US-12623995-B2 - Method of preparing heterogeneous linear carbonate using amine-based compound catalyst

US12623995B2US 12623995 B2US12623995 B2US 12623995B2US-12623995-B2

Abstract

The present invention is directed to providing a method of preparing a heterogeneous linear carbonate, including: performing a transesterification reaction of dimethyl carbonate (DMC) and ethanol (EtOH) in the presence of a catalyst, wherein the catalyst is an amine-based compound having a boiling point of 150° C. or more.

Inventors

Jong Myung Choi
Mi Hwa Baek
Wang Gyu KIM
Eun Hye HAN
Jin Hyung Kim

Assignees

LOTTE CHEMICAL CORPORATION

Dates

Publication Date: 20260512
Application Date: 20211104
Priority Date: 20201126

Claims (5)

1 . A method of preparing a heterogeneous linear carbonate, comprising performing a transesterification reaction of dimethyl carbonate (DMC) and ethanol (EtOH) in the presence of a catalyst, wherein the catalyst is an amine-based compound comprising polyetheramine (PEA) having a boiling point of 150° C. or more.
2 . The method of claim 1 , wherein the catalyst has a boiling point of 150° C. or more and 400° C. or less.
3 . The method of claim 1 , wherein the amine-based compound has a weight average molecular weight of 150 g/mol or more and 500 g/mol or less.
4 . The method of claim 1 , wherein the catalyst is added in an amount of 0.1% by weight or more and 30% by weight or less based on a weight of the dimethyl carbonate.
5 . The method of claim 1 , wherein the transesterification reaction is performed in a continuous stirred tank reactor (CSTR).

Description

TECHNICAL FIELD The present invention relates to a method of preparing a heterogeneous linear carbonate using an amine-based compound catalyst. BACKGROUND ART It is well known that a method of preparing ethyl methyl carbonate (EMC) and diethyl carbonate (DEC), which are used as organic solvents for battery electrolytes is through a transesterification reaction of dimethyl carbonate (DMC) and ethanol. At this time, a catalyst is used for the reaction, and as the catalyst, sodium methoxide (NaOCH3, SME) and sodium hydroxide (NaOH), which have excellent activity, are mainly used. However, since the SME or NaOH has low solubility in organic solvents and is insoluble in DMC, EMC, and DEC, it causes column plugging in a reactive distillation process or a purification process, so that process trouble occurs. In this regard, Patent Document 1 discloses that DEC is produced at a high rate by utilizing the SME catalyst, which is a basic homogeneous catalyst, and reactive distillation. However, in this case, the catalyst may pass into the distillation system and cause a reverse reaction during the distillation process, or may be precipitated to block a pipe or adsorbed inside the distillation column to cause corrosion. Accordingly, Patent Document 2 discloses that DEC was prepared using a strongly basic anion exchange resin as a heterogeneous catalyst instead of using SME as a basic homogeneous catalyst, thereby facilitating the separation of a reaction product and a catalyst, however, productivity is low due to insufficient catalytic activity. In addition, product production has to be stopped periodically and the catalyst needed to be regenerated due to the catalyst deactivation problem, which further lowers product productivity and increases production costs. Therefore, there is a need for research on a method for effectively preparing a heterogeneous linear carbonate for a battery electrolyte by solving the above problems. RELATED ART DOCUMENTS Patent Document (Patent Document 1) Korean Patent Publication No. 10-1668571(Patent Document 2) Japanese Patent Publication No. 3340188 DISCLOSURE Technical Problem The present invention provides a method of preparing a heterogeneous linear carbonate, wherein since the method uses an amine-based compound with a relatively high boiling point as a catalyst, which has better catalytic activity than basic anion exchange resins and can obtain high productivity, and a catalyst precipitation problem does not occur, and a desired compound can be easily separated by distillation due to the large boiling point difference, the desired compound can be obtained in excellent yield. Technical Solution One embodiment of the present invention provides a method of preparing a heterogeneous linear carbonate, the method including performing a transesterification reaction of dimethyl carbonate (DMC) and ethanol (EtOH) in the presence of a catalyst, wherein the catalyst is an amine-based compound having a boiling point of 150° C. or more. Advantageous Effects In a method of preparing a heterogeneous linear carbonate according to the present invention, by using an amine-based compound having a relatively high boiling point as a catalyst, catalytic activity is superior to that of the basic anion exchange resin, and there is no problem of stopping production due to catalyst regeneration, so that higher productivity can be obtained. In addition, when the amine-based compound having a high boiling point is used, it is well soluble in dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, and ethanol, so that catalyst precipitation problems do not occur, and as a result, since the boiling point difference from synthesized diethyl carbonate and ethyl methyl carbonate is large, they can be easily separated through distillation, so that a desired compound can be obtained in excellent yield. Furthermore, according to the present invention, by using a CSTR for the transesterification reaction, it is easy to adjust a production ratio of the desired heterogeneous linear carbonate through adjusting a ratio of dimethyl carbonate and ethanol as raw materials. MODES OF THE INVENTION Throughout the specification, when a part is said to “include” a component, this means that the part may further include other components rather than excluding other components unless specifically stated to the contrary. In the present specification, the unit “% by weight” may mean the ratio of the weight of a certain component to total components. Hereinafter, the present invention will be described in detail. One embodiment of the present invention provides a method of preparing a heterogeneous linear carbonate, the method including performing a transesterification reaction of dimethyl carbonate (DMC) and ethanol (EtOH) in the presence of a catalyst, wherein the catalyst is an amine-based compound having a boiling point of 150° C. or more. In the present invention, the heterogeneous linear carbonate means a species of carbon