JP2012092074A - Method for producing ester plasticizer - Google Patents
Method for producing ester plasticizer Download PDFInfo
- Publication number
- JP2012092074A JP2012092074A JP2010242469A JP2010242469A JP2012092074A JP 2012092074 A JP2012092074 A JP 2012092074A JP 2010242469 A JP2010242469 A JP 2010242469A JP 2010242469 A JP2010242469 A JP 2010242469A JP 2012092074 A JP2012092074 A JP 2012092074A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- anhydride
- producing
- ester plasticizer
- alcohol
- 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.)
- Pending
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
本発明は塩化ビニル系樹脂用として主に用いられるエステル可塑剤の製造方法に関し、特に芳香族カルボン酸エステルの製造方法に関する。 The present invention relates to a method for producing an ester plasticizer mainly used for vinyl chloride resin, and more particularly to a method for producing an aromatic carboxylic acid ester.
エステル可塑剤の製造方法として有機金属化合物触媒の存在下で、有機酸またはその無水物とアルコールとを脱水エステル化反応させることにより、エステル可塑剤を製造する方法がある（特許文献１）。しかしながらこの文献によれば、エステル化率99.9モル％の粗エステルを得るには190℃〜220℃において3時間加熱攪拌する必要があり、反応時間を長時間にする必要がある。 As a method for producing an ester plasticizer, there is a method for producing an ester plasticizer by subjecting an organic acid or an anhydride thereof and an alcohol to a dehydration esterification reaction in the presence of an organometallic compound catalyst (Patent Document 1). However, according to this document, in order to obtain a crude ester having an esterification rate of 99.9 mol%, it is necessary to heat and stir at 190 ° C. to 220 ° C. for 3 hours, and the reaction time must be prolonged.
また、常圧もしくは減圧下、180℃〜250℃において3〜6時間反応させることでジエステル化率99.9%の粗エステルを得る製造方法もある（特許文献２）。この文献の実施例によれば、210℃で減圧下に反応させているものの、あまり減圧度を上げると原料アルコールの急激な還流を伴うことから好ましくなく、そのため4〜5時間と長時間の反応が必要であった。 There is also a production method for obtaining a crude ester having a diesterification rate of 99.9% by reacting at 180 ° C. to 250 ° C. for 3 to 6 hours under normal pressure or reduced pressure (Patent Document 2). According to the example of this document, although the reaction is carried out at 210 ° C. under reduced pressure, it is not preferable because the raw alcohol is rapidly refluxed if the degree of vacuum is increased too much, and therefore the reaction takes a long time of 4 to 5 hours. Was necessary.
本発明の目的は、塩化ビニル系樹脂用として主に用いられるエステル可塑剤の製造方法に関し、特に芳香族カルボン酸エステルを製造する方法を提供することにある。 An object of the present invention relates to a method for producing an ester plasticizer mainly used for vinyl chloride resin, and particularly to provide a method for producing an aromatic carboxylic acid ester.
本発明者らは鋭意検討を行った結果、180〜200℃以下の温度において、温度が低下しないように減圧度を80〜20kPaに調整し、原料であるアルコールを還流させながら反応させることで、エステル化反応率99.9モル％以上に到達させることを見出した。 As a result of intensive studies, the inventors adjusted the degree of vacuum to 80 to 20 kPa so that the temperature does not decrease at a temperature of 180 to 200 ° C., and reacting the alcohol as a raw material while refluxing, It was found that the esterification reaction rate reached 99.9 mol% or more.
塩化ビニル系樹脂用として主に用いられるエステル可塑剤の製造方法に関し、特に芳香族カルボン酸エステルを低温で短時間に製造する方法を提供できる。 With respect to a method for producing an ester plasticizer mainly used for vinyl chloride resins, it is possible to provide a method for producing an aromatic carboxylic acid ester at a low temperature in a short time.
本発明は、塩化ビニル系樹脂用として主に用いられるエステル可塑剤の製造方法に関する。 The present invention relates to a method for producing an ester plasticizer mainly used for vinyl chloride resins.
本発明でエステル化反応に用いられる有機金属化合物触媒には、テトライソプロピルチタネート、テトラ−ｎ−ブチルチタネート、テトラ−２−エチルヘキシルチタネートのようなアルキルチタネート類や、スズテトラエチレート、ブチルスズマレートのような有機スズ化合物が好適に用いられ、これらの１種または２種以上を混合して使用しても良い。 Examples of the organometallic compound catalyst used in the esterification reaction in the present invention include alkyl titanates such as tetraisopropyl titanate, tetra-n-butyl titanate, tetra-2-ethylhexyl titanate, tin tetraethylate, and butyltin malate. Such organotin compounds are suitably used, and one or more of these may be used in combination.
エステル化反応に用いられる有機酸またはその無水物には、安息香酸、トルイル酸で代表される芳香族モノカルボン酸；フタル酸、無水フタル酸、イソフタル酸、テレフタル酸、トリメシン酸、トリメリット酸、無水トリメリット酸、ピロメリット酸、無水ピロメリット酸、ベンゾフェノンテトラカルボン酸、無水ベンゾフェノンテトラカルボン酸で代表される芳香族多価カルボン酸またはその無水物；アジピン酸、セバシン酸、アゼライン酸等の脂肪族多価カルボン酸；マレイン酸、フマル酸等の脂肪族不飽和多価カルボン酸；オレイン酸、ステアリン酸等の脂肪族モノカルボン酸等が挙げられ、これらの１種または２種以上を混合して使用しても良い。 Organic acids or their anhydrides used in the esterification reaction include aromatic monocarboxylic acids represented by benzoic acid and toluic acid; phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, trimesic acid, trimellitic acid, Trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, benzophenone tetracarboxylic acid, aromatic polyvalent carboxylic acid represented by benzophenone tetracarboxylic anhydride or its anhydride; fat such as adipic acid, sebacic acid, azelaic acid Aliphatic polycarboxylic acids such as maleic acid and fumaric acid; aliphatic monocarboxylic acids such as oleic acid and stearic acid, etc., and one or more of these may be mixed May be used.
エステル化反応に用いられるアルコールには、脂肪族飽和一価アルコールとして、メタノール、エタノール、プロパノール、イソプロパノール、ブタノール、イソブタノール、ｓｅｃ−ブタノール、ヘプタノール、オクタノール、２−エチルヘキサノール、イソオクタノール、ブテン二量体のオキソ反応により製造されるイソノニルアルコール、デカノール、プロピレン三量体のオキソ反応により製造されるイソデシルアルコール、ウンデカノール、トリデカノール等；脂肪族多価アルコールとして、エチレングリコール、プロピレングリコール、ジエチレングリコール等が挙げられ、これらの１種または２種以上を混合して使用しても良い。 The alcohol used for the esterification reaction includes aliphatic saturated monohydric alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, heptanol, octanol, 2-ethylhexanol, isooctanol, butene dimer. Isononyl alcohol, decanol, and propylene trimer produced by isononyl alcohol, decanol, tridecanol, etc. produced by oxo reaction of the body; aliphatic polyhydric alcohols include ethylene glycol, propylene glycol, diethylene glycol, etc. 1 type or 2 types or more may be mixed and used.
本発明のエステル可塑剤は、有機酸またはその無水物とアルコールとを、有機金属化合物触媒の存在下、180℃〜200℃において、温度が低下しないように減圧度を80〜20kPaに調整し、アルコールの還流を行わせながら生成水を系外に除去し、エステル化反応させる。 The ester plasticizer of the present invention adjusts the degree of vacuum to 80 to 20 kPa so that the temperature does not decrease at 180 ° C. to 200 ° C. in the presence of an organic metal compound catalyst in the presence of an organic acid or its anhydride and alcohol. The produced water is removed out of the system while refluxing the alcohol, and an esterification reaction is performed.
反応温度が180℃未満だと、有機金属触媒の活性が低く、エステル化反応率99.9モル％に到達するのは困難となり、好ましくない。また200℃を超えると原料アルコールの急激な還流を伴うため好ましくない。 When the reaction temperature is less than 180 ° C., the activity of the organometallic catalyst is low, and it is difficult to reach an esterification reaction rate of 99.9 mol%, which is not preferable. On the other hand, when the temperature exceeds 200 ° C., it is not preferable because the raw material alcohol is rapidly refluxed.
反応は減圧下で行う。反応圧力は80〜20kPaが好ましく、より好ましくは70〜30kPa、さらに好ましくは60〜35kPaである。80kPa以上だと、原料アルコールの還流が少なく、生成水の除去が困難となり、エステル化反応率99.9モル％に到達するのは困難となり、好ましくない。20kPa以下の場合は原料アルコールの急激な還流を伴うため好ましくない。 The reaction is carried out under reduced pressure. The reaction pressure is preferably 80 to 20 kPa, more preferably 70 to 30 kPa, and even more preferably 60 to 35 kPa. If it is 80 kPa or more, the reflux of raw material alcohol is small, it is difficult to remove the produced water, and it is difficult to reach an esterification reaction rate of 99.9 mol%, which is not preferable. When the pressure is 20 kPa or less, it is not preferable because the raw alcohol is rapidly refluxed.
エステル化反応に有機酸を用いる場合は、有機酸中のCOOHモル数に対するアルコールのモル比を、1/1.0〜1/1.4とするのが好ましく、より好ましくは1/1.1〜1.35、さらに好ましくは1/1.15〜1.3である。
また、エステル化反応に有機酸の無水物を用いる場合は、該無水物中の加水分解により有水化したCOOHモル数に対するアルコールのモル比を、1/1.0〜1/1.4とするのが好ましく、より好ましくは1/1.1〜1.35、さらに好ましくは1/1.15〜1.3である。
アルコールのモル比が1.0より少ないとアルコールの還流が実質的にできなくなり、好ましくない。またアルコールの仕込み量が1.4モルより多いと、減圧によるアルコールの還流が多すぎるため、好ましくない。
When an organic acid is used for the esterification reaction, the molar ratio of alcohol to the number of moles of COOH in the organic acid is preferably 1 / 1.0 to 1 / 1.4, more preferably 1 / 1.1-1.35, still more preferably 1 / 1.15-1.3.
When an organic acid anhydride is used for the esterification reaction, the molar ratio of alcohol to the number of moles of COOH hydrated by hydrolysis in the anhydride is preferably 1 / 1.0 to 1 / 1.4. More preferably, it is 1 / 1.1-1.35, More preferably, it is 1 / 1.15-1.3.
If the molar ratio of alcohol is less than 1.0, the alcohol cannot be refluxed substantially, which is not preferable. On the other hand, when the amount of the alcohol charged is more than 1.4 mol, the reflux of the alcohol due to the reduced pressure is excessive, which is not preferable.
エステル化反応で有機酸を用いる場合は、有機酸中のCOOHモル数に対する触媒の仕込み量を0.1〜1.0g/COOHモルとするのが好ましく、より好ましくは0.2〜0.8g/COOHモル、さらに好ましくは0.3〜0.6g/COOHモルである。
また、エステル化反応に有機酸の無水物を用いる場合は、該無水物中の加水分解により有水化したCOOHモル数に対する触媒の仕込み量を0.1〜1.0g/COOHモルとするのが好ましく、より好ましくは0.2〜0.8g/COOHモル、さらに好ましくは0.3〜0.6g/COOHモルである。
触媒量が0.1g/COOHモルより少ないと反応が十分に行えず、好ましくない。また触媒量が1.0 g/COOHモルより多いと、それ以上の触媒効果は望めず、経済的に好ましくない。
When an organic acid is used in the esterification reaction, the amount of catalyst charged relative to the number of moles of COOH in the organic acid is preferably 0.1 to 1.0 g / COOH mole, more preferably 0.2 to 0.8 g / COOH mole, and still more preferably Is 0.3-0.6 g / COOH mole.
Further, when an organic acid anhydride is used for the esterification reaction, the amount of catalyst charged relative to the number of moles of COOH hydrated by hydrolysis in the anhydride is preferably 0.1 to 1.0 g / COOH mole, More preferably, it is 0.2-0.8 g / COOH mol, More preferably, it is 0.3-0.6 g / COOH mol.
If the amount of catalyst is less than 0.1 g / COOH mol, the reaction cannot be sufficiently performed, which is not preferable. On the other hand, if the amount of catalyst is more than 1.0 g / COOH mol, no further catalytic effect can be expected, which is economically undesirable.
反応時間は3時間を超えない範囲が好ましく、より好ましくは2時間以内である。反応が3時間以上だと、反応時間が長すぎるため、経済的に好ましくない。 The reaction time is preferably within a range not exceeding 3 hours, more preferably within 2 hours. If the reaction is longer than 3 hours, the reaction time is too long, which is not economical.
以下、本発明を実施例によりさらに詳細に説明するが、本発明は、これらの例によってなんら限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
＜エステル化反応率＞
反応液の中和滴定により酸価（mgKOH/g）を測定し、下記計算式により反応率を算出する。
式１：残存COOHモル数＝反応液量×酸価÷56100
式２：残存有機酸またはその無水物モル数＝残存COOHモル数÷原料カルボニル基当量
[たたし、原料カルボニル基当量とは、原料有機酸またはその無水物１分子あたりに存在するCOOH数であり、無水物の場合は加水分解により有水化した場合のCOOH数。]
式３：エステル化率モル％＝（１−残存有機酸またはその無水物モル数÷反応前の有機酸またはその無水物モル数）×100
<Esterification reaction rate>
The acid value (mgKOH / g) is measured by neutralization titration of the reaction solution, and the reaction rate is calculated by the following formula.
Formula 1: Number of moles of residual COOH = reaction liquid amount × acid value ÷ 56100
Formula 2: Number of moles of residual organic acid or anhydride = number of moles of residual COOH ÷ equivalent carbonyl group of raw material
[However, the raw material carbonyl group equivalent is the number of COOH present per molecule of the raw organic acid or its anhydride, and in the case of an anhydride, the number of COOH when hydrophilized. ]
Formula 3: Esterification rate mol% = (1-residual organic acid or its anhydride moles ÷ organic acid or its anhydride mole before reaction) × 100
＜実施例１＞
無水フタル酸2960ｇ（20モル）と２−エチルヘキサノール5980ｇ（46モル）を混合し、これにテトライソプロピルチタネート6ｇを添加して、180℃に昇温し、35kPaに減圧し、2時間反応させた。この時点でのエステル化反応率は99.98モル％であった。
<Example 1>
2960 g (20 mol) of phthalic anhydride and 5980 g (46 mol) of 2-ethylhexanol were mixed, 6 g of tetraisopropyl titanate was added thereto, the temperature was raised to 180 ° C., the pressure was reduced to 35 kPa, and the mixture was reacted for 2 hours. . The esterification reaction rate at this time was 99.98 mol%.
＜実施例２＞
イソフタル酸3320ｇ（20モル）と２−エチルヘキサノール6240ｇ（48モル）を混合し、これにテトライソプロピルチタネート6ｇを添加して、200℃に昇温し、45kPaに減圧し、2時間反応させた。この時点でのエステル化反応率は99.97モル％であった。
<Example 2>
3320 g (20 mol) of isophthalic acid and 6240 g (48 mol) of 2-ethylhexanol were mixed, 6 g of tetraisopropyl titanate was added thereto, the temperature was raised to 200 ° C., the pressure was reduced to 45 kPa, and the mixture was reacted for 2 hours. The esterification reaction rate at this point was 99.97 mol%.
＜実施例３＞
無水トリメリット酸3840ｇ（20モル）と２−エチルヘキサノール8850ｇ（68モル）を混合し、これにテトライソプロピルチタネート9ｇを添加して、200℃に昇温し、30kPaに減圧し、2時間反応させた。この時点でのエステル化反応率は99.96モル％であった。
<Example 3>
Mix 3840 g (20 mol) of trimellitic anhydride and 8850 g (68 mol) of 2-ethylhexanol, add 9 g of tetraisopropyl titanate, raise the temperature to 200 ° C, reduce the pressure to 30 kPa, and react for 2 hours. It was. The esterification reaction rate at this point was 99.96 mol%.
＜実施例４＞
無水フタル酸2960ｇ（20モル）とイソノニルアルコール6630ｇ（46モル）を混合し、これにテトライソプロピルチタネート6ｇを添加して、180℃に昇温し、50kPaに減圧し、2時間反応させた。この時点でのエステル化反応率は99.93モル％であった。
<Example 4>
2960 g (20 mol) of phthalic anhydride and 6630 g (46 mol) of isononyl alcohol were mixed, 6 g of tetraisopropyl titanate was added thereto, the temperature was raised to 180 ° C., the pressure was reduced to 50 kPa, and the mixture was reacted for 2 hours. The esterification reaction rate at this time was 99.93 mol%.
＜比較例１＞
無水フタル酸2960ｇ（20モル）と２−エチルヘキサノール5980ｇ（46モル）を混合し、これにテトライソプロピルチタネート6ｇを添加して、170℃に昇温し、35kPaに減圧し、2時間反応させた。この時点でのエステル化反応率は95.78モル％であった。
<Comparative Example 1>
2960 g (20 mol) of phthalic anhydride and 5980 g (46 mol) of 2-ethylhexanol were mixed, 6 g of tetraisopropyl titanate was added thereto, the temperature was raised to 170 ° C., the pressure was reduced to 35 kPa, and the mixture was reacted for 2 hours. . The esterification reaction rate at this time was 95.78 mol%.
＜比較例２＞
無水フタル酸2960ｇ（20モル）と２−エチルヘキサノール5980ｇ（46モル）を混合し、これにテトライソプロピルチタネート6ｇを添加して、200℃に昇温し、90kPaで2時間反応させた。この時点でのエステル化反応率は98.14モル％であった。
<Comparative example 2>
2960 g (20 mol) of phthalic anhydride and 5980 g (46 mol) of 2-ethylhexanol were mixed, 6 g of tetraisopropyl titanate was added thereto, the temperature was raised to 200 ° C., and the mixture was reacted at 90 kPa for 2 hours. The esterification reaction rate at this point was 98.14 mol%.
＜比較例３＞
イソフタル酸3320ｇ（20モル）と２−エチルヘキサノール6240ｇ（48モル）を混合し、これにテトライソプロピルチタネート6ｇを添加して、200℃に昇温し、90kPaに減圧し、2時間反応させた。この時点でのエステル化反応率は92.10モル％であった。
<Comparative Example 3>
3320 g (20 mol) of isophthalic acid and 6240 g (48 mol) of 2-ethylhexanol were mixed, 6 g of tetraisopropyl titanate was added thereto, the temperature was raised to 200 ° C., the pressure was reduced to 90 kPa, and the reaction was performed for 2 hours. The esterification reaction rate at this time was 92.10 mol%.
以上の結果から、180〜200℃以下の温度において、温度が低下しないように減圧度を調整し、原料であるアルコールを還流させながら反応させることで、短時間にエステル化反応率99.9モル％以上に到達させることを見出した。 From the above results, at a temperature of 180 to 200 ° C. or less, the degree of reduced pressure is adjusted so that the temperature does not decrease, and the reaction is performed while refluxing the alcohol as a raw material, so that the esterification reaction rate is 99.9 mol% or more in a short time. Found to reach.
本発明のエステル可塑剤の製造方法は、塩化ビニル系樹脂用として主に用いられるエステル可塑剤の製造方法に関し、特に芳香族カルボン酸エステルの製造方法に利用可能である。 The method for producing an ester plasticizer of the present invention relates to a method for producing an ester plasticizer mainly used for vinyl chloride resins, and is particularly applicable to a method for producing an aromatic carboxylic acid ester.
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010242469A JP2012092074A (en) | 2010-10-28 | 2010-10-28 | Method for producing ester plasticizer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010242469A JP2012092074A (en) | 2010-10-28 | 2010-10-28 | Method for producing ester plasticizer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2012092074A true JP2012092074A (en) | 2012-05-17 |
Family
ID=46385869
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2010242469A Pending JP2012092074A (en) | 2010-10-28 | 2010-10-28 | Method for producing ester plasticizer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2012092074A (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103073428A (en) * | 2012-12-21 | 2013-05-01 | 中国石油集团东北炼化工程有限公司吉林设计院 | Process for improving production device of dioctyl phthalate |
| KR101458311B1 (en) * | 2013-04-23 | 2014-11-04 | 주식회사 엘지화학 | Plasticizer, resin composition and method for preparing them |
| WO2015119443A1 (en) * | 2014-02-07 | 2015-08-13 | 주식회사 엘지화학 | Ester compound, plasticizer composition comprising same, method for manufacturing ester composition, and resin composition comprising ester composition |
| US9714211B2 (en) | 2014-02-07 | 2017-07-25 | Lg Chem, Ltd. | Plasticizer and resin composition, and preparation method thereof |
| CN107250098A (en) * | 2014-12-02 | 2017-10-13 | 埃默里油脂化学有限公司 | Ester plasticiser based on ethyl hexanol and propyl enanthol |
| CN107540550A (en) * | 2017-09-28 | 2018-01-05 | 江苏正丹化学工业股份有限公司 | A kind of high-efficiency synthesis method of trioctyl trimellitate (TOTM) |
| CN109053444A (en) * | 2018-09-05 | 2018-12-21 | 安徽泰达新材料股份有限公司 | A kind of high- and low-temperature resistance type trimesic acid class synthesis ester plasticiser and preparation method thereof |
| KR20190022286A (en) * | 2017-08-25 | 2019-03-06 | 애경유화주식회사 | Composite plasticizer composition, and method for preparing the same, and polymer resin composition using the same |
| CN109503371A (en) * | 2018-12-17 | 2019-03-22 | 江苏森禾化工科技有限公司 | A kind of preparation method of low VOC environment-friendlyweather-proof weather-proof plasticizer |
| WO2019239294A1 (en) * | 2018-06-11 | 2019-12-19 | Sabic Global Technologies B.V. | Methods of manufacture of trialkyl tricarboxylates, and trialkyl tricarboxylates made by the methods |
| US10640446B2 (en) | 2016-05-25 | 2020-05-05 | Sabic Global Technologies B.V. | Synthesis of alkyl tribenzanoate |
| WO2020111475A1 (en) * | 2018-11-28 | 2020-06-04 | 주식회사 엘지화학 | Method for preparing terephthalate-based composition, comprising pressurization section |
| CN111606803A (en) * | 2020-06-20 | 2020-09-01 | 南通百川新材料有限公司 | Production method of trioctyl trimellitate plasticizer with high volume resistivity |
| CN114075326A (en) * | 2020-08-20 | 2022-02-22 | 南亚塑胶工业股份有限公司 | Plasticizer and manufacturing method thereof |
-
2010
- 2010-10-28 JP JP2010242469A patent/JP2012092074A/en active Pending
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103073428A (en) * | 2012-12-21 | 2013-05-01 | 中国石油集团东北炼化工程有限公司吉林设计院 | Process for improving production device of dioctyl phthalate |
| KR101458311B1 (en) * | 2013-04-23 | 2014-11-04 | 주식회사 엘지화학 | Plasticizer, resin composition and method for preparing them |
| WO2015119443A1 (en) * | 2014-02-07 | 2015-08-13 | 주식회사 엘지화학 | Ester compound, plasticizer composition comprising same, method for manufacturing ester composition, and resin composition comprising ester composition |
| US9714211B2 (en) | 2014-02-07 | 2017-07-25 | Lg Chem, Ltd. | Plasticizer and resin composition, and preparation method thereof |
| US10150727B2 (en) | 2014-02-07 | 2018-12-11 | Lg Chem, Ltd. | Ester compound, plasticizer composition including the same, preparation method of the plasticizer composition and resin composition including the plasticizer composition |
| CN107250098A (en) * | 2014-12-02 | 2017-10-13 | 埃默里油脂化学有限公司 | Ester plasticiser based on ethyl hexanol and propyl enanthol |
| US10640446B2 (en) | 2016-05-25 | 2020-05-05 | Sabic Global Technologies B.V. | Synthesis of alkyl tribenzanoate |
| KR102108875B1 (en) | 2017-08-25 | 2020-05-20 | 애경유화주식회사 | Composite plasticizer composition, and method for preparing the same, and polymer resin composition using the same |
| KR20190022286A (en) * | 2017-08-25 | 2019-03-06 | 애경유화주식회사 | Composite plasticizer composition, and method for preparing the same, and polymer resin composition using the same |
| CN107540550A (en) * | 2017-09-28 | 2018-01-05 | 江苏正丹化学工业股份有限公司 | A kind of high-efficiency synthesis method of trioctyl trimellitate (TOTM) |
| WO2019239294A1 (en) * | 2018-06-11 | 2019-12-19 | Sabic Global Technologies B.V. | Methods of manufacture of trialkyl tricarboxylates, and trialkyl tricarboxylates made by the methods |
| CN109053444A (en) * | 2018-09-05 | 2018-12-21 | 安徽泰达新材料股份有限公司 | A kind of high- and low-temperature resistance type trimesic acid class synthesis ester plasticiser and preparation method thereof |
| CN109053444B (en) * | 2018-09-05 | 2021-04-20 | 安徽泰达新材料股份有限公司 | High and low temperature resistant pyromellitic trimethyl acid synthetic ester plasticizer and preparation method thereof |
| WO2020111475A1 (en) * | 2018-11-28 | 2020-06-04 | 주식회사 엘지화학 | Method for preparing terephthalate-based composition, comprising pressurization section |
| KR20200063577A (en) * | 2018-11-28 | 2020-06-05 | 주식회사 엘지화학 | A Method for Manufacturing Terephthalate-based Composition Comprising Applying Pressure |
| KR102325729B1 (en) | 2018-11-28 | 2021-11-15 | 주식회사 엘지화학 | A Method for Manufacturing Terephthalate-based Composition Comprising Applying Pressure |
| US11407706B2 (en) | 2018-11-28 | 2022-08-09 | Lg Chem, Ltd. | Method for manufacturing terephthalate-based composition comprising applying pressure |
| CN109503371A (en) * | 2018-12-17 | 2019-03-22 | 江苏森禾化工科技有限公司 | A kind of preparation method of low VOC environment-friendlyweather-proof weather-proof plasticizer |
| CN111606803A (en) * | 2020-06-20 | 2020-09-01 | 南通百川新材料有限公司 | Production method of trioctyl trimellitate plasticizer with high volume resistivity |
| CN114075326A (en) * | 2020-08-20 | 2022-02-22 | 南亚塑胶工业股份有限公司 | Plasticizer and manufacturing method thereof |
| US20220056203A1 (en) * | 2020-08-20 | 2022-02-24 | Nan Ya Plastics Corporation | Plasticizer and method for producing the same |
| CN114075326B (en) * | 2020-08-20 | 2023-09-26 | 南亚塑胶工业股份有限公司 | Plasticizer and manufacturing method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2012092074A (en) | Method for producing ester plasticizer | |
| KR101240113B1 (en) | Catalyst and Process | |
| EP0812818B1 (en) | Esterification process | |
| JP2003500492A (en) | Esterification catalyst | |
| PL192913B1 (en) | Estrification reaction catalyst | |
| TWI242002B (en) | Optimized catalyst addition to enhance esterification catalyst performance | |
| CN108350154B (en) | Plasticizer composition, resin composition and method for producing the same | |
| JP2007507577A (en) | Catalyst for ester production | |
| US6255441B1 (en) | Titanium-containing catalyst composition and processes therefor and therewith | |
| WO1999054039A1 (en) | Catalyst composition comprising a titanium compound, a phosphorus compound and a solubility promoter; preparation and use thereof | |
| EP3194357B1 (en) | Process for preparing carboxylic acid esters in the presence of a titanium-containing catalyst | |
| JP5895292B2 (en) | Process for alkoxycarbonylation of functionalized alkenes | |
| EP3652143B1 (en) | Process for the production of bis-hydroxyalkylene dicarboxylates | |
| JP4120123B2 (en) | Method for producing ester | |
| JP3861945B2 (en) | Method for producing ester plasticizer | |
| GB2314081A (en) | Esterification Process | |
| WO2017115243A1 (en) | Process for the preparation of a dialkyl arylate | |
| JPH07278056A (en) | Production of organic acid ester | |
| JP2001270846A (en) | Method for producing ester | |
| JPH06279364A (en) | Production of ester | |
| JP6154289B2 (en) | Method for producing ester compound | |
| JP2001278840A (en) | Method for producing ester | |
| JPS6150094B2 (en) | ||
| AU2017341386A1 (en) | Method of preparing hydroxyalkylcarboxylic acid esters | |
| JPH0132815B2 (en) |