WO1999041226A1 - Procede de production d'esters - Google Patents

Procede de production d'esters Download PDF

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Publication number
WO1999041226A1
WO1999041226A1 PCT/JP1999/000591 JP9900591W WO9941226A1 WO 1999041226 A1 WO1999041226 A1 WO 1999041226A1 JP 9900591 W JP9900591 W JP 9900591W WO 9941226 A1 WO9941226 A1 WO 9941226A1
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WO
WIPO (PCT)
Prior art keywords
reaction
alcohol
pressure
producing
acid
Prior art date
Application number
PCT/JP1999/000591
Other languages
English (en)
Japanese (ja)
Inventor
Tomoyuki Mori
Masaki Takai
Kazuhiko Kurita
Takeshi Ishikawa
Kazuo Murase
Nobuo Toratani
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
Priority to AU23003/99A priority Critical patent/AU2300399A/en
Publication of WO1999041226A1 publication Critical patent/WO1999041226A1/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 an ester such as a plasticizer used for a vinyl chloride resin.
  • an acid catalyst such as sulfuric acid or paratoluenesulfonic acid or an organic metal catalyst such as Ti or Sn is generally used as a catalyst.
  • an acid catalyst such as p-toluenesulfonic acid
  • the reaction can be performed at a relatively low temperature, but there is a problem that a large amount of by-products are generated.
  • the reaction temperature needs to be raised and the energy cost increases.
  • This esterification reaction is a typical equilibrium reaction, and in order to increase the yield of the desired ester, the starting alcohol is generally used in excess of the stoichiometric amount (stoichiometric amount). It is common practice to produce by-produced water by continuously drawing it out of the system. As a method of removing water outside the system, the raw material alcohol and water are distilled off by azeotropic distillation, the distillate is cooled, then only water is separated by phase separation, and the alcohol is refluxed to the reactor. The method has been adopted.
  • the azeotropic point of alcohol and by-produced water is lower than the boiling point of alcohol. If the reaction is carried out at normal pressure or reduced pressure in the initial stage of the reaction, the boiling state continues at a temperature lower than the target reaction temperature, and water is removed by azeotropy. There is a problem in that the temperature of the reaction solution does not increase until it decreases, that is, the reaction speed does not increase, and the reaction takes a long time. In addition, the latent heat of evaporation Energy is wasted in raising the reaction temperature.
  • Japanese Unexamined Patent Publications Nos. 55-38334 and 615-405 describe a dehydration column for removing water in refluxing alcohol in order to increase the reaction rate at the end of the reaction.
  • the method of setting up a refuge is disclosed. However, this method does not improve the reaction rate in the initial stage of the reaction, and has a problem that special equipment such as a dehydration column is required.
  • International Publication WO95 / 298888 discloses a method for shortening the reaction time by changing the charging ratio of alcohol and acid.
  • An object of the present invention is to provide a method for producing an ester from an organic carboxylic acid and / or an anhydride thereof and an alcohol having 4 to 18 carbon atoms, to increase the reaction rate in the initial stage of the reaction, shorten the reaction time, and reduce energy cost. It is to provide an economically advantageous method.
  • the present invention provides a method for producing an ester from an organic carboxylic acid and Z or an anhydride thereof with an alcohol having 4 to 18 carbon atoms, wherein the reaction is carried out at a pressure of 0.02 to 5 kg Z cm 2 G. And Further, in the present invention, in addition to the reaction under the pressurized condition, the starting material alcohol having 4 to 18 carbon atoms has a boiling point under the pressure in the reactor or 20 * C lower than that.
  • a method for producing an ester characterized in that the reaction is performed by supplying the ester within a temperature range.
  • Examples of the organic carboxylic acid and / or anhydride thereof used in the present invention include aliphatic monocarboxylic acids such as acetic acid, propionic acid, and butyric acid, and Z or anhydride thereof, adipic acid, sebacic acid, oleic acid, and fumaric acid.
  • Aliphatic dicarboxylic acids and aromatic dicarboxylic acids such as Z or anhydrides thereof, phthalic acid, isophthalic acid, terephthalic acid and / or aromatics such as trimellitic acid, pyromellitic acid, biphenyltetracarboxylic acid and the like Group polycarboxylic acids and z or its anhydride.
  • phthalic acid isophthalic acid, terephthalic acid, trimellitic acid, biphenyltetracarboxylic acid and / or anhydride thereof are preferred, and phthalic acid and / or anhydride thereof are most preferred. That is, the present invention is particularly preferable as a method for obtaining a diester of an aromatic dicarboxylic acid such as phthalic acid.
  • Examples of the alcohol having 4 to 18 carbon atoms used in the present invention include aliphatic primary acids such as butanol, hexanol nole, heptano monole, n-octano nore, 2-ethynole hexanosle, nonyl alcohol, decyl alcohol and lauryl alcohol. Alcohols and mixtures thereof, aromatic primary alcohols such as butynolebenzyl alcohol and cresyl alcohol, glycols such as ethylene glycol, propylene glycol and butanediol, polyhydric alcohols such as pentaerythritol and And mixtures thereof.
  • aliphatic primary acids such as butanol, hexanol nole, heptano monole, n-octano nore, 2-ethynole hexanosle, nonyl alcohol, decyl alcohol and lauryl alcohol. Alcohols and mixtures thereof, aromatic primary alcohols such as butynoleben
  • aliphatic primary alcohols having 7 to 13 carbon atoms are preferred, and 2-ethylhexyl alcohol, nonyl alcohol, and decyl alcohol are particularly preferred.
  • the amount of the alcohol used is preferably from the stoichiometric amount to 2.0 times the amount of the organic carboxylic acid and Z or its anhydride, but industrially 2.5 times the amount is used. More preferred.
  • the reaction it is necessary to carry out the reaction at a pressure of 0.02 to 5 kgZcm2G.
  • the preferred range of pressure is from 0.03 to 2 kg Z cm 2 G. If the pressure is less than 0.02 kg Zcm2G, the mixture of alcohol having 4 to 18 carbon atoms and water as a by-product tends to azeotrope, and the reaction takes a long time.
  • the predetermined Since its purpose if the pressure at the reaction temperature of over vapor pressure exhibited by the mixture of water alcohol by-product of 4-1 8 carbon atoms is achieved, until the pressure exceeds a 5 kg / cm 2 G There is no point in giving it.
  • the raw material alcohol in order to quickly raise the temperature of the reactor ⁇ to a predetermined reaction temperature, the raw material alcohol is heated and supplied to a boiling point under the pressure in the reactor or a temperature range lower by 20 than this. Is preferred.
  • the pressure be applied from the beginning of the reaction from the outside with an inert gas such as nitrogen from the viewpoint of operability.
  • the period during which the reaction is carried out under pressure is preferably a period from the start of the reaction until the reaction rate reaches 90%, more preferably a period from the start of the reaction until the reaction rate reaches 80%.
  • the reaction rate refers to the yield of ester relative to the starting organic carboxylic acid.
  • the starting organic carboxylic acid is an aromatic dicarboxylic acid such as phthalic acid
  • the reaction from carboxylic acid to the monoester is performed.
  • the reaction from a carboxylic acid to a diester is shown here, since is often relatively quick and almost complete.
  • the reaction rate is 90%, preferably 80. / 0 becomes up period, as reaction pressure as defined in the present invention is zero. 0 2-5 range kg Z cm 2 G, the initial pressurized reaction, Metsu ⁇ from appropriate time It is desirable to gradually promote the removal of water for the first time, and to make the pressure negative at the end of the reaction when the reaction rate exceeds 90%.
  • the production method of the present invention can be carried out without a catalyst, sulfuric acid, aliphatic sulfonic acids, acid catalysts such as aromatic sulfonic acids such as para-toluenesulfonic acid, alkyl titanates such as tetrabutyl titanate and tetraisopropyl titanate, Organometallic catalysts such as Ti and Sn such as tin tetramaleate and butyltin maleate can be used. Of these, organometallic catalysts such as Ti and Sn are preferred, and alkyl titanates are most preferred.
  • the reaction temperature is a temperature higher than the azeotropic point at normal pressure of the alcohol having 4 to 18 carbon atoms and water produced as a result of the reaction, which is achieved by pressurization.
  • the range from 120 to 25 O ⁇ C is preferred. If the temperature is less than 120 ° C., the reaction rate tends to be low. If the temperature exceeds 250 ° C., the reaction solution may be colored or a by-product may be formed, which may impair the performance of the plasticizer.
  • the preferable range of the reaction temperature depends on the catalyst to be used. In particular, when the acid catalyst is used, the preferable range of the reaction temperature is 120 to 160, with no catalyst or organic catalyst. When a metal catalyst is used, a preferred range is 160 to 250 °, and a more preferred range is 180 to 230.
  • esterification reaction of the present invention is completed, purification is performed by a known method such as distillation of excess alcohol, removal of a catalyst, neutralization, washing with water, treatment with activated carbon or activated clay, and filtration to obtain an ester as a product.
  • a known method such as distillation of excess alcohol, removal of a catalyst, neutralization, washing with water, treatment with activated carbon or activated clay, and filtration to obtain an ester as a product.
  • Reaction rate (%) [1-(moles of phthalic acid monoester calculated from acid value) /
  • the titer was 37.5 mg KOHZg.
  • the pressure inside the reactor became negative, and the reaction rate exceeded 92%.
  • the pressure was 55 OmmHg (—0.276 kg / cm 2 G), and the time required for the final reaction was 150 minutes.
  • Example 2 Using the same apparatus as in Example 1, 459 g of phthalic anhydride, 1009 g of 2-ethylhexanol and 0.63 ml of tetraisopropyl titanate were charged in the same manner.
  • the temperature of the reaction solution was raised from 17 to 220 ° C. over 35 minutes while maintaining the pressure at 100 OmmHg (0.316 kg ⁇ cm 2 G) from the start of the reaction. Then, while maintaining the temperature of the reaction solution at 220, the pressure was reduced with a vacuum pump. Started. From 75 minutes after the start of the reaction (40 minutes after the start of depressurization), the temperature was lowered to 185 ⁇ over 80 minutes while continuing the depressurization, and the reaction was terminated thereafter.
  • Comparative Example 2 requires a long time for the reaction and also requires much energy for heating.
  • the second embodiment is an example in which optimization is performed to save necessary energy. Even in this case, the reaction time is 85% of Comparative Example 1, and the required energy is about 70%. It is 79% of Comparative Example 2, and the required energy is about 60%.
  • the reaction time can be reduced and the energy can be reduced as compared with the conventional method.

Landscapes

  • 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

L'invention concerne un procédé permettant de produire des esters à partir d'acides carboxyliques organiques, et/ou d'anhydrides de ceux-ci, et d'alcools C4-18. Selon ce procédé, on peut diminuer le temps de réaction en augmentant la vitesse de réaction à l'étape initiale de cette réaction, permettant ainsi de faire baisser les coûts énergétiques, ce qui constitue un avantage économique considérable. Le procédé susmentionné consiste à produire une réaction à une pression variant entre 0,02 et 5 kg/cm2, la charge d'alcool étant alimentée dans une gamme de températures allant d'une température inférieure de 20 °C au point d'ébullition de l'alcool sous pression dans le réacteur, au point d'ébullition de cet alcool.
PCT/JP1999/000591 1998-02-16 1999-02-12 Procede de production d'esters WO1999041226A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU23003/99A AU2300399A (en) 1998-02-16 1999-02-12 Process for producing esters

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP10/32668 1998-02-16
JP3266898A JP3799796B2 (ja) 1998-02-16 1998-02-16 エステルの製造方法

Publications (1)

Publication Number Publication Date
WO1999041226A1 true WO1999041226A1 (fr) 1999-08-19

Family

ID=12365261

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1999/000591 WO1999041226A1 (fr) 1998-02-16 1999-02-12 Procede de production d'esters

Country Status (4)

Country Link
JP (1) JP3799796B2 (fr)
CN (1) CN1190408C (fr)
AU (1) AU2300399A (fr)
WO (1) WO1999041226A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010516809A (ja) * 2007-01-30 2010-05-20 イーストマン ケミカル カンパニー テレフタル酸ジエステルの製造
US8344174B2 (en) 2007-03-13 2013-01-01 Exxonmobil Chemical Patents Inc. Batch esterification
EP4219442A4 (fr) * 2020-09-24 2024-04-03 Lg Chemical Ltd Procédé de production d'une composition à base d'ester

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* Cited by examiner, † Cited by third party
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TWI466863B (zh) * 2013-03-21 2015-01-01 Chang Chun Plastics Co Ltd 對苯二甲酸二（２－乙基己酯）之製造方法
CN103319346A (zh) * 2013-05-24 2013-09-25 中国林业科学研究院林产化学工业研究所 调节压力合成增塑剂的方法及其装置
KR20160060641A (ko) * 2013-09-25 2016-05-30 가부시키가이샤 아데카 에스테르 화합물의 제조 방법
TWI654177B (zh) 2013-10-31 2019-03-21 德商巴斯夫歐洲公司 製備羧酸酯的方法及其作爲塑化劑的用途
CN105985240A (zh) * 2015-02-04 2016-10-05 华东理工大学 增塑剂生产酯化过程强化新工艺
CN108003024B (zh) * 2016-11-02 2019-10-18 中国科学院大连化学物理研究所 一种丙酸甲酯的制备方法
CN108003023B (zh) * 2016-11-02 2019-10-18 中国科学院大连化学物理研究所 一种制备丙酸甲酯的方法
CN108003022B (zh) * 2016-11-02 2020-01-07 中国科学院大连化学物理研究所 一种制备酯类化合物的方法
CN108997123B (zh) * 2018-09-11 2021-04-09 山东元利科技股份有限公司 一种以邻二甲苯或萘的催化氧化产物合成邻苯二甲酸酯的方法
CN112125799A (zh) * 2020-10-14 2020-12-25 重庆欣欣向荣精细化工有限公司 一种异丁酸香兰素酯的生产方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS604151A (ja) * 1983-06-20 1985-01-10 Mitsubishi Monsanto Chem Co テレフタル酸ジエステルの製造方法
JPH04504410A (ja) * 1989-01-17 1992-08-06 デイヴイ・プロセス・テクノロジー・リミテッド プロセス及び装置
JPH08198812A (ja) * 1995-01-31 1996-08-06 Rikagaku Kenkyusho ジカルボン酸モノエステルの製造方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2707063B2 (ja) * 1993-12-13 1998-01-28 花王株式会社 脂肪酸低級アルキルエステルの製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS604151A (ja) * 1983-06-20 1985-01-10 Mitsubishi Monsanto Chem Co テレフタル酸ジエステルの製造方法
JPH04504410A (ja) * 1989-01-17 1992-08-06 デイヴイ・プロセス・テクノロジー・リミテッド プロセス及び装置
JPH08198812A (ja) * 1995-01-31 1996-08-06 Rikagaku Kenkyusho ジカルボン酸モノエステルの製造方法

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010516809A (ja) * 2007-01-30 2010-05-20 イーストマン ケミカル カンパニー テレフタル酸ジエステルの製造
KR101543808B1 (ko) 2007-01-30 2015-08-11 이스트만 케미칼 캄파니 테레프탈산 다이에스터의 생산
US8344174B2 (en) 2007-03-13 2013-01-01 Exxonmobil Chemical Patents Inc. Batch esterification
EP4219442A4 (fr) * 2020-09-24 2024-04-03 Lg Chemical Ltd Procédé de production d'une composition à base d'ester

Also Published As

Publication number Publication date
AU2300399A (en) 1999-08-30
CN1190408C (zh) 2005-02-23
CN1291180A (zh) 2001-04-11
JP3799796B2 (ja) 2006-07-19
JP2002155026A (ja) 2002-05-28

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