Process for producing dimethyl carbonate

Patent metadata

Field	Value
Publication number	US-9656943-B2
Application number	US-201514918015-A
Country	US
Kind code	B2
Filing date	Oct 20, 2015
Priority date	Oct 20, 2015
Publication date	May 23, 2017
Grant date	May 23, 2017

Abstract

The present disclosure relates to a recycling method for producing dimethyl carbonate. The process is unique in that it produces a by-product that can be re-used in the process as a raw material for repeating the process. For example, when the process is directed to synthesizing dimethyl carbonate, glycerol is used as a starting material. Glycerol is also a by-product produced during formation of dimethyl carbonate, and therefore it can be re-used as starting material to generate more dimethyl carbonate.

First claim

The invention claimed is:

1. A process for producing a compound of formula (VI) comprising:
(a) reacting a compound of formula (I)

with a halogenating agent to form a compound of formula (II)

wherein, the halogenating agent is represented by HX, wherein X is F, Cl, Br, or I; and R 1 is selected from the group consisting of, hydroxyl, C 1 -C 8 alkyl, C 1 -C 8 alkenyl, C 1 -C 8 alkoxy, C 3 -C 8 cycloalkyl, C 6 -C 10 aryl group and a 5-10 member heteroaryl group having 1-3 heteroatoms selected from the group consisting of N, O and S, wherein the alkyl, alkenyl, cycloalkyl, aryl group and heteroaryl group can optionally be substituted by one or more hydroxyl groups;

(b) reacting the compound of formula (II) with a base in a solvent selected from the group consisting of C 1 -C 6 alcohol to form a compound of formula (III)

(c) reacting the compound of formula (III) with carbon dioxide to form a compound of formula (IV)

(d) reacting the compound of formula (IV) with an alcohol to form a compound of formula (VI) and the compound of formula (I)

wherein,
the alcohol is represented by ROH, wherein R is selected from the group consisting of a C 1 -C 8 alkyl, C 1 -C 8 alkenyl, C 1 -C 8 alkoxy, C 3 -C 8 cycloalkyl, C 6 -C 10 aryl group and a 5-10 member heteroaryl group having 1-3 heteroatoms selected from the group consisting of N, O and S, wherein the alkyl, alkenyl, cycloalkyl, aryl group and heteroaryl group can optionally be substituted by one or more hydroxyl groups; and

(e) recycling the compound of formula (I) formed in (d) into (a) and repeating the chemical reactions of (a)-(d) using the compound of formula (I) formed in (d) as starting material.

2. The process of claim 1 , wherein the halogenating agent in (a) is hydrogen chloride or a mixture of gaseous hydrogen chloride and an aqueous solution of hydrogen chloride.

3. The process of claim 1 , wherein the reaction of the compound of formula (I) with an acid in (a) is carried out in the presence of a catalyst.

4. The process of claim 3 , wherein the catalyst is an organic acid catalyst, an inorganic acid catalyst, or a heterogeneous acid catalyst.

5. The process of claim 4 , wherein the catalyst is an organic acid catalyst selected from the group consisting of a carboxylic, a sulfonic, and a phosphoric acid.

6. The process of claim 1 , wherein the base in (b) is selected from the group consisting of a hydroxide, a carbonate and a bicarbonate of alkali metal, alkaline earth metal, and a basic ion exchange resin.

7. The process of claim 6 , wherein the base in (b) is selected from the group consisting of LiOH, NaOH, KOH, CsOH, RbOH, Mg(OH) 2 , Ca(OH) 2 , Sr(OH) 2 , NH 4 OH, Ba(OH) 2 , Na 2 CO 3 , and K 2 CO 3 , NaHCO 3 and KHCO 3 .

8. The process of claim 1 , wherein the reaction of the compound of formula (III) with carbon dioxide in (c) is carried out in the presence of a catalyst.

9. The process of claim 8 , wherein the catalyst is an alkali metal halide salt.

10. The process of claim 9 , wherein the alkali metal halide salt is selected from NaCl, NaBr, NaI, KCl, KBr and KI.

11. The process of claim 1 , wherein the reaction of the compound of formula (IV) with alcohol in (d) is carried out in the presence of a catalyst.

12. The process of claim 11 , wherein the catalyst is selected from the group consisting of a hydroxide, and a carbonate and a bicarbonate of alkali metal and alkaline earth metal.

13. The process of claim 12 , wherein the catalyst is a base selected from the group consisting of LiOH, NaOH, KOH, CsOH, RbOH, Mg(OH) 2 , Ca(OH) 2 , Sr(OH) 2 , NH 4 OH, Ba(OH) 2 , Na 2 CO 3 , NaHCO 3 , K 2 CO 3 and KHCO 3 .

14. The process of claim 13 , wherein the base is KOH.

15. The process of claim 1 , wherein the alcohol in (d) is methanol.

16. A process for producing dimethyl carbonate comprising:
(a) reacting glycerol with hydrochloric acid to form 3-chloropropane-1,2-diol and water,
(b) reacting 3-chloropropane-1,2-diol with sodium hydroxide in a solvent selected from the group consisting of C 1 -C 6 alcohol to form glycidol, sodium chloride, and water,
(c) reacting glycidol with carbon dioxide in the presence of potassium bromide to form glycerol carbonate,
(d) reacting the glycerol carbonate with methanol in the presence of potassium hydroxide to form dimethyl carbonates and glycerol, and
(e) recycling the glycerol formed in (d) into (a) and repeating the chemical reactions of (a)-(d) using the glycerol formed in (d) as starting material.

17. The process of claim 16 , wherein the reaction of the glycerol with hydrochloric acid in (a) is carried out in the presence of a catalyst.

18. The process of claim 17 , wherein the catalyst is an organic acid catalyst selected from the group consisting of carboxylic, sulfonic, and phosphoric acids.

19. The process of claim 18 , wherein the organic acid catalyst is acetic acid.

Assignees

• Chang Chun Plastics Co Ltd

Inventors

• Huang Chien Fu
• Tsai Yi Ta

Classifications

• C07D213/68

  attached in position 4 · CPC title

• C07C68/065 Primary

  from alkylene carbonates · CPC title

• C07C29/62

  by introduction of halogen; by substitution of halogen atoms by other halogen atoms · CPC title