JP2002155026A - Method for producing ester - Google Patents
Method for producing esterInfo
- Publication number
- JP2002155026A JP2002155026A JP03266898A JP3266898A JP2002155026A JP 2002155026 A JP2002155026 A JP 2002155026A JP 03266898 A JP03266898 A JP 03266898A JP 3266898 A JP3266898 A JP 3266898A JP 2002155026 A JP2002155026 A JP 2002155026A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- alcohol
- ester
- producing
- pressure
- 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.)
- Granted
Links
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
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
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、塩化ビニル樹脂に
使用される可塑剤等のエステルの製造方法に関する。[0001] The present invention relates to a method for producing an ester such as a plasticizer used for a vinyl chloride resin.
【０００２】[0002]
【従来の技術】従来より、酸とアルコールをエステル化
反応させ、可塑剤等に使用するエステルを製造する方法
は広く工業的に行われている。このエステルの製造法に
おいては、触媒として硫酸やパラトルエンスルホン酸等
の酸触媒やＴｉ、Ｓｎ等の有機金属触媒が一般に用いら
れている。そして、パラトルエンスルホン酸等の酸触媒
を使用する場合は、比較的低温で反応させることが可能
であるが副生成物を多く生成する等の問題があり、有機
金属触媒を使用すると副生成物の生成は少ないが反応温
度を高くする必要があり、エネルギーコストが高くなる
という問題がある。2. Description of the Related Art Hitherto, a method for producing an ester used as a plasticizer or the like by subjecting an acid and an alcohol to an esterification reaction has been widely industrially performed. In the method for producing this ester, 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. When an acid catalyst such as paratoluenesulfonic acid is used, the reaction can be performed at a relatively low temperature, but there is a problem that a large amount of by-products is generated. However, there is a problem that the reaction temperature needs to be raised and the energy cost increases.
【０００３】このエステル化反応は典型的な平衡反応で
あり、目的とするエステルの収率を上げるために一般に
は原料アルコールを理論量（化学量論量）に比べて過剰
に使用し、エステル化反応に伴い副生する水を連続的に
系外に抜き出すことにより製造する方法が一般的に行わ
れている。この系外に水を除去する方法としては、原料
アルコールと水を共沸により留去し、留出液を冷却した
後、相分離により水のみを分離し、アルコールを反応器
に還流させる方法が採られている。アルコールと副生す
る水の共沸点はアルコールの沸点以下であり、反応初期
に常圧もしくは減圧下で反応を行えば目的の反応温度よ
り低い温度で沸騰状態が続き、水が共沸により除去され
て減少するまでの間は反応液の温度が上がらず、即ち反
応速度が上がらず、反応に長時間を要するという問題が
ある。また、共沸により蒸発潜熱を奪われるため、反応
温度を上げるためのエネルギーが無駄に使われるという
問題もある。[0003] This esterification reaction is a typical equilibrium reaction, and in order to increase the yield of a desired ester, generally, a starting alcohol is used in excess of a stoichiometric amount (stoichiometric amount). A method of producing by continuously extracting water produced as a by-product of the reaction outside the system is generally performed. As a method of removing water outside the system, a method of distilling off the raw material alcohol and water by azeotropic distillation, cooling the distillate, separating only water by phase separation, and refluxing the alcohol to the reactor. 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 azeotropic distillation. Until the temperature decreases, the temperature of the reaction solution does not increase, that is, the reaction speed does not increase, and there is a problem that a long time is required for the reaction. In addition, since latent heat of evaporation is deprived by azeotropic distillation, there is a problem that energy for raising the reaction temperature is wasted.
【０００４】特開昭５５−３８３３４号公報、特開平６
−１５７４０５号公報には、反応末期の反応速度を速く
するため、還流アルコール中の水分除去のため脱水カラ
ムを設置する等の方法が開示されている。しかしこの方
法では反応初期の反応速度の向上は見られず、また脱水
カラムのような特別な設備を必要とする問題がある。ま
た、国際公開ＷＯ９５２９８８８号公報にはアルコール
と酸の仕込み比を変更することにより反応時間を短縮す
る方法が開示されている。即ち、アルコールを理論量よ
り少な目に加え、その後アルコールの量をモニターしな
がら段階的に加えることにより、反応液の沸点、即ち反
応温度を上げることにより反応速度を速くする方法が開
示されている。しかし、この方法でも過剰のアルコール
を加える場合に比べて反応速度が遅くなる等の問題点が
ある。Japanese Patent Application Laid-Open No. 55-38334,
JP-A-157405 discloses a method of installing a dehydration column for removing water in refluxing alcohol in order to increase the reaction rate at the end of the reaction. 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. Further, International Publication WO9529888 discloses a method for shortening the reaction time by changing the charging ratio of alcohol and acid. That is, a method is disclosed in which the alcohol is added to a smaller amount than the theoretical amount, and then the amount of the alcohol is monitored and added stepwise, thereby increasing the boiling point of the reaction solution, that is, the reaction temperature to increase the reaction rate. However, this method also has problems such as a slower reaction rate than the case where an excess alcohol is added.
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は、有機
カルボン酸および／またはその無水物と炭素数４〜１８
のアルコールからエステルを製造する方法において、反
応初期の反応速度を上げて反応時間を短縮し、かつエネ
ルギーコストが低く経済的に有利な方法を提供すること
にある。SUMMARY OF THE INVENTION It is an object of the present invention to provide an organic carboxylic acid and / or an anhydride thereof having 4 to 18 carbon atoms.
An object of the present invention is to provide an economically advantageous method for producing an ester from an alcohol by shortening the reaction time by increasing the reaction rate at the beginning of the reaction and reducing the energy cost.
【０００６】[0006]
【課題を解決するための手段】本発明は、有機カルボン
酸および／またはその無水物と炭素数４〜１８のアルコ
ールからエステルを製造する方法において、０．０２〜
５ｋｇ／ｃｍ2Ｇの圧力で反応させることを特徴とする
エステルの製造方法、に存する。The present invention provides a process for producing an ester from an organic carboxylic acid and / or an anhydride thereof and an alcohol having 4 to 18 carbon atoms.
Reacting at a pressure of 5 kg / cm 2 G.
【０００７】[0007]
【発明の実施の形態】以下、本発明を詳細に説明する。
本発明において用いられる有機カルボン酸および／また
はその無水物としては、酢酸、プロピオン酸、酪酸等の
脂肪族一塩基酸類および／またはその無水物、アジピン
酸、セバシン酸、オレイン酸、フマル酸等の脂肪族二塩
基酸類および／またはその無水物、フタル酸、イソフタ
ル酸、テレフタル酸等の芳香族二塩基酸類および／また
はその無水物、トリメリット酸、ピロメリット酸、ビフ
ェニルテトラカルボン酸等の芳香族多塩基酸類および／
またはその無水物等が挙げられる。これらの中でフタル
酸、イソフタル酸、テレフタル酸、トリメリット酸、ビ
フェニルテトラカルボン酸および／またはその無水物が
好ましく、フタル酸および／またはその無水物が最も好
ましい。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
Examples of the organic carboxylic acids and / or anhydrides used in the present invention include aliphatic monobasic acids such as acetic acid, propionic acid, and butyric acid and / or anhydrides thereof, adipic acid, sebacic acid, oleic acid, and fumaric acid. Aromatic dibasic acids and / or anhydrides thereof, aromatic dibasic acids such as phthalic acid, isophthalic acid, terephthalic acid and / or anhydrides thereof, and aromatics such as trimellitic acid, pyromellitic acid and biphenyltetracarboxylic acid Polybasic acids and / or
Or an anhydride thereof. Of these, 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.
【０００８】本発明において用いられる炭素数４〜１８
のアルコールとしては、ブタノール、ヘキサノール、ヘ
プタノール、ｎ−オクタノール、２−エチルヘキサノー
ル、ノニルアルコール、デシルアルコール、ラウリルア
ルコール等の脂肪族１価アルコール類およびそれらの混
合物、ブチルベンジルアルコール、クレジルアルコール
等の芳香族１価アルコール類、エチレングリコール、プ
ロピレングリコール、ブタンジオール等のグリコール
類、ペンタエリスリトール等の多価アルコール類等およ
びそれらの混合物が挙げられる。これらの中で炭素数７
〜１３の脂肪族１級アルコール類が好ましく、２−エチ
ルヘキシルアルコール、ノニルアルコール、デシルアル
コールが特に好ましい。アルコールの使用量は、有機カ
ルボン酸および／またはその無水物に対して化学量論量
からその２倍使用するのが好ましく、化学量論量からそ
の１．５倍がより好ましい。[0008] The carbon number 4-18 used in the present invention
Examples of alcohols include aliphatic monohydric alcohols such as butanol, hexanol, heptanol, n-octanol, 2-ethylhexanol, nonyl alcohol, decyl alcohol, and lauryl alcohol, and mixtures thereof, butylbenzyl alcohol, cresyl alcohol, and the like. Examples include aromatic monohydric alcohols, glycols such as ethylene glycol, propylene glycol, and butanediol, polyhydric alcohols such as pentaerythritol, and mixtures thereof. Among them, carbon number 7
To 13 aliphatic primary alcohols are preferable, and 2-ethylhexyl alcohol, nonyl alcohol and decyl alcohol are particularly preferable. The amount of the alcohol to be used is preferably stoichiometric to twice that of the organic carboxylic acid and / or anhydride, and more preferably 1.5 times that of the stoichiometric amount.
【０００９】本発明の製造方法においては０．０２〜５
ｋｇ／ｃｍ2の圧力で反応させることが必要である。圧
力の好ましい範囲は０．０３〜２ｋｇ／ｃｍ2である。
圧力が０．０２ｋｇ／ｃｍ2未満では、炭素数４〜１８
のアルコールと副生する水との混合物が共沸し易く、反
応に長時間を要する。また、本発明においては、所定の
反応温度における圧力を炭素数４〜１８のアルコールと
副生する水との混合物が呈する蒸気圧以上にすればその
目的は達成されるので、圧力を５ｋｇ／ｃｍ2を超えて
まであげても意味がない。In the production method of the present invention, 0.02 to 5
It is necessary to react at a pressure of kg / cm 2 . The preferred range of the pressure is 0.03 to 2 kg / cm 2 .
When the pressure is less than 0.02 kg / cm 2 , the carbon number is 4 to 18;
The mixture of the alcohol and the by-produced water easily azeotropes, and the reaction takes a long time. In the present invention, if the pressure at a predetermined reaction temperature is equal to or higher than the vapor pressure of a mixture of alcohol having 4 to 18 carbon atoms and water by-produced, the object is achieved, and the pressure is set to 5 kg / cm. There is no point in giving up to more than two .
【００１０】圧力のかけ方は、窒素等の不活性ガスによ
り外部からかけることも可能であるが、反応器を密閉系
にさえしておけば、反応液の蒸気圧によってもある程度
は達成できる。経済性の面からは、後者の方法が好まし
い。加圧下で反応を行う期間は、反応開始からエステル
化率が５〜９５％になるまでの期間、より好ましくは反
応開始からエステル化率が１０〜９０％になるまでの期
間が好ましい。エステル化反応は平衡反応であるため、
反応の後半には副生する水分を除去することにより、エ
ステルの収率を上げる必要がある。従って、反応末期に
は、減圧して系中の水分を除去することが望ましい。The pressure can be applied from the outside by an inert gas such as nitrogen, but can be achieved to some extent by the vapor pressure of the reaction solution as long as the reactor is closed. The latter method is preferred from the viewpoint of economy. The period during which the reaction is performed under pressure is preferably a period from the start of the reaction until the esterification ratio becomes 5 to 95%, more preferably a period from the start of the reaction until the esterification ratio becomes 10 to 90%. Since the esterification reaction is an equilibrium reaction,
In the latter half of the reaction, it is necessary to increase the yield of the ester by removing water produced as a by-product. Therefore, at the end of the reaction, it is desirable to reduce the pressure to remove water in the system.
【００１１】本発明の製造方法において、反応温度は１
２０〜２５０℃が好ましい。１２０℃未満では反応速度
が遅くなる傾向があり、２５０℃を超えると反応液が着
色したり、副生成物ができて可塑剤性能等を阻害する虞
がある。なお本発明の製造方法において、反応温度の好
ましい範囲は用いる触媒によって左右され、硫酸、パラ
トルエンスルホン酸等の酸触媒を用いる場合の反応温度
の好ましい範囲は１２０〜１６０℃であり、無触媒また
は有機金属触媒を用いる場合の好ましい範囲は１６０〜
２５０℃、より好ましい範囲は１８０〜２３０℃であ
る。In the production method of the present invention, the reaction temperature is 1
20-250 ° C is preferred. If the temperature is lower than 120 ° C., the reaction rate tends to be slow. If the temperature is higher than 250 ° C., the reaction solution may be colored or a by-product may be formed, which may impair the performance of the plasticizer. In the production method of the present invention, the preferred range of the reaction temperature depends on the catalyst used, and the preferred range of the reaction temperature in the case of using an acid catalyst such as sulfuric acid or paratoluenesulfonic acid is 120 to 160 ° C. The preferred range when using an organometallic catalyst is 160 to
250 ° C, more preferably 180 to 230 ° C.
【００１２】上述したように本発明の製造方法は無触媒
でも行うことができるが、硫酸、脂肪族スルホン酸類、
パラトルエンスルホン酸等の芳香族スルホン酸類等の酸
触媒、テトラブチルチタネート、テトライソプロピルチ
タネート等のアルキルチタネート類、錫テトラマレエー
ト、ブチル錫マレエート等のＴｉ、Ｓｎ等の有機金属触
媒を用いることができる。これらの中でＴｉ、Ｓｎ等の
有機金属触媒が好ましく、アルキルチタネートが最も好
ましい。なお本発明の製造方法においては、エステル化
反応終了後、過剰のアルコールの留去、触媒の除去、中
和、水洗、活性炭もしくは活性白土による処理、濾過な
ど公知の方法で精製を行い、製品としてのエステルを得
ることができる。As described above, the production method of the present invention can be carried out without a catalyst, but sulfuric acid, aliphatic sulfonic acids,
Acid catalysts such as aromatic sulfonic acids such as p-toluenesulfonic acid, alkyl titanates such as tetrabutyl titanate and tetraisopropyl titanate, and organic metal catalysts such as Ti and Sn such as tin tetramaleate and butyltin maleate can be used. it can. Of these, organometallic catalysts such as Ti and Sn are preferred, and alkyl titanates are most preferred. In the production method of the present invention, after completion of the esterification reaction, excess alcohol is distilled off, the catalyst is removed, neutralized, washed with water, treated with activated carbon or activated clay, purified by a known method such as filtration, and purified. Can be obtained.
【００１３】[0013]
【実施例】以下、本発明を実施例、比較例により、更に
詳細に説明するが、本発明は、その要旨を越えない限
り、以下の実施例に限定されるものではない。 ＜実施例１＞撹拌機、蒸留塔、凝縮器、油水分離器、ア
ルコール還流ラインを備えた２リットルの四つ口フラス
コをオイルバスで予熱しておき、窒素ガスで１０００ｍ
ｍＨｇ（０．３１６ｋｇ／ｃｍ2Ｇ）に加圧した。１４
０℃以上に加熱溶融させた無水フタル酸４５９ｇ（３．
１モル）を３５分かけてポンプを用いて仕込み、同時に
１７０℃の２−エチルヘキサノール１００９ｇ（７．７
５モル）をポンプを用いてフィードし始め、最初の８０
７ｇを４０分かけて、残りの２０２ｇを４０分かけて仕
込んだ。またテトライソプロピルチタネート０．６３ｍ
ｌ（対エステル０．０５重量％）を無水フタル酸の仕込
み終了後に添加した。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to the following examples unless it exceeds the gist. <Example 1> A 2 liter four-necked flask equipped with a stirrer, a distillation column, a condenser, an oil-water separator, and an alcohol reflux line was preheated in an oil bath, and then 1000 m2 with nitrogen gas.
The pressure was increased to mHg (0.316 kg / cm 2 G). 14
459 g of phthalic anhydride (3.
1 mol) over 35 minutes using a pump, and at the same time, 1009 g (7.7) of 2-ethylhexanol at 170 ° C.
5 mol) using a pump.
7 g was charged over 40 minutes, and the remaining 202 g was charged over 40 minutes. 0.63m of tetraisopropyl titanate
1 (0.05% by weight relative to the ester) was added after the phthalic anhydride was charged.
【００１４】無水フタル酸および２−エチルヘキサノー
ルの仕込みを開始した時点（これを反応開始点とす
る。）から圧力を１０００ｍｍＨｇに保持したまま、２
−エチルヘキサノールの還流を続けた（副生する水と２
−エチルヘキサノールは、油水分離器で分離し、水は系
外に除去し、２−エチルヘキサノールは還流ラインから
フラスコに戻す。）。反応開始より４０分後より徐々に
減圧し、反応開始後約６０分（減圧開始後約２０分）で
の圧力は約９００ｍｍＨｇで、このときの酸価は３７．
５ｍｇＫＯＨ／ｇであった。そして反応液の酸価が０．
１ｍｇＫＯＨ／ｇになった時点で反応を終了した。この
ときの圧力は５５０ｍｍＨｇ、反応に要した時間は１５
０分であった。From the time when the charging of phthalic anhydride and 2-ethylhexanol was started (this is referred to as the reaction starting point), the pressure was kept at 1000 mmHg and the pressure was kept at 2 mm.
-The reflux of ethylhexanol was continued (by-produced water and 2
-Ethylhexanol is separated by an oil-water separator, water is removed out of the system, and 2-ethylhexanol is returned from the reflux line to the flask. ). The pressure was gradually reduced 40 minutes after the start of the reaction. The pressure at about 60 minutes after the start of the reaction (about 20 minutes after the start of the pressure reduction) was about 900 mmHg, and the acid value at this time was 37.
It was 5 mgKOH / g. Then, the acid value of the reaction solution is 0.1.
The reaction was completed when the concentration reached 1 mgKOH / g. The pressure at this time was 550 mmHg, and the time required for the reaction was 15
It was 0 minutes.
【００１５】＜実施例２＞実施例１と同様の装置を用
い、同様の方法で無水フタル酸４５９ｇ、２−エチルヘ
キサノール１００９ｇ、テトライソプロピルチタネート
０．６３ｍｌを仕込んだ。実施例１と同様反応開始から
圧力を１０００ｍｍＨｇに保持したまま、３５分かけて
反応液の温度を１７０℃から２２０℃に昇温した。次い
で、反応液の温度を２２０℃に保持したまま、真空ポン
プで減圧を開始した。反応開始後７５分（減圧開始後４
０分）から減圧を継続したまま８０分かけて１８５℃ま
で降温し、以後反応終了（反応液の酸価が０．１ｍｇＫ
ＯＨ／ｇになった時点）までこの温度で保持した。反応
開始６０分後の圧力は８００ｍｍＨｇ、酸価は４０．１
ｍｇＫＯＨ／ｇ、反応終了時の圧力は２００ｍｍＨｇ、
反応に要した時間は１８０分であった。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. As in Example 1, the temperature of the reaction solution was raised from 170 ° C. to 220 ° C. over 35 minutes while maintaining the pressure at 1000 mmHg from the start of the reaction. Next, pressure reduction was started with a vacuum pump while maintaining the temperature of the reaction solution at 220 ° C. 75 minutes after the start of the reaction (4
0 minutes), the temperature was lowered to 185 ° C. over 80 minutes while continuing the reduced pressure, and the reaction was terminated (the acid value of the reaction solution was 0.1 mgK).
OH / g). The pressure 60 minutes after the start of the reaction was 800 mmHg, and the acid value was 40.1.
mgKOH / g, the pressure at the end of the reaction was 200 mmHg,
The time required for the reaction was 180 minutes.
【００１６】＜比較例１＞圧力を７００ｍｍＨｇ（−
０．０７９ｋｇ／ｃｍ2Ｇ）に保持した以外は実施例１
と同様に仕込みを行い、オイルバスの昇温速度も実施例
１と同様にして、反応液を１７０℃から昇温した。反応
開始後７０分後から７００ｍｍＨｇから更に減圧しなが
ら反応液の昇温を継続し、反応開始後１２０分後に反応
液の温度が２１０℃に到達した。以後反応液の温度を２
１０℃に保持したまま反応を継続し、反応液の酸価が
０．１ｍｇＫＯＨ／ｇになった時点で反応を終了した。
このときの圧力は３８０ｍｍＨｇ、反応に要した時間は
２４０分であった。Comparative Example 1 A pressure of 700 mmHg (-
Example 1 except that the pressure was maintained at 0.079 kg / cm 2 G).
The reaction solution was heated from 170 ° C. in the same manner as in Example 1 with the same preparation as in Example 1. After 70 minutes from the start of the reaction, the temperature of the reaction solution was continuously increased while further reducing the pressure from 700 mmHg, and the temperature of the reaction solution reached 210 ° C. 120 minutes after the start of the reaction. Thereafter, the temperature of the reaction solution is set to 2
The reaction was continued while maintaining the temperature at 10 ° C., and the reaction was terminated when the acid value of the reaction solution reached 0.1 mgKOH / g.
At this time, the pressure was 380 mmHg, and the time required for the reaction was 240 minutes.
【００１７】＜結果の評価＞実施例１、２および比較例
１の温度、圧力条件からコンピュータシミュレーション
を用いて、加熱に必要なエネルギーの計算を行った。用
いたソフトは、「ｇＰＲＯＭＳ」（Ｂａｒｔｏｎ ａｎ
ｄ Ｐａｎｔｅｌｉｄｅｓ，１９９４ Ｉｍ−ｐｅｒｉ
ａｌ Ｃｏｌｌｅｇｅ ｏｆ Ｓｉｅｎｃｅ，Ｔｅｃｈ
ｎｏｌｏｇｙａｎｄ Ｍｅｄｉｃｉｎｅ）である。加熱
に必要なエネルギーは、比較例１を１００％とすると、
実施例１は６４．４％、実施例２は５５．６％であっ
た。従来の方法（比較例１）では、反応に長時間を要す
る上、加熱に必要なエネルギーも多く要することが明ら
かである。なお、実施例２は必要なエネルギーを節約す
るための最適化を行った例である。この場合でも反応時
間は、比較例２の３／４であり、必要なエネルギーは約
１／２となる。<Evaluation of Results> Energy required for heating was calculated from the temperature and pressure conditions of Examples 1 and 2 and Comparative Example 1 by using computer simulation. The software used was “gPROMS” (Barton and
d Pantellides, 1994 Im-peri
al College of Science, Tech
Nologyand Medicine). The energy required for heating is 100% in Comparative Example 1.
Example 1 was 64.4%, and Example 2 was 55.6%. It is clear that the conventional method (Comparative Example 1) requires a long time for the reaction and also requires much energy for heating. The second embodiment is an example in which optimization for saving necessary energy is performed. Also in this case, the reaction time is 3/4 of that of Comparative Example 2, and the required energy is about 1/2.
【００１８】[0018]
【発明の効果】本発明のエステルの製造方法によれば、
従来の方法に比べ反応時間を短縮でき、なおかつエネル
ギーの削減ができる。According to the method for producing an ester of the present invention,
The reaction time can be reduced and the energy can be reduced as compared with the conventional method.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 栗田 和彦 岡山県倉敷市潮通三丁目10番地 三菱化学 株式会社水島事業所内 (72)発明者 石川 矯 東京都千代田区丸の内二丁目５番２号 三 菱化学株式会社内 Ｆターム(参考） 4H006 AA02 AC48 BA10 BA11 BA32 BA36 BA52 BC10 BC11 KA04 4H039 CA66 CD10 CD30 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kazuhiko Kurita 3-10 Ushidori, Kurashiki-shi, Okayama Prefecture, Mizushima Works, Mitsubishi Chemical Corporation (72) Inventor Tadashi Ishikawa 2-5-2, Marunouchi, Chiyoda-ku, Tokyo 3 F term (reference) 4H006 AA02 AC48 BA10 BA11 BA32 BA36 BA52 BC10 BC11 KA04 4H039 CA66 CD10 CD30
Claims (7)
物と炭素数４〜１８のアルコールからエステルを製造す
る方法において、０．０２〜５ｋｇ／ｃｍ2Ｇの圧力で
反応させることを特徴とするエステルの製造方法。1. 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, wherein the ester is reacted at a pressure of 0.02 to 5 kg / cm 2 G. Manufacturing method.
水との混合物が呈する常圧における共沸点よりも高い温
度で反応を行う請求項１に記載のエステルの製造方法。2. The process for producing an ester according to claim 1, wherein the reaction is carried out at a temperature higher than the azeotropic point at normal pressure of a mixture of an alcohol having 4 to 18 carbon atoms and water as a by-product.
％になるまでの期間、０．０２〜５ｋｇ／ｃｍ2Ｇの圧
力で反応させる請求項１または２に記載のエステルの製
造方法。3. An ester yield of 5 to 95 from the start of the reaction.
%. The method for producing an ester according to claim 1, wherein the reaction is carried out at a pressure of 0.02 to 5 kg / cm 2 G until the amount of the ester reaches 0.1%.
項１〜３いずれか１項に記載のエステルの製造方法。4. The method for producing an ester according to claim 1, wherein the reaction temperature is 120 to 250 ° C.
いずれか１項に記載のエステルの製造方法。5. The catalyst according to claim 1, wherein the catalyst is an organometallic catalyst.
A method for producing an ester according to any one of the preceding claims.
物が芳香族ジカルボン酸および／またはその無水物であ
る請求項１〜５いずれか１項に記載のエステルの製造方
法。6. The method for producing an ester according to claim 1, wherein the organic carboxylic acid and / or an anhydride thereof is an aromatic dicarboxylic acid and / or an anhydride thereof.
級アルコールである請求項１〜６いずれか１項に記載の
エステルの製造方法。7. The method for producing an ester according to claim 1, wherein the alcohol having 4 to 18 carbon atoms is an aliphatic primary alcohol.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3266898A JP3799796B2 (en) | 1998-02-16 | 1998-02-16 | Method for producing ester |
| PCT/JP1999/000591 WO1999041226A1 (en) | 1998-02-16 | 1999-02-12 | Process for producing esters |
| AU23003/99A AU2300399A (en) | 1998-02-16 | 1999-02-12 | Process for producing esters |
| CN 99802957 CN1190408C (en) | 1998-02-16 | 1999-02-12 | Process for producing ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3266898A JP3799796B2 (en) | 1998-02-16 | 1998-02-16 | Method for producing ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2002155026A true JP2002155026A (en) | 2002-05-28 |
| JP3799796B2 JP3799796B2 (en) | 2006-07-19 |
Family
ID=12365261
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3266898A Expired - Lifetime JP3799796B2 (en) | 1998-02-16 | 1998-02-16 | Method for producing ester |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP3799796B2 (en) |
| CN (1) | CN1190408C (en) |
| AU (1) | AU2300399A (en) |
| WO (1) | WO1999041226A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014185150A (en) * | 2013-03-21 | 2014-10-02 | Chang Chun Plastic Co Ltd | Method for manufacturing di(2-ethylhexyl) terephthalate |
| WO2015045969A1 (en) * | 2013-09-25 | 2015-04-02 | 株式会社Adeka | Method for producing ester compound |
| JP2016536313A (en) * | 2013-10-31 | 2016-11-24 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Method for producing carboxylic acid ester and use of said carboxylic acid ester as plasticizer |
| CN116209653A (en) * | 2020-09-24 | 2023-06-02 | 株式会社Lg化学 | Process for the preparation of ester compositions |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7799942B2 (en) | 2005-08-12 | 2010-09-21 | Eastman Chemical Company | Production of terephthalic acid di-esters |
| KR101506046B1 (en) * | 2007-03-13 | 2015-03-25 | 엑손모빌 케미칼 패턴츠 인코포레이티드 | batch esterification |
| CN103319346A (en) * | 2013-05-24 | 2013-09-25 | 中国林业科学研究院林产化学工业研究所 | Method and device for synthesizing plasticizer by regulating pressure |
| CN105985240A (en) * | 2015-02-04 | 2016-10-05 | 华东理工大学 | Novel process for reinforcement of esterification process in production of plasticizer |
| CN108003022B (en) * | 2016-11-02 | 2020-01-07 | 中国科学院大连化学物理研究所 | Method for preparing ester compound |
| CN108003024B (en) * | 2016-11-02 | 2019-10-18 | 中国科学院大连化学物理研究所 | A kind of preparation method of methyl propionate |
| CN108003023B (en) * | 2016-11-02 | 2019-10-18 | 中国科学院大连化学物理研究所 | A method of preparing methyl propionate |
| CN108997123B (en) * | 2018-09-11 | 2021-04-09 | 山东元利科技股份有限公司 | Method for synthesizing phthalate by catalytic oxidation product of o-xylene or naphthalene |
| WO2022065851A1 (en) * | 2020-09-24 | 2022-03-31 | 주식회사 엘지화학 | Batch preparation method for ester-based material |
| EP4219442A4 (en) * | 2020-09-24 | 2024-04-03 | Lg Chem, Ltd. | Method for producing ester-based composition |
| CN112125799A (en) * | 2020-10-14 | 2020-12-25 | 重庆欣欣向荣精细化工有限公司 | Production method of vanillin isobutyrate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS604151A (en) * | 1983-06-20 | 1985-01-10 | Mitsubishi Monsanto Chem Co | Production of terephthalic acid diester |
| JPH04504410A (en) * | 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 | Process and equipment |
| JPH07224002A (en) * | 1993-12-13 | 1995-08-22 | Kao Corp | Production of fatty acid lower alkyl esters |
| JPH08198812A (en) * | 1995-01-31 | 1996-08-06 | Rikagaku Kenkyusho | Production of dicarboxylic acid monoester |
-
1998
- 1998-02-16 JP JP3266898A patent/JP3799796B2/en not_active Expired - Lifetime
-
1999
- 1999-02-12 CN CN 99802957 patent/CN1190408C/en not_active Expired - Fee Related
- 1999-02-12 AU AU23003/99A patent/AU2300399A/en not_active Abandoned
- 1999-02-12 WO PCT/JP1999/000591 patent/WO1999041226A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS604151A (en) * | 1983-06-20 | 1985-01-10 | Mitsubishi Monsanto Chem Co | Production of terephthalic acid diester |
| JPH04504410A (en) * | 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 | Process and equipment |
| JPH07224002A (en) * | 1993-12-13 | 1995-08-22 | Kao Corp | Production of fatty acid lower alkyl esters |
| JPH08198812A (en) * | 1995-01-31 | 1996-08-06 | Rikagaku Kenkyusho | Production of dicarboxylic acid monoester |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014185150A (en) * | 2013-03-21 | 2014-10-02 | Chang Chun Plastic Co Ltd | Method for manufacturing di(2-ethylhexyl) terephthalate |
| WO2015045969A1 (en) * | 2013-09-25 | 2015-04-02 | 株式会社Adeka | Method for producing ester compound |
| JPWO2015045969A1 (en) * | 2013-09-25 | 2017-03-09 | 株式会社Adeka | Method for producing ester compound |
| JP2016536313A (en) * | 2013-10-31 | 2016-11-24 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Method for producing carboxylic acid ester and use of said carboxylic acid ester as plasticizer |
| US10106486B2 (en) | 2013-10-31 | 2018-10-23 | Basf Se | Method for producing carboxylic acid esters and the use thereof as plasticizers |
| CN116209653A (en) * | 2020-09-24 | 2023-06-02 | 株式会社Lg化学 | Process for the preparation of ester compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1190408C (en) | 2005-02-23 |
| AU2300399A (en) | 1999-08-30 |
| WO1999041226A1 (en) | 1999-08-19 |
| JP3799796B2 (en) | 2006-07-19 |
| CN1291180A (en) | 2001-04-11 |
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