WO2018124613A1 - Procédé de préparation de diester d'acide carbonique aromatique - Google Patents

Procédé de préparation de diester d'acide carbonique aromatique Download PDF

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WO2018124613A1
WO2018124613A1 PCT/KR2017/015149 KR2017015149W WO2018124613A1 WO 2018124613 A1 WO2018124613 A1 WO 2018124613A1 KR 2017015149 W KR2017015149 W KR 2017015149W WO 2018124613 A1 WO2018124613 A1 WO 2018124613A1
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carbonate
catalyst
aromatic
reaction
parts
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PCT/KR2017/015149
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English (en)
Korean (ko)
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배진용
서명도
이승환
지준호
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롯데첨단소재(주)
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Publication of WO2018124613A1 publication Critical patent/WO2018124613A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/02—Preparation of carboxylic acid esters by interreacting ester groups, i.e. transesterification
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/49—Esterification or transesterification
    • 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
    • Y02P20/584—Recycling of catalysts

Definitions

  • the present invention relates to a method for producing aromatic diester carbonate. More specifically, the present invention relates to a method for producing an aromatic diester which can recover the catalyst in a high yield from the by-products produced when producing the aromatic diester carbonate.
  • Aromatic carbonate diester compounds are prepared using toxic toxic, but toxic, toxic toxic, excessive alkali salts, there is a problem using an organic solvent.
  • a method for producing an aromatic carbonate diester compound by reacting an aliphatic carbonate diester compound and an aromatic alcohol in the presence of an organometallic catalyst has been developed.
  • the reaction between the aliphatic carbonate diester compound and the aromatic alcohol has a small equilibrium constant so that the productivity can be improved through a reaction distillation method of improving the forward reaction by removing alcohol as a byproduct under high temperature and high pressure conditions.
  • the by-products generated in the process has a high boiling point, it is not easy to separate from the catalyst by a simple distillation method. Even if the separation is possible, a large amount of energy is required at a high temperature, and the method is not suitable for synthesizing the aromatic carbonic acid diester through aliphatic carbonic acid diester and aromatic alcohol, which consumes a lot of energy.
  • Another method for preventing the loss of the catalyst is to apply a heterogeneous catalyst in which the catalyst is supported on a metal oxide.
  • the catalyst since the catalyst is bound to the metal oxide support, the amount of the by-products incorporated into the by-products is extremely low, so even if the by-products are disposed of, the content of the catalyst contained in the waste is extremely low, so that no separate separation process is required.
  • it can be applied through the new process or the improvement of the existing equipment, but it is less effective when applied in the operation process because it is more complicated and expensive compared to the construction of the catalyst recovery process. A problem arises.
  • An object of the present invention is to provide a method for producing an aromatic diester carbonate that can recover the catalyst from the reused by-products without discarding the by-products produced when producing the aromatic diester carbonate.
  • Another object of the present invention is to provide an aromatic diester carbonate production method which minimizes energy consumption by not using distillation when recovering a catalyst.
  • Still another object of the present invention is to provide an aromatic diester carbonate production method capable of recovering the catalyst used in the production of the aromatic diester carbonate in high yield.
  • the present invention relates to a method for producing aromatic diester carbonate.
  • the method comprises transesterifying aliphatic diester carbonate and an aromatic alcohol in the presence of an organometallic catalyst to prepare a reaction mixture; Separating a carbonate reaction by-product containing an aromatic diester carbonate and an organometallic catalyst from the reaction mixture; Preparing a first reactant in which a byproduct is dissolved by mixing a polar solvent with the carbonate reaction byproduct containing the organometallic catalyst; Adding a nonpolar solvent to the first reactant to precipitate an organometallic catalyst; Recovering the precipitated organometallic catalyst and injecting it into the transesterification reaction; Steps.
  • the polar solvent may include one or more of anisole, aliphatic alcohol, aromatic alcohol, ketone, aldehyde, glycol, carbonate.
  • the nonpolar solvent may include at least one of pentane, hexane, heptane, octane, decane, dodecane, cyclopentane, cyclohexane, and cyclooctane.
  • the polar solvent is anisole
  • the non-polar solvent may be hexane
  • the polar solvent may be acetone, and the nonpolar solvent may be cyclohexane.
  • the polar solvent may be about 50 parts by weight to about 500 parts by weight based on 100 parts by weight of the carbonate reaction by-product.
  • the nonpolar solvent may be about 50 parts by weight to about 200 parts by weight based on 100 parts by weight of the polar solvent.
  • the organometallic catalyst may include one or more of metals of Ti, Pb, Ce, Cu, Zn, Fe, Co, Ni, Al, V, Sm, Sn, and Zr.
  • the organometallic catalyst may be an unsupported homogeneous catalyst.
  • the present invention can recover the catalyst from the by-product without disposing the by-products produced when producing the aromatic diester carbon dioxide can be reused, the energy consumption can be minimized by using a distillation method when the catalyst is recovered, high yield as a catalyst It has the effect of providing an aromatic diester carbonate production method which can be recovered.
  • 1 is a process chart showing an aromatic carbonate diester production method according to an embodiment of the present invention.
  • a method for producing an aromatic diester carbonate according to the present invention comprises transesterification of an aliphatic carbonate diester and an aromatic alcohol in the presence of an organometallic catalyst to prepare a reaction mixture; Separating a carbonate reaction by-product containing an aromatic diester carbonate and an organometallic catalyst from the reaction mixture; Preparing a first reactant in which a byproduct is dissolved by mixing a polar solvent with the carbonate reaction byproduct containing the organometallic catalyst; Adding a nonpolar solvent to the first reactant to precipitate an organometallic catalyst; Recovering the precipitated organometallic catalyst and injecting it into the transesterification reaction; Steps.
  • 1 is a process chart showing an aromatic carbonate diester production method according to an embodiment of the present invention.
  • aliphatic carbonic acid diester, aromatic alcohol, and the like which are reaction raw materials, are introduced into a transesterification reactor R1 through a line L1. Although illustrated as one line L1 in the figure, each may be input through a separate line.
  • transesterification reactor (R1) an aliphatic diester and an aromatic alcohol are transesterified in the presence of an organometallic catalyst to prepare a reaction mixture.
  • the organometallic catalyst may be introduced via line (L1), after which the recovered catalyst is introduced via line (L5).
  • the aliphatic diester carbonate may be represented by the following Chemical Formula 1.
  • R 1 is each independently a substituted or unsubstituted C1 to C10 alkyl group or C3 to C10 cycloalkyl group.
  • aliphatic carbonic acid diesters include dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, dipentyl carbonate, dihexyl carbonate, diheptyl carbonate, dioctyl carbonate, dinonyl carbonate, didecyl carbonate, and dish Clopentylcarbonate, dicyclohexylcarbonate, dicycloheptylcarbonate, di (methoxymethyl) carbonate, di (methoxyethyl) carbonate, di (chloroethyl) carbonate, di (cyanoethyl) carbonate, and the like.
  • the aromatic alcohols include phenol, cresol, xenol, trimethylphenol, tetramethylphenol, ethylphenol, propylphenol, butylphenol, diethylphenol, methylethylphenol, methylpropylphenol, dipropylphenol, methylbutylphenol, and pentyl.
  • Various alkylphenols such as phenol, hexylphenol, cyclohexylphenol, various alkoxyphenols such as methoxyphenol and ethoxyphenol, and arylalkylphenols such as phenyl propylphenol can be used.
  • the organometallic catalyst may include one or more of metals of Ti, Pb, Ce, Cu, Zn, Fe, Co, Ni, Al, V, Sm, Sn, and Zr.
  • said organometallic catalyst is an unsupported homogeneous catalyst.
  • the reaction mixture prepared by transesterification of the aliphatic diester and the aromatic alcohol is mixed with the aromatic diester and the by-product.
  • the reaction mixture is discharged through line (L2), the aromatic diester carbonic acid product is discharged through line (L4), and by-products are recovered in the catalytic recovery reactor (R2) without being discarded through line (L3).
  • the by-products are organometallic catalysts, unreacted raw materials, aromatic alcohols, carbonate derivatives, carbonyl acids, esters, and the like as carbonate reaction by-products containing organometallic catalysts.
  • the first reactant is prepared by mixing and dissolving a polar solvent in a carbonate reaction by-product containing the organometallic catalyst.
  • the carbonate reaction by-product containing the organometallic catalyst contains a metal catalyst which is a Lewis acid and an aliphatic carbonate, an aromatic carbonate, an aromatic alcohol, a carbonate derivative, carbonyl acid, an ester, and the like, polar substances such as anisole and aliphatic alcohol Excellent solubility in aromatic alcohols, ketones, aldehydes, glycols, carbonates and the like can be dissolved well without forming precipitates.
  • the polar solvent is about 50 parts by weight to about 500 parts by weight, for example 50 parts by weight, 100 parts by weight, 150 parts by weight, 200 parts by weight, 250 parts by weight, based on 100 parts by weight of the carbonate reaction by-product. 300 parts by weight, 350 parts by weight, 400 parts by weight, 450 parts by weight, and 500 parts by weight. While completely dissolving the metal catalyst and the high by-products in the composition, even when a small amount of nonpolar solvent is used, the metal catalyst forms a precipitate, and the by-products can be maintained in a liquid phase at room temperature to facilitate catalyst separation through filtering.
  • the polar solvent is soluble in both by-products and organometallic catalysts, and may include, for example, one or more of anisole, aliphatic alcohol, aromatic alcohol, ketone, aldehyde, glycol, carbonate.
  • a nonpolar solvent is added to the first reactant to precipitate an organometallic catalyst.
  • a nonpolar solvent is added to the polar first reactant, only the polar metal catalyst forms a precipitate.
  • nonpolar solvent is insoluble in organometallic catalysts, those having solubility in by-products can be used.
  • the nonpolar solvent may include, for example, one or more of pentane, hexane, heptane, octane, decane, dodecane, cyclopentane, cyclohexane, cyclooctane.
  • pentane hexane
  • heptane octane
  • decane dodecane
  • cyclopentane cyclohexane
  • cyclooctane cycloctane
  • the polar solvent is anisole
  • the non-polar solvent may be hexane.
  • the combination of such a polar solvent and a non-polar solvent has the advantage of excellent catalyst recovery and easy handling, and low cost.
  • the polar solvent may be acetone, and the nonpolar solvent may be cyclohexane.
  • the combination of such a polar solvent and a non-polar solvent has an advantage of excellent catalyst recovery.
  • the nonpolar solvent may be about 50 parts by weight to about 200 parts by weight, for example 50 parts by weight, 100 parts by weight, 150 parts by weight, and 200 parts by weight based on 100 parts by weight of the polar solvent. In the above range, only the metal catalyst selectively forms precipitates, and organic byproducts have a dissolving effect.
  • R2 catalytic recovery reactor
  • the organometallic catalyst is precipitated and precipitated due to the difference in solubility, and then the organometallic catalyst and residual by-products are separated by filtration.
  • the organometallic catalyst thus separated is introduced into the transesterification reactor (R1) through the line (L5) to participate in the aromatic diester carbonate synthesis.
  • the filtrate remaining after the filtration does not leave the metal oxide of the organometallic catalyst, the unreacted raw materials such as aliphatic carbonate diester, phenol, etc. are left in the filtrate. Therefore, these unreacted raw materials can be recovered and reused.
  • Example 2 The same procedure as in Example 1 was conducted except that 3 g of hexane was added.
  • Example 2 The same procedure as in Example 1 was conducted except that 5 g of hexane was added.
  • Example 2 The same procedure as in Example 1 was carried out except that 7 g of hexane was added.
  • Example 2 The same procedure as in Example 1 was conducted except that 10 g of hexane was added.
  • Example 2 The same procedure as in Example 1 was conducted except that no hexane was added.
  • Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Raw Material Input By Product Input (g) 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 - 5.0 - Acetone input (g) - - - - - 5.0 - - Hexane Input (g) 1.0 3.0 5.0 7.0 10.0 - - 5.0 Cyclohexane Input (g) 5.0 Methylene chloride dosage (g) - - - - - - - - 5.0 Toluene Input (g) - - - - - - 5.0 Catalyst concentration Before filtration (ppm) 3,455 2,923 2,533 2,235 1,900 2,533 3,800 2,533 After filtration (ppm) 3,094 2,108 1,576 1,214 764 1,601 3,649 2,508 Recovery rate (%) 10.44 27.88 37.79
  • Example 7 The same process as in Example 7 was carried out except that 30 ppm of the catalyst recovered in Example 1 was added.
  • Example 7 The same process as in Example 7 was carried out except that 40 ppm of the catalyst recovered in Example 1 was added.
  • Example 7 Example 8 Example 9 Comparative Example 1 Comparative Example 2 Comparative Example 3 Raw Material Input Phenolic Dose (g) 12.29 12.29 12.29 12.29 12.29 DMC input (g) 5.88 5.88 5.88 5.88 5.88 5.88 Catalyst concentration Recovery catalyst (ppm) 20 30 40 - - - Fresh catalyst (ppm) - - - 20 30 40 Reaction temperature (°C) 235 235 235 235 235 235 235 235 235 Reaction time (min) 15 15 15 15 15 15 15 15 MPC yield (%) 4.15 6.56 7.94 4.27 6.39 7.90
  • the aromatic carbonate diester production method of the present invention even if the recovery catalyst is applied, the yield of the aromatic carbonate diester is similar or higher than that of Comparative Example 1-3 to which a fresh catalyst is applied. Can be.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé de préparation d'un diester d'acide carbonique aromatique comprenant les étapes consistant à : effectuer une réaction de transestérification d'un diester d'acide carbonique aliphatique et d'un alcool aromatique en présence d'un catalyseur organométallique pour préparer un mélange réactionnel ; séparer, à partir du mélange réactionnel, le diester d'acide carbonique aromatique et un sous-produit de réaction de carbonate contenant le catalyseur organométallique ; mélanger un solvant polaire avec le sous-produit de réaction de carbonate contenant le catalyseur organométallique pour préparer un premier produit de réaction dans lequel le sous-produit est dissous ; ajouter un solvant non polaire au premier produit de réaction pour précipiter le catalyseur organométallique ; et récupérer le catalyseur organométallique précipité et introduire le catalyseur organométallique précipité dans la réaction de transestérification.
PCT/KR2017/015149 2016-12-30 2017-12-20 Procédé de préparation de diester d'acide carbonique aromatique WO2018124613A1 (fr)

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KR10-2016-0184172 2016-12-30
KR1020160184172A KR102014585B1 (ko) 2016-12-30 2016-12-30 방향족 탄산디에스테르 제조방법

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KR102256129B1 (ko) * 2020-11-11 2021-05-24 한국화학연구원 에스테르 교환반응의 반응 폐액을 이용한 금속산화물의 제조 및 이의 사용방법
KR102644180B1 (ko) * 2020-11-26 2024-03-05 롯데케미칼 주식회사 우수한 용해도를 가지는 촉매를 이용한 이종 선형 카보네이트를 제조하는 방법

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5284965A (en) * 1992-03-12 1994-02-08 Bayer Aktiengesellschaft Process for preparing aromatic carbonates
JPH07227546A (ja) * 1993-12-20 1995-08-29 Nippon Shokubai Co Ltd 芳香族炭酸エステル製造用触媒およびそれを用いた芳香族炭酸エステルの製造法
US20030162989A1 (en) * 2000-04-07 2003-08-28 Ohashi Kenji E Method of separating and recovering aromatic carbonate and production process
CN1670011A (zh) * 2004-03-17 2005-09-21 中国科学院成都有机化学有限公司 一种从酯交换反应液中分离催化剂的方法
KR20150027203A (ko) * 2012-06-29 2015-03-11 사빅 글로벌 테크놀러지스 비.브이. 디아릴 카보네이트의 제조방법 및 장치

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5284965A (en) * 1992-03-12 1994-02-08 Bayer Aktiengesellschaft Process for preparing aromatic carbonates
JPH07227546A (ja) * 1993-12-20 1995-08-29 Nippon Shokubai Co Ltd 芳香族炭酸エステル製造用触媒およびそれを用いた芳香族炭酸エステルの製造法
US20030162989A1 (en) * 2000-04-07 2003-08-28 Ohashi Kenji E Method of separating and recovering aromatic carbonate and production process
CN1670011A (zh) * 2004-03-17 2005-09-21 中国科学院成都有机化学有限公司 一种从酯交换反应液中分离催化剂的方法
KR20150027203A (ko) * 2012-06-29 2015-03-11 사빅 글로벌 테크놀러지스 비.브이. 디아릴 카보네이트의 제조방법 및 장치

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