WO2016064210A1 - Procédé de préparation de téréphtalate de diméthyle avec utilisation d'acétylène - Google Patents

Procédé de préparation de téréphtalate de diméthyle avec utilisation d'acétylène Download PDF

Info

Publication number
WO2016064210A1
WO2016064210A1 PCT/KR2015/011184 KR2015011184W WO2016064210A1 WO 2016064210 A1 WO2016064210 A1 WO 2016064210A1 KR 2015011184 W KR2015011184 W KR 2015011184W WO 2016064210 A1 WO2016064210 A1 WO 2016064210A1
Authority
WO
WIPO (PCT)
Prior art keywords
trans
dimethyl terephthalate
reaction
dimethyl
acetylene
Prior art date
Application number
PCT/KR2015/011184
Other languages
English (en)
Korean (ko)
Inventor
신용준
박정호
박재균
Original Assignee
에스케이케미칼주식회사
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 에스케이케미칼주식회사 filed Critical 에스케이케미칼주식회사
Publication of WO2016064210A1 publication Critical patent/WO2016064210A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
    • 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
    • C07C69/80—Phthalic acid esters
    • C07C69/82—Terephthalic acid esters
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel

Definitions

  • the present invention relates to a method for preparing dimethyl terephthalate using acetylene, and more particularly, to dimethyl by one-pot using addition cyclization and dehydrogenation using acetylene, dimethyl muconate and catalyst. It relates to a method for preparing terephthalate.
  • biodiesel which produces fuels that can be used in diesel engines by esterifying oils extracted from plants such as fluid oil, soybean oil, and palm oil.
  • biologically-derived materials are being actively researched in the traditional polymer industry as well as the replacement of energy-based materials.
  • polylactic acid a biodegradable polymer produced from lactic acid as a raw material
  • PTT Polytrimethylterephthalate
  • 'DMT' dimethyl terephthalate
  • 'DMT' dimethyl terephthalate
  • DMT is a paraxylene (PX) in the acetic acid solution using a metal catalyst such as cobalt (Co), manganese (Mn) and a strong acid as a catalyst to prepare a terephthalic acid (terephthalic acid (TPA) by oxidation reaction, It is known to obtain by esterification, distillation and purification under reduced pressure of TPA and methanol prepared above.
  • the synthesized and purified DMT has a high purity of 99.99% or more, and can be used as a main raw material for polyester synthesis such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polytrimethylene terephthalate (PTT). .
  • DMT can be prepared using dimethyl muconate and ethylene as raw materials.
  • the manufacturing process is carried out in two stages, and because different solvents and catalysts are used for each stage, There is the same fundamental weakness.
  • the reaction goes through several stages.
  • the process of creating a single product increases the cost of investment and the complexity of the design of the reaction, making it economical.
  • the yield of each step is high, the type and amount of impurities are increased by going through several steps, and as a result, the yield and purity of the product are lowered.
  • the present inventors while studying the method for producing DMT using the material of muconic acid, which is a biological material, confirmed that DMT was produced at a high conversion rate by addition cyclization reaction between dimethyl muconate and acetylene in the presence of a catalyst.
  • the present invention has been completed.
  • DMT dimethyl terephthalate
  • the reaction step can be reduced by using acetylene in the synthesis process of DMT using dimethyl muconate, and it is economical because the process design is easy and the investment cost is low by using a low-cost catalyst having a low economic burden of reuse.
  • the method of the present invention can produce a high yield of DMT having a higher or equivalent level of purity compared to the final material prepared by the conventional method, thereby reducing the production cost, and using environmentally-derived raw materials, environmental problems It can correspond to.
  • the addition cyclization reaction and the dehydrogenation reaction can be carried out in one-pot.
  • the present invention relates to a process for the preparation of dimethyl terephthalate via an addition cyclization step of dimethyl muconate and acetylene, wherein the process according to the invention comprises one low reaction step, using a low cost metal catalyst. It features.
  • the method for producing DMT according to the present invention is a conventional method that is very complicated and commercially possible to generate a large amount of impurities due to different steps of the catalyst and solvent conditions of each reaction through different reaction paths (eg, international Compared to the patent publication WO 2012/082725), high purity DMT can be produced economically, efficiently and with high yield.
  • the present invention provides a method for producing DMT comprising the step of adding dimethyl muconate and acetylene gas to the reactor and reacting in a solvent in the presence of a catalyst to obtain an addition cyclization reactant and a dehydrogenation reactant.
  • DMT by adding dimethyl muconate and acetylene gas to the reactor, stirring the mixture in a solvent, heating and raising the mixture to proceed the addition cyclization reaction and dehydrogenation reaction to one-pot Can be prepared.
  • the myuko dimethyl carbonate used as starting material in the production method of the present invention is trans, trans- may be myuko dimethyl carbonate (trans, trans -dimethylmuconate).
  • the trans, trans-dimethylmuconate may be prepared from muconic acid in the presence of a catalyst in a solvent.
  • the solvent is, for example, alcohols such as methanol and ethanol; Polar solvents such as methyl iodide (MeI), dimethylformamide (DMF), and dimethyl sulfoxide (DMSO); Alkyl ethers such as tetrahydrofuran (THF), diethyl ether and dimethylethylene glycol; Alkyl acetates such as ethyl acetate and methyl acetate; Ketones such as methyl ethyl ketone (MEK) and acetone; Aromatic solvents such as benzene, toluene, xylene, chlorobenzene, cresol, and methyl phenyl ester; Organic solvents such as methylene chloride and chloroform; And it may be selected from the group consisting of, but is not limited thereto.
  • Polar solvents such as methyl iodide (MeI), dimethylformamide (DMF), and dimethyl sulfoxide (DMSO)
  • the catalyst is an acid such as methanesulfonic acid, paratoluenesulfonic acid, phosphoric acid, hydrochloric acid, sulfuric acid; Bases such as potassium carbonate and sodium hydroxide; And it may be selected from the group consisting of, but is not limited thereto.
  • the acetylene gas may be introduced at a pressure of 1 bar or more, 1 to 20 bar, preferably 3 to 20 bar, more preferably 5 to 18 bar.
  • the addition cyclization and dehydrogenation reaction may be carried out at 100 °C or more, 100 °C to 400 °C, 110 °C to 400 °C, 110 °C to 190 °C or 130 °C to 300 °C, the reaction time for 1 to 48 hours , But may be performed for 4 to 24 hours, but is not limited thereto.
  • the addition cyclization and dehydrogenation reaction can be carried out in a solvent, which solvent is for example an aromatic solvent such as benzene, toluene, chlorobenzene, cresol, methylphenylester and xylene, tetrahydrofuran and dimethylethylene glycol Alkyl ether solvents such as methyl acetate, ethyl acetate and ethyl acetate solvents such as butyl acetate, ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone, N-methylpyrrolidone (NMP), dimethylformamide, dimethyl sulfoxide It may be an organic solvent selected from the group consisting of the side, and mixtures thereof, but is not limited thereto.
  • aromatic solvent such as benzene, toluene, chlorobenzene, cresol, methylphenylester and xylene
  • it may be selected from the group consisting of metaxylene, tetrahydrofuran, ethyl acetate, dimethylethylene glycol, N-methylpyrrolidone, dimethyl sulfoxide and mixtures thereof.
  • the solvent may be used in an amount of 1 to 200 equivalents, preferably 10 to 100 equivalents based on dimethylmuconate.
  • the catalyst may be a metal halide, specifically, BeCl 2 , MgCl 2 , CaCl 2 , SrCl 2 , BaCl 2 , BCl 3 , AlCl 3 , GaCl 3 , InCl 3 , TiCl 3 , TiCl 4 , ZnCl 2 , CrCl 2 , CrCl 3 , CrCl 4 , FeCl 2 , FeCl 3 , FeCl 4 , Fe 2 Cl 6 , CoCl 2 , CoCl 3 , CuCl 2 , CuCl 3 and mixtures thereof It may be selected but is not limited thereto.
  • the halogenated metal catalyst may be used in an amount of 0.001 to 10 molar equivalents, 0.01 to 5 molar equivalents, 0.02 to 3 molar equivalents, 0.03 to 1 molar equivalents, or 0.05 to 0.2 molar equivalents based on dimethyl muconate.
  • dimethylcyclohexa-2,5-diene-1,4-carboxylate can be produced as the addition cyclization reactant as DMT and an intermediate (see Example 2).
  • the process of the present invention may further comprise the step of aromatization by heating said addition cyclization reactant, preferably dimethylcyclohexa-2,5-diene-1,4-carboxylate intermediate.
  • dimethyl muconate and acetylene gas are charged to a reactor, the mixture is stirred in a catalyst and a solvent, heated and heated to give an additional cyclization reactant, and then the addition cyclization reactant is heated to aromatization.
  • DMT can be manufactured by making it react.
  • the aromatization reaction is added at least 100 °C, 100 °C to 400 °C, 110 °C to 400 °C, 110 °C to 190 °C or 130 °C to 300 °C sealed by adding the addition cyclization reaction of dimethyl muconate and acetylene to the reactor It can be carried out by heating.
  • the reaction time may be performed for 1 to 48 hours, preferably 4 to 24 hours, but is not limited thereto.
  • the aromatization reaction may be pressurized using an oxidizing agent.
  • the oxidizing agent may be used without limitation as long as it is a component widely used in the art.
  • the oxidizing agent may be selected from the group consisting of, for example, hydrogen peroxide, perchloric acid, potassium permanganate, ozone, oxygen, and combinations thereof, and it is preferable to inject a gas containing oxygen because it is easy to use and economical.
  • the gas containing oxygen may be, for example, air, mixed gas of oxygen and nitrogen, mixed gas of oxygen and helium, mixed gas of oxygen and inert gas, or oxygen, but is not limited thereto.
  • a solvent may be further used.
  • the kind of the solvent is not particularly limited, and a solvent used in the addition cyclization reaction may be used, and other solvents may be used.
  • the aromatization reaction can be used for the aromatization reaction without special treatment of the addition cyclization reaction, it is preferable to perform the aromatization reaction after removing the acetylene gas used in the addition cyclization reaction by air.
  • the conventional method is a one-step reaction step in the presence of a catalyst, compared to the commercial process design is very complicated and the impurities content is high through a multi-step reaction route It is possible to manufacture high-purity DMT with high yield alone, so it is economical and easy to commercialize.
  • DMT which is commercially produced using petroleum-derived PX as a raw material
  • muconic acid which is a biological material, as a raw material, and thus may be an appropriate alternative in an eco-friendly and high oil price era.
  • trans, trans-muconic acid 100 g was reacted with 5 g of concentrated sulfuric acid as a catalyst under reflux conditions in 1,000 ml of methanol to obtain 110 g of trans, trans-dimethylmuconate.
  • trans, trans-muconic acid 100 g was reacted with 5 g of p-toluenesulfonic acid as a catalyst under reflux conditions in 1,000 ml of methanol to obtain 111 g of trans, trans-dimethylmuconate.
  • trans, trans-dimethylmuconate thus prepared was cooled to room temperature and then crystallized by filtration.
  • the trans, trans-dimethylmuconate prepared in Method 3 was added to 100 mL of methanol to crystallize and then filtered to obtain a high purity of 99.66%.
  • trans, trans-dimethylmuconate synthesized in Method 1 of Example 1 was subjected to an additional cyclization reaction with acetylene in a m-xylene solvent.
  • trans, trans-dimethylmuconate synthesized in Method 1 of Example 1 was subjected to an additional cyclization reaction with acetylene in a m-xylene solvent.
  • Comparative Example 3 hardly proceeded the addition cyclization reaction, and produced about 70% of carbonized by-products.
  • the addition cyclization reaction was slightly progressed, but was only about 0.1% converted to TPA, and Comparative Example 5 was mostly carbonated by-products, and almost no DMT was produced.
  • Example 5 menstruum Trans, trans-dimethylmuconate Intermediate 1 DMT Other
  • THF 25.3% 24.5% 29.4% 20.8%
  • Example 6 EA 29.1% 26.6% 25.8% 19.5%
  • Example 7 meta-Xylene 32.5% 17.0% 35.1% 15.4%
  • Example 8 NMP 27.8% 20.3% 29.0% 22.9%
  • Example 9 DMSO 26.8% 23.7% 26.4% 23.1%
  • trans trans-dimethylmuconate was converted to tetrahydrofuran (THF), ethyl acetate (EA), metaxylene, N-methylpyrrolidone (NMP) and dimethyl sulfoxide.
  • THF tetrahydrofuran
  • EA ethyl acetate
  • NMP N-methylpyrrolidone
  • DMSO organic solvent
  • addition cyclization in the presence of acetylene and a catalyst was found to convert to a high proportion of DMT.

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

La présente invention concerne un procédé de préparation monotope de téréphtalate de diméthyle au moyen d'une réaction de cycloaddition, avec utilisation d'acétylène et de muconate de diméthyle. Le procédé de préparation de la présente invention est très simple, sans danger pour l'environnement étant donné qu'il est possible d'utiliser de l'acide muconique d'origine biologique et de l'acétylène d'origine biologique, tout en étant économique et efficace.
PCT/KR2015/011184 2014-10-24 2015-10-22 Procédé de préparation de téréphtalate de diméthyle avec utilisation d'acétylène WO2016064210A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020140145512A KR102250750B1 (ko) 2014-10-24 2014-10-24 아세틸렌을 사용한 디메틸테레프탈레이트의 제조방법
KR10-2014-0145512 2014-10-24

Publications (1)

Publication Number Publication Date
WO2016064210A1 true WO2016064210A1 (fr) 2016-04-28

Family

ID=55761165

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2015/011184 WO2016064210A1 (fr) 2014-10-24 2015-10-22 Procédé de préparation de téréphtalate de diméthyle avec utilisation d'acétylène

Country Status (2)

Country Link
KR (1) KR102250750B1 (fr)
WO (1) WO2016064210A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102595610B1 (ko) * 2016-09-20 2023-10-31 에스케이케미칼 주식회사 디메틸테레프탈레이트의 제조방법
KR102394369B1 (ko) * 2017-11-27 2022-05-04 에스케이케미칼 주식회사 디메틸테레프탈레이트의 제조방법

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110124911A1 (en) * 2009-08-05 2011-05-26 Burk Mark J Semi-synthetic terephthalic acid via microorganisms that produce muconic acid
KR20120027531A (ko) * 2009-06-16 2012-03-21 아미리스 인코퍼레이티드 시클로헥센 1,4-카르복실레이트
WO2013109865A2 (fr) * 2012-01-20 2013-07-25 Genomatica, Inc. Microorganismes et procédés de production d'acide téréphtalique et ses sels

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7385081B1 (en) * 2007-11-14 2008-06-10 Bp Corporation North America Inc. Terephthalic acid composition and process for the production thereof
WO2012082725A1 (fr) 2010-12-15 2012-06-21 Amyris, Inc. Déshydrogénation en continu de cyclohexènes substitués par 1,4-carboxylate

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20120027531A (ko) * 2009-06-16 2012-03-21 아미리스 인코퍼레이티드 시클로헥센 1,4-카르복실레이트
US20110124911A1 (en) * 2009-08-05 2011-05-26 Burk Mark J Semi-synthetic terephthalic acid via microorganisms that produce muconic acid
WO2013109865A2 (fr) * 2012-01-20 2013-07-25 Genomatica, Inc. Microorganismes et procédés de production d'acide téréphtalique et ses sels

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
J. SAUER: "Diels-Alder Reactions II: The Reaction Mechanism", ANGEWANDTE CHEMIE INTERNATIONAL EDITION, vol. 6, no. 1, 1967, pages 16 - 33 *

Also Published As

Publication number Publication date
KR20160048578A (ko) 2016-05-04
KR102250750B1 (ko) 2021-05-11

Similar Documents

Publication Publication Date Title
WO2016064210A1 (fr) Procédé de préparation de téréphtalate de diméthyle avec utilisation d'acétylène
KR102194626B1 (ko) 아세틸렌을 사용한 디메틸테레프탈레이트의 제조방법
WO2020130280A1 (fr) Procédés de récupération et de réutilisation d'un catalyseur d'hydrogénation homogène sélectif
US6803489B2 (en) Purification process of fluorenylidenediallylphenol
WO2018056577A1 (fr) Procédé de production de téréphtalate de diméthyle
KR20170047802A (ko) 디메틸테레프탈레이트의 제조 방법
JPH0616656A (ja) 含フッ素無水フタル酸類の製造方法
JPS61254670A (ja) 線状キナクリドンの製法
JP2012136470A (ja) ３，４’−オキシビスフタルイミド化合物とその製造方法
WO2015088178A1 (fr) Procédé de production à rendement élevé de 1,3-butadiène
CN115536627B (zh) 一种二苯醚四酸二酐的制备方法
WO2019103549A2 (fr) Procédé de préparation de téréphtalate de diméthyle
WO2018062965A1 (fr) Procédé de production d'un copolymère d'ester et de polyéther
WO2019124674A1 (fr) Procédé de purification de maléimide n-substitué
EP1293495B1 (fr) Procede de preparation de composes d'acide bromoisophtalique
JP4238214B2 (ja) ２，６−ナフタレンジカルボン酸の精製方法
WO2019139264A1 (fr) Procédé de cycloaddition de muconate de diméthyle
WO2023219334A1 (fr) Procédé de purification d'une composition de 1,4-cyclohexanediméthanol
CN108299501B (zh) 一种环磷烯氧化物的制备方法、取代的环磷烯氧化物及其制备方法
CN102557850B (zh) 一种具有取代基的环酸酐的制备方法
WO2022124863A1 (fr) Procédés de récupération et de réutilisation d'un catalyseur d'hydrogénation homogène sélectif
WO2023003058A1 (fr) Procédé de préparation d'un composé à base de phtalonitrile
WO2009093862A2 (fr) Procédé écologique permettant de préparer de l'acide téréphtalique par oxydation en plusieurs étapes
Sato et al. A novel polycyclic system: synthesis of 1, 3, 5-tri (1-azulenyl) benzenes by cyclotrimerization of 1-acetylazulenes
CN115583928A (zh) 一类邻苯二甲酸酐衍生物的制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15852786

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15852786

Country of ref document: EP

Kind code of ref document: A1