellent quality by controlling specific aldehydes in acrylic acid.
  • the present invention uses acrylic acid containing 100 ppm by weight or less of aldehydes when producing high boiling acrylic acid ester by esterification reaction of acrylic acid and high boiling point alcohol, and acrylic acid as a purification step.
  • APHA is 100 or less acrylic ester production method characterized by not using ester distillation.
  • a high-boiling acrylic ester with little coloring can be easily produced.
  • a composition containing such an acrylate ester can be suitably used in fields requiring high colorless transparency such as optical materials.
  • the acrylic acid of the present invention needs to contain aldehydes in an amount of lOOppm or less. If it exceeds ⁇ m, it cannot be used for applications such as optical members where the final product is highly colored.
  • the preferred amount of aldehydes is 45 ppm or less.
  • aldehydes include acrolein, furfural, and benzaldehyde. Particularly, furfural affects coloring. Give a sound. Therefore, when the aldehyde is only furfural, lOppm or less is preferable, and 5ppm or less is particularly preferable.
  • furfural when it contains furfural, even if all aldehydes are lOOppm, it is preferable that furfural is 5 ppm or less, and 2.5 ppm or less is particularly preferable. Unless otherwise specified, ppm in the present invention indicates ppm by weight.
  • Furfural is not so large in boiling point with acrylic acid, so it is mixed in acrylic acid. This contamination is not preferable for the production of high boiling acrylic acid esters without purification by distillation. Therefore, it is necessary to use acrylic acid as the raw material that does not contain furfural at first.
  • furfural has a property of becoming greased through yellowish yellow when exposed to light in the air. It may be colored by heating or the like during removal.
  • the acrylic acid in the present invention is an acrylic acid produced by a gas-phase acid reaction of propylene.
  • acrylic acid used in the present invention those obtained by any production method can be used as long as they contain aldehydes in an amount of lOOppm or less.
  • a method of distilling the crude acrylic acid obtained after reacting propylene with a gas phase acid can be mentioned.
  • a preferred method for producing acrylic acid so that the aldehyde is reduced to lOOppm or less propylene is subjected to a gas phase oxidation reaction according to a conventional method, and then the obtained crude attalic acid is converted into hydrazine water.
  • Examples include distillation in the presence of a hydrate (hydraulic hydrazine).
  • the ratio of hydrazine hydrate to crude acrylic acid in this case is preferably 0.01 to 5% by mass.
  • distillation conditions in this case it is preferable to distill at a lower temperature in order to suppress decomposition of the compound in which aldehydes are captured with hydrazine hydrate. Specifically, it is preferable to distill under reduced pressure.
  • the pressure in this case 5 ⁇ 50torr is preferred as the temperature is 70 ⁇ : LOO Q C force S preferred ⁇ .
  • the high-boiling acrylic ester produced in the present invention preferably has a boiling point of 100 ° C or higher under the pressure of lOtorr.
  • Examples of powerful esters include acrylic acid esters of alkylene oxide modified phenols, acrylic acid esters of alkylene oxide modified norphenols, acrylic esters of (poly) alkylene glycols, acrylic esters of alkylene oxide modified bisphenol A, and alkylene oxide modified.
  • P-cumylphenol acrylate ester alkylene oxide modified 2-ethylhexyl acrylate ester, alkylene oxide modified bisphenol F acrylate ester, tricyclodecane dimethylol acrylate ester, alkylene oxide modified (di) Glycerin (Di) pentaerythritol acrylate, (di) trimethylolpropane acrylate, alkylene Examples thereof include acrylic acid esters of xoxide-modified (di) trimethylolpropane and acrylic acid esters of alkylene oxide-modified pentaerythritol.
  • an alcohol corresponding to the high boiling acrylic acid ester may be used.
  • Monovalent, divalent, and polyvalent alcohols can be used as the alcohol.
  • the acrylic ester is produced by an esterification reaction of acrylic acid and alcohol.
  • the esterification reaction may be carried out in accordance with a conventional method, for example, a method in which acrylic acid and alcohol are heated and stirred in an organic solvent in the presence of an acid catalyst.
  • the reaction ratio of acrylic acid (COOH) to alcohol (OH) is preferably such that the molar ratio of atalic acid to alcohol is 1.1 to 1.5 times.
  • Preferred acid catalysts include sulfuric acid, paratoluenesulfonic acid, methanesulfonic acid and the like.
  • the preferred use amount of the acid catalyst is about 0.01 to 0.20 times that of acrylic acid.
  • organic solvent benzene, toluene, n-hexane, cyclohexane, methylcyclohexane and water which are azeotropic with water are preferable because water generated in the esterification reaction can be efficiently removed.
  • examples include diisopropyl ether, and toluene is preferred.
  • the amount of the organic solvent used relative to the acid or alcohol is preferably such that the concentration of the resulting ester is 30 to 80% by mass.
  • hydroquinone (hereinafter referred to as HQ) is contained in the reaction solution to prevent polymerization. It is preferable to add one or more polymerization inhibitors such as hydroquinone monomethyl ether (hereinafter referred to as MEHQ), phenothiazine, copper sulfate and copper chloride. Preferably, the amount used is 100 to 5000 ppm with respect to the total liquid volume.
  • the esterification reaction can be carried out at a temperature of 80 to 120 ° C for 5 to 20 hours.
  • the reaction is carried out while supplying a mixed gas of oxygen and nitrogen with an oxygen concentration of 3% to 10%.
  • the alkaline aqueous solution a sodium hydroxide aqueous solution or the like is preferable.
  • concentration of the aqueous alkal solution is preferably about 10-30% by mass. If it exceeds 30% by mass, a precipitate may be generated in the aqueous phase from which the acid has been extracted. If it is less than 10% by mass, the amount of use increases and the time for liquid-liquid separation between the organic phase and the aqueous phase increases. become longer.
  • the amount of alkali used is preferably 1.0 times or more, specifically about 1.1 to 2.0 times the acid value of the reaction solution.
  • a solvent may be added to accelerate the liquid-liquid separation between the organic and aqueous phases.
  • An acrylic ester can be obtained by removing the solvent after washing the organic phase with water.
  • a compound having a boiling point lower than that of acrylic acid is preferable. Examples thereof include benzene, toluene, diisopropyl ether, dibutyl ether, ethyl acetate, isopropyl acetate and butyl acetate.
  • toluene is preferably used, and toluene is more preferable as an additional solvent.
  • Distillation may be a shift of notch distillation or continuous distillation.
  • the distillation conditions for solvent cutting may be known conditions depending on the type of solvent.
  • a pressure of 5 to 50 torr and a can liquid temperature of 50 to: LOO ° C are preferred.
  • LOO ° C When the temperature of the can exceeds 100 ° C, polymerization of the acrylate ester tends to occur during distillation.
  • Distillation is preferably carried out until the solvent content is 1% by weight or less. At the time of distillation, it is preferable to pass a mixed gas containing oxygen gas through the can liquid to prevent polymerization.
  • Acrylic acid was obtained by distilling crude acrylic acid obtained from propylene gas phase acid in the presence of hydrazine hydrate.
  • a 1 L flask is charged with 240 g of atanolenolic acid containing 0.8 ppm funolefuranore, 120 g of dipentaerythritol, 370 g of toluene, 5 g of sulfuric acid as an acid catalyst, HQ lg as a polymerization inhibitor, a pressure of 60 kPa, and an oil bath temperature of 120 g.
  • the reaction was stopped for 10 hours while removing water by azeotropy with toluene at ° C.
  • Acrylic acid was obtained by distilling crude acrylic acid obtained from propylene gas phase acid in the presence of hydrazine hydrate.
  • the synthesis was carried out in the same manner as in Example 1 except that acrylic acid containing 5 ppm of furfural was used.
  • the color tone of the obtained ester was 60 (APHA).
  • the synthesis was carried out in the same manner as in Example 1 except that acrylic acid containing 1.5 ppm of furfural was used in which the total amount of aldehydes such as acetoaldehyde, benzaldehyde, and furfural was 25 ppm.
  • the color tone of the obtained ester was 60 (APHA).
  • the synthesis was performed in the same manner as in Example 1 except that acrylic acid containing 28 lppm of furfural was used.
  • the color tone of the obtained ester was 200 (APHA).
  • the synthesis was performed in the same manner as in Example 2 except that acrylic acid containing 281 ppm of furfural was used.
  • the resulting ester had a color tone of 150 (APHA)
  • the production method of the present invention can be applied to any kind as long as it is a high boiling acrylic acid ester. According to the present invention, the coloration of the acrylic ester can be greatly reduced.

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

Abstract

Le problème à résoudre dans le cadre de la présente invention est de fournir un procédé pour produire un ester acrylique de température d’ébullition élevée ayant une décoloration réduite sans utiliser de distillation dans le procédé de purification. La solution proposée consiste en un procédé pour produire un ester acrylique de température d’ébullition élevée ayant un APHA de 100 ou moins, caractérisé en ce que dans la production d’un ester acrylique de température d’ébullition élevée par la réaction d'estérification d’un acide acrylique et d’un alcool, l'acide acrylique contient un aldéhyde en une quantité de 100 ppm en poids ou moins et l'ester acrylique résultant n'est pas distillé dans un procédé de purification. L'aldéhyde est de préférence le furfuraldéhyde contenu en une quantité de 45 ppm ou moins, plus préférablement, en une quantité de 10 ppm ou moins.
PCT/JP2006/310133 2005-05-23 2006-05-22 Procede pour produire un ester acrylique WO2006126479A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2005-149087 2005-05-23
JP2005149087 2005-05-23

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WO2006126479A1 true WO2006126479A1 (fr) 2006-11-30

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TW (1) TW200704637A (fr)
WO (1) WO2006126479A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104193622A (zh) * 2013-09-29 2014-12-10 安庆飞凯高分子材料有限公司 一种壬基酚聚氧乙烯醚丙烯酸酯的制备方法
CN104803852A (zh) * 2015-03-11 2015-07-29 张家港康得新光电材料有限公司 一种用于光学膜的紫外光固化单体的后处理方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01299254A (ja) * 1988-05-25 1989-12-04 Mitsubishi Rayon Co Ltd メタクリル酸メチルの精製法
JPH07330672A (ja) * 1994-06-10 1995-12-19 Rohm & Haas Co α，β−不飽和カルボン酸からのカルボニル不純物の除去方法
JPH1067702A (ja) * 1996-05-07 1998-03-10 Rohm & Haas Co α，β−不飽和カルボン酸およびそれらのエステル中のカルボニル不純物を減少させる方法
JP2002509904A (ja) * 1998-03-31 2002-04-02 ビーエーエスエフ アクチェンゲゼルシャフト （メタ）アクリル酸および（メタ）アクリル酸エステルの製造方法
JP2002173465A (ja) * 2000-09-29 2002-06-21 Sanyo Chem Ind Ltd 脱水縮合物の製造方法
JP2004339116A (ja) * 2003-05-14 2004-12-02 Nippon Shokubai Co Ltd 易重合性物質の製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01299254A (ja) * 1988-05-25 1989-12-04 Mitsubishi Rayon Co Ltd メタクリル酸メチルの精製法
JPH07330672A (ja) * 1994-06-10 1995-12-19 Rohm & Haas Co α，β−不飽和カルボン酸からのカルボニル不純物の除去方法
JPH1067702A (ja) * 1996-05-07 1998-03-10 Rohm & Haas Co α，β−不飽和カルボン酸およびそれらのエステル中のカルボニル不純物を減少させる方法
JP2002509904A (ja) * 1998-03-31 2002-04-02 ビーエーエスエフ アクチェンゲゼルシャフト （メタ）アクリル酸および（メタ）アクリル酸エステルの製造方法
JP2002173465A (ja) * 2000-09-29 2002-06-21 Sanyo Chem Ind Ltd 脱水縮合物の製造方法
JP2004339116A (ja) * 2003-05-14 2004-12-02 Nippon Shokubai Co Ltd 易重合性物質の製造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104193622A (zh) * 2013-09-29 2014-12-10 安庆飞凯高分子材料有限公司 一种壬基酚聚氧乙烯醚丙烯酸酯的制备方法
CN104803852A (zh) * 2015-03-11 2015-07-29 张家港康得新光电材料有限公司 一种用于光学膜的紫外光固化单体的后处理方法

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