Method for preparing dialkyl carbonate

Patent metadata

Field	Value
Publication number	US-9371269-B2
Application number	US-201314100078-A
Country	US
Kind code	B2
Filing date	Dec 9, 2013
Priority date	Jul 31, 2009
Publication date	Jun 21, 2016
Grant date	Jun 21, 2016

Abstract

The present invention provides a method for preparing dialkyl carbonate from urea or alkyl carbamate and alkyl alcohol using an ionic liquid comprising a cation, which produces a hydrogen ion, and a hydrophobic anion containing fluorine with high temperature stability in the presence of catalyst containing a metal oxide or hydrotalcite. Since the present invention can prepare dialkyl carbonate at a pressure lower than those of existing methods, it does not require an expensive pressure control device and peripheral devices for maintaining high pressure including the installation cost. It is also the method for preparing a dialkyl carbonate with high yield, thus improving economical efficiency. Moreover, the method of the present invention hardly produces any waste during the process and is thus an eco-friendly method.

First claim

The invention claimed is:

1. A method for preparing dialkyl carbonate by reacting alkyl alcohol with urea or alkyl carbamate in the presence of: an ionic liquid comprising a cation capable of generating a hydrogen ion (H+), and a hydrophobic anion containing fluorine, and a catalyst,
wherein said cation is a quaternary ammonium cation, an imidazolium cation, a pyridium cation, a pyrazolium cation, a pyrrolinium cation, a quaternary phosphonium cation, a thiazolium cation, or a sulfonium cation, and said hydrophobic anion is bis(trifluoromethylsulfonyl)imide, trifluoromethanesulfonate, or tris(trifluoromethylsulfonyl)methanide.

2. The method for preparing dialkyl carbonate according to claim 1 , wherein the quaternary ammonium cation contains at least one substituent selected from the group consisting of a C 1 -C 5 hydroxyalkyl group, a C 1 -C 5 alkoxy group, and a C 1 -C 5 alkyl group.

3. The method for preparing dialkyl carbonate according to claim 2 , wherein the quaternary ammonium cation is a hydroxymethyltrimethylammonium cation, a hydroxyethyltrimethylammonium cation, a hydroxyethyltriethylammonium cation, a hydroxyethyltripropylammonium cation, a hydroxyethyltributylammonium cation, a tetraethylammonium cation, or a tetrabutylammonium cation.

4. The method for preparing dialkyl carbonate according to claim 3 , wherein the imidazolium cation is a 1,3-di(C 1 -C 5 )alkyl-imidazolium cation or a 1-hydroxy(C 1 -C 5 )alkyl-3-(C 1 -C 5 )alkyl imidazolium cation.

5. The method for preparing dialkyl carbonate according to claim 1 , wherein the hydrophobic anion is bis(trifluoromethylsulfonyl)imide.

6. The method for preparing dialkyl carbonate according to claim 1 , wherein the ionic liquid is [ethyltrimethylammonium][bis(trifluoromethylsulfonyl)imide], [hydroxyethyltriethylammonium][bis(trifluoromethylsulfonyl)imide], [1-hydroxyethyl-3-methyl-imidazolium][bis(trifluoromethylsulfonyl)imide], or [1-ethyl-3-methylimidazolium][bis(trifluoromethylsulfonyl)imide].

7. The method for preparing dialkyl carbonate according to claim 1 , wherein the catalyst comprises at least one selected from the group consisting of CaO, MgO, ZnO, PbO, La 2 O 3 , Y 2 O 3 and hydrotalcite.

8. The method for preparing dialkyl carbonate according to claim 1 , wherein the catalyst is used in an amount of 1 to 10 parts by weight per 100 parts by weight of the ionic liquid.

9. The method for preparing dialkyl carbonate according to claim 1 , wherein the urea or alkyl carbamate is used in an amount of 1 to 30 parts by weight per 100 parts by weight of the ionic liquid and the alkyl alcohol is used in a molar ratio of 5 to 25 per mole of the urea or alkyl carbamate.

10. The method for preparing dialkyl carbonate according to claim 1 , wherein the reaction is carried out in a temperature range from 140 to 240° C.

11. The method for preparing dialkyl carbonate according to claim 10 , wherein the reaction pressure is carried out below a saturated vapor pressure of alkyl alcohol or atmospheric pressure at reaching the reaction temperature.

12. The method for preparing dialkyl carbonate according to claim 10 , wherein the reaction is carried out at or below atmospheric pressure.

13. A method for preparing dialkyl carbonate by reacting alkyl alcohol with urea or alkyl carbamate in the presence of: an ionic liquid comprising a cation capable of generating a hydrogen ion (H+), and a hydrophobic anion containing fluorine, and a catalyst,
wherein said cation is a hydroxymethyltrimethylammonium cation, a hydroxyethyltrimethylammonium cation, a hydroxyethyltriethylammonium cation, a hydroxyethyltripropylammonium cation, a hydroxyethyltributylammonium cation, a tetraethylammonium cation, or a tetrabutylammonium cation, and said hydrophobic anion is bis(trifluoromethylsulfonyl)imide.

14. The method for preparing dialkyl carbonate according to claim 13 , wherein the ionic liquid is [ethyltrimethylammonium][bis(trifluoromethylsulfonyl)imide], [hydroxyethyltriethylammonium][bis(trifluoromethylsulfonyl)imide], [1-hydroxyethyl-3-methyl-imidazolium][bis(trifluoromethylsulfonyl)imide], or [1-ethyl-3-methylimidazolium][bis(trifluoromethylsulfonyl)imide].

15. The method for preparing dialkyl carbonate according to claim 13 , wherein the catalyst comprises at least one selected from the group consisting of CaO, MgO, ZnO, PbO, La 2 O 3 , Y 2 O 3 and hydrotalcite.

16. The method for preparing dialkyl carbonate according to claim 13 , wherein the catalyst is used in an amount of 1 to 10 parts by weight per 100 parts by weight of the ionic liquid.

17. The method for preparing dialkyl carbonate according to claim 13 , wherein the urea or alkyl carbamate is used in an amount of 1 to 30 parts by weight per 100 parts by weight of the ionic liquid and the alkyl alcohol is used in a molar ratio of 5 to 25 per mole of the urea or alkyl carbamate.

18. The method for preparing dialkyl carbonate according to claim 13 , wherein the reaction is carried out in a temperature range from 140 to 240° C.

19. The method for preparing dialkyl carbonate according to claim 18 , wherein the reaction pressure is carried out below a saturated vapor pressure of alkyl alcohol or atmospheric pressure at reaching the reaction temperature.

20. The method for preparing dialkyl carbonate according to claim 18 , wherein the reaction is carried out at or below atmospheric pressure.

Assignees

• Res Inst Ind Science & Tech

Inventors

• Koh Jae Cheon
• Kim Chul Ung
• Kim Yun Min

Classifications

• C07C68/00 Primary

  Preparation of esters of carbonic or haloformic acids · CPC title

• C07C69/96

  Esters of carbonic or haloformic acids · CPC title