WO2006054833A1 - Procede pour preparer un carbonate lineaire asymetrique - Google Patents

Procede pour preparer un carbonate lineaire asymetrique Download PDF

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Publication number
WO2006054833A1
WO2006054833A1 PCT/KR2005/003490 KR2005003490W WO2006054833A1 WO 2006054833 A1 WO2006054833 A1 WO 2006054833A1 KR 2005003490 W KR2005003490 W KR 2005003490W WO 2006054833 A1 WO2006054833 A1 WO 2006054833A1
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WO
WIPO (PCT)
Prior art keywords
carbonate
linear carbonate
linear
reaction
asymmetric linear
Prior art date
Application number
PCT/KR2005/003490
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English (en)
Inventor
Min-Hyuk Lee
Jeong-Ho Park
Seung-Hwan Kim
Seong-Sam Park
Original Assignee
Sk Chemicals Co., Ltd.
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 Sk Chemicals Co., Ltd. filed Critical Sk Chemicals Co., Ltd.
Publication of WO2006054833A1 publication Critical patent/WO2006054833A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C68/00—Preparation of esters of carbonic or haloformic acids
    • C07C68/08—Purification; Separation; Stabilisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C68/00—Preparation of esters of carbonic or haloformic acids
    • C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/96—Esters of carbonic or haloformic acids

Definitions

  • This invention relates to a method for preparing asymmetric linear carbonate, and more specifically to a method for preparing asymmetric linear carbonate useful as a solvent for lithium secondary battery, etc.
  • Asymmetric linear carbonate such as ethyl methyl carbonate (EMC) has been generally used as a solvent (electrolyte) for lithium secondary battery, and the lithium secondary battery using the asymmetric linear carbonate as an electrolyte has improved characteristics including increased energy density, increased discharge capacity, longer life cycle and higher safety performance in comparison with the battery using a con ⁇ ventional electrolyte. Accordingly, the asymmetric linear carbonate is mainly used as an electrolyte for lithium secondary battery.
  • a conventional method of preparing the asymmetric linear carbonate is an esterification of alkyl chloroformate with alcohol in the presence of a basic catalyst, but the method has problems in that the esterification reaction is very reactive and requires highly toxic starting materials such as phosgene and bisphenol A.
  • a method for preparing asymmetric linear carbonate is disclosed in Japanese Laid - Open patent Publication No. H6- 166660. The method uses a transesterification of symmetric linear carbonate with alkyl alcohol in the presence of a basic catalyst such as metal carbonate salt.
  • a method for preparing the asymmetric linear carbonate disclosed in U.S. patent No. 5,962,720 uses a transes ⁇ terification of two different symmetric carbonates in the presence of a basic catalyst such as a Group IA or Group 2 A metal alkoxide salt or a Group IA or Group 2 A metal amide salt which is a nucleophilic or reductive catalyst.
  • a basic catalyst such as a Group IA or Group 2 A metal alkoxide salt or a Group IA or Group 2 A metal amide salt which is a nucleophilic or reductive catalyst.
  • the method has advantages in that the reaction yield is high, and alcohol is not necessary for the transesterification, but the method has disadvantages in that the basic catalyst should be separated from the reaction product with an Alumina or Silica Gel column, and the trace of water or alcohol in the reactants should be eliminated out before the transesterification reaction to prevent the deterioration of a catalyst activity due to water or alcohol in the reactants.
  • a method disclosed in Japanese Laid-Out Patent publication Nos. 2000-344715 and 2000-344718 produces the asymmetric linear carbonate in the presence of water or alcohol, by using the oxides of rare earth metals of a Group 3B.
  • the method has the problems in that the reaction is carried out at high pressure of 5 to 10 atm, and for long time interval of 200 hours or more. Disclosure of Invention
  • the present invention provides the method for preparing asymmetric linear carbonate, which comprises the steps of: carrying out a transesterification of symmetric linear carbonate with linear ester compound in the presence of a basic catalyst; and separating the asymmetric linear carbonate from the transesterification product.
  • the preferable ester compound includes acetate compound
  • the preferable basic catalyst includes lithium methoxide, lithium ethoxide, sodium methoxide, lithium amide, calcium hydride and the mixtures thereof.
  • R , R , and R can be independently a linear alkyl group, a branched alkyl group, or a cyclic alkyl group.
  • R and R are different from each other and independently a Cl-ClO linear alkyl group, a C3-C10 branched alkyl group, or a C5-C10 cyclic alkyl group, and R is preferably a methyl group or an ethyl group.
  • Cl-ClO represents the number of carbon atoms is 1 to 10.
  • the symmetric linear carbonate can be a linear alkyl carbonate, a branched alkyl carbonate, or a cyclic alkyl carbonate, and preferably can be a Cl-ClO linear alkyl carbonate, a C3-C10 branched alkyl carbonate, or a C5-C10 cyclic alkyl carbonate.
  • the symmetric linear carbonate may include dimethyl carbonate, diethyl carbonate, dipropyl carbonate, di-n-butyl carbonate, and di-t-butyl carbonate having C1-C4 linear alkyl groups.
  • the linear ester compound can be represented by formula RCOOR , wherein R and R are independently an organic group such as a linear alkyl group, a branched alkyl group, or a cyclic alkyl group.
  • R is a methyl group or an ethyl group
  • R is a Cl-ClO linear alkyl group, a C3-C10 branched alkyl group, or a C5-C10 cyclic alkyl group.
  • the preferable linear ester compound is acetate compound
  • the exemplary acetate compound includes methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, n-butyl acetate, t-butyl acetate, the mixtures thereof, and so on.
  • the symmetric linear carbonate and the linear ester compound are used in the molar ratio of 1: 10 to 10: 1, and more preferably in the molar ratio of 1: 9 to 9: 1, and most preferably in the molar ratio of 1: 1.5 to 1: 4 to maximize the reaction yield. If the amounts of the symmetric linear carbonate and the linear ester compound are beyond the above mentioned range, the reaction yield of the final product, namely asymmetric linear carbonate decreases.
  • the basic catalyst for the transesterification reaction may include nucleophilic or reductive metal salt.
  • the preferable basic catalyst includes alkoxide salt of a group IA or a group 2A metal, amide salt of a group IA or a group 2A metal, metal hydride, more preferably hydride of a group IA or a group 2A metal, and the mixtures thereof.
  • Examples of the basic catalyst include lithium methoxide(LiOCH ), lithium ethoxide(LiOC H ), sodium methoxide(NaOCH ), lithium amide(LiNH ), calcium hydride(CaH ) and so on.
  • the preferable amount of the catalyst in the present invention is 0.01 to 10 weight% with respect to the total amount of the symmetric linear carbonate and the linear ester compound, and more preferably 0.1 to 5 weight%. If the amount of the catalyst is less than 0.01 weight% with respect to the total amount of the symmetric linear carbonate and the linear ester compound, the reaction rate decreases. If the amount of the catalyst is more than 10 weight% with respect to the total amount of the symmetric linear carbonate and the linear ester compound, it is eco ⁇ nomically unfavorable without additional advantages.
  • the transesterification reaction can be carried out in a conventional reactor by a conventional batch process or continuous process.
  • the preferable transesterification reaction temperature is 50 0 C to 250 0 C.
  • the preferable reaction temperature is 70 0 C to 120 0 C. If the reaction temperature is less than 50 0 C, the productivity of the reaction decreases because of the slowdown of reaction rate. If the reaction temperature is more than 250 0 C, the reactants may be decomposed, and various byproducts can be produced.
  • the pressure of the transesterification reaction can be widely varied without limitation, but the transesterification reaction can be preferably carried out in atmospheric pressure.
  • the reaction time of the transesterification reaction can also be widely varied without limitation.
  • the transesterification reaction can be carried out for 0.1 hour to 10 hour, and more preferably for 0.5 hour to 4 hour.
  • the transesterification reaction can be carried out until the composition of reaction product is not changed.
  • the variation in the composition of reaction product can be determined by sampling the reaction product periodically during the reaction, and by analyzing the sampled reaction product with a gas chromatography.
  • the asymmetric linear carbonate is separated from the transesterification product.
  • the separation of the asymmetric linear carbonate can be carried out by using a conventional distillation process at atmospheric or reduced pressure.
  • the reaction product is distillated at atmospheric or reduced pressure, compounds in the reaction product are successively distilled according to their boiling points.
  • the reaction product is successively distilled in order of methyl acetate (boiling point: 58°C), ethyl acetate (boiling point: 77°C) dimethyl carbonate (boiling point: 90 0 C), ethyl methyl carbonate, and diethyl carbonate (boiling point: 127°C).
  • methyl acetate boiling point: 58°C
  • ethyl acetate 77°C
  • dimethyl carbonate boiling point: 90 0 C
  • ethyl methyl carbonate ethyl methyl carbonate
  • diethyl carbonate diethyl carbonate
  • the reaction product was analyzed with a gas chromatography.
  • the gas chromatography analysis indicated that methyl acetate(MA) and ethyl methyl carbonate(EMC) were newly generated, and the molar ratio of methyl acetate(MA): ethyl acetate(EA) was determined to be 1 : 1, and the molar ratio of dimethyl carbonate(DMC): ethyl methyl carbonate(EMC): diethyl carbonate(DEC) was determined to be 1 : 2 : 1, and the reaction yield of ethyl methyl carbonate(EMC) was 50% with respect to dimethyl carbonate(DMC).
  • the reaction product was distilled at atmospheric pressure in a distillation tower having the number of theoretical plates of 50 and reflux ratio of more than 5 to produce ethyl methyl carbonate
  • the reaction product was distilled at atmospheric pressure in a dis ⁇ tillation tower having the number of theoretical plates of 50 and reflux ratio of more than 5 to produce ethyl methyl carbonate having the purity of 99% (Distillation yield: 81%).
  • the method for preparing asymmetric linear carbonate according to the present invention can prevent the deterioration of the catalyst activity, and accordingly can produce the asymmetric linear carbonate with high yield in a short time.
  • byproducts are not produced, and the asymmetric linear carbonate and a catalyst can be easily separated, which results in the production of the asymmetric linear carbonate of high purity.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L’invention décrit un procédé pour préparer un carbonate linéaire asymétrique utile en tant qu'électrolyte pour une batterie secondaire au lithium. Le procédé comprend les étapes consistant à : effectuer une transestérification du carbonate linéaire asymétrique avec un composé ester linéaire en présence d’un catalyseur basique ; et séparer le carbonate linéaire asymétrique du produit de la transestérification. Le composé ester linéaire est de préférence un composé acétate.
PCT/KR2005/003490 2004-11-16 2005-10-19 Procede pour preparer un carbonate lineaire asymetrique WO2006054833A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2004-0093601 2004-11-16
KR1020040093601A KR20060054533A (ko) 2004-11-16 2004-11-16 비대칭 선형 카보네이트의 제조방법

Publications (1)

Publication Number Publication Date
WO2006054833A1 true WO2006054833A1 (fr) 2006-05-26

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PCT/KR2005/003490 WO2006054833A1 (fr) 2004-11-16 2005-10-19 Procede pour preparer un carbonate lineaire asymetrique

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KR (1) KR20060054533A (fr)
TW (1) TW200633973A (fr)
WO (1) WO2006054833A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103172519A (zh) * 2011-12-23 2013-06-26 中国科学院兰州化学物理研究所 一种碳酸甲乙酯的合成方法
EP3363779A4 (fr) * 2015-11-24 2019-06-19 Daikin Industries, Ltd. Procédé de production de carbonate à chaîne asymétrique

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102644180B1 (ko) * 2020-11-26 2024-03-05 롯데케미칼 주식회사 우수한 용해도를 가지는 촉매를 이용한 이종 선형 카보네이트를 제조하는 방법
KR102644183B1 (ko) * 2020-11-27 2024-03-05 롯데케미칼 주식회사 산성 이온교환수지를 이용한 이종 선형 카보네이트 제조방법
WO2023096301A1 (fr) * 2021-11-23 2023-06-01 주식회사 엘지화학 Carbonate linéaire asymétrique et procédé de préparation de carbonate linéaire asymétrique

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0710811A (ja) * 1993-06-24 1995-01-13 Mitsubishi Chem Corp ジアルキルカーボネートの製造方法
US5760273A (en) * 1995-10-25 1998-06-02 Mitsubishi Chemical Corporation Process for producing unsymmetrical chain carbonic acid ester
US5962720A (en) * 1997-05-29 1999-10-05 Wilson Greatbatch Ltd. Method of synthesizing unsymmetric organic carbonates and preparing nonaqueous electrolytes for alkali ion electrochemical cells
KR20000055022A (ko) * 1999-02-02 2000-09-05 유현식 비대칭 선형 탄산 에스테르의 제조방법

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0710811A (ja) * 1993-06-24 1995-01-13 Mitsubishi Chem Corp ジアルキルカーボネートの製造方法
US5760273A (en) * 1995-10-25 1998-06-02 Mitsubishi Chemical Corporation Process for producing unsymmetrical chain carbonic acid ester
US5962720A (en) * 1997-05-29 1999-10-05 Wilson Greatbatch Ltd. Method of synthesizing unsymmetric organic carbonates and preparing nonaqueous electrolytes for alkali ion electrochemical cells
KR20000055022A (ko) * 1999-02-02 2000-09-05 유현식 비대칭 선형 탄산 에스테르의 제조방법

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103172519A (zh) * 2011-12-23 2013-06-26 中国科学院兰州化学物理研究所 一种碳酸甲乙酯的合成方法
EP3363779A4 (fr) * 2015-11-24 2019-06-19 Daikin Industries, Ltd. Procédé de production de carbonate à chaîne asymétrique
US10774028B2 (en) 2015-11-24 2020-09-15 Daikin Industries, Ltd. Production method of asymmetric chain carbonate

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Publication number Publication date
KR20060054533A (ko) 2006-05-22
TW200633973A (en) 2006-10-01

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