Method for synthesizing cyclic carbonates

Abstract

The present invention relates to a method for synthesizing cyclocarbonates by reacting an epoxy compound and carbon dioxide at atmospheric pressure and elevated temperature in the presence of a heterogeneous catalyst system comprising an alkali metal halide and silica as well as the use of said catalyst system for the synthesis of cyclocarbonates.

Claims

1. A method for synthesizing a cyclocarbonate, comprising: providing at least one epoxy compound; providing carbon dioxide; providing a heterogeneous catalyst system; reacting the at least one epoxy compound and the carbon dioxide at atmospheric pressure and a temperature in the range of 100 to 150 C. in the presence of the heterogeneous catalyst system, wherein the catalyst system comprises (a) at least one alkali metal halide selected from the group consisting of alkali metal iodides and alkali metal bromides, and (b) silica (SiO.sub.2).

2. The method according to claim 1, wherein the at least one alkali metal halide is selected from the group consisting of lithium iodide (LiI), sodium iodide (NaI), potassium iodide (KI), lithium bromide (LiBr), sodium bromide (NaBr), potassium bromide (KBr) and combinations thereof.

3. The method according to claim 1, wherein the at least one epoxy compound (a) is a multifunctional epoxy resin; and/or (b) is a liquid epoxy resin; and/or (c) is an aliphatic epoxy resin; and/or (d) has a molecular weight of 200 to 1000 g/mol.

4. The method according to claim 3, wherein the at least one epoxy compound (d) has a molecular weight of 400 to 600 g/mol.

5. The method according to claim 1, wherein the reaction temperature is in the range of 120 to 140 C.

6. The method according to claim 1, wherein the carbon dioxide is provided in form of carbon dioxide gas, wherein the reaction is carried out under a carbon dioxide atmosphere.

7. The method according to claim 4, wherein the carbon dioxide is provided in solid form (dry ice) and the method further comprises allowing the solid carbon dioxide to sublimate to gas in the reaction.

8. The method according to claim 1, wherein the heterogeneous catalyst system comprises 0.5 to 5% by weight of the alkali metal halide relative to the epoxy compound and 0.5 to 5% by weight of the silica relative to the epoxy compound.

9. The method according to claim 1, wherein the heterogeneous catalyst system comprises 1.5 to 2.5% by weight of the alkali metal halide relative to the epoxy compound and 1.5 to 2.5% by weight of the silica relative to the epoxy compound.

10. The method according to claim 1, wherein the silica is in form of silica gel particles having a mean diameter of 35 to 70 m.

11. The method according to claim 3, wherein the at least one epoxy compound is a liquid epoxy resin having a viscosity of less than 110 mPas at 25 C.

12. The method according to claim 1 wherein the at least one epoxy compound comprises at least one terminal 1,2-epoxy group.

13. The method according to claim 1 wherein the at least one epoxy compound is selected from: formula (1) ##STR00013## wherein Z represents hydrogen, methyl or ethyl, and X represents a halogen atom or an OH group; or formula (2) ##STR00014## wherein Z represents hydrogen, methyl or ethyl; or the at least one epoxy compound is a glycidyl ester of saturated or ethylenically unsaturated carboxylic acids with at least one substituted or unsubstituted glycidylester group of formula (3) ##STR00015## wherein Z represents hydrogen, methyl or ethyl.

Description

EXAMPLES

Comparative Example 1: Reaction Between Polyethyleneglycol Diglycidyl Ether (PEGDE) and SiO2

(1) ##STR00004##

(2) Polyethyleneglycol diglycidyl ether (PEGDE, 1 g, M.sub.n=500 g/mol) and SiO.sub.2 (20 mg, silica gel mesh 60) were stirred in a glass round bottom flask under CO.sub.2 atmospheric pressure (the air inside the flask was displaced by CO.sub.2 with the help of carbon dioxide filled balloons) at 130 C.

(3) No cyclic carbonate was observed by means of .sup.1H-NMR or IR spectroscopy after 4 h. Only hydrolysis products of the epoxides were detected after 8 h.

Comparative Example 2: Reaction Between Polyethyleneglycol Diglycidyl Ether (PEGDE) and NaI

(4) ##STR00005##

(5) Polyethyleneglycol diglycidyl ether (PEGDE, 1 g, M.sub.n=500 g/mol) and NaI (20 mg) were stirred in a glass round bottom flask under CO.sub.2 atmospheric pressure (the air inside the flask was displaced by CO.sub.2 with the help of carbon dioxide filled balloons) at 130 C.

(6) 100% conversion into the corresponding cyclic carbonate was observed after 4 h by means of .sup.1H-NMR and IR spectroscopy. No side products were observed.

Example 3: Reaction Between Polyethyleneglycol Diglycidyl Ether (PEGDE), SiO2, and NaI

(7) ##STR00006##

(8) Polyethyleneglycol diglycidyl ether (PEGDE, 1 g, M.sub.n=500 g/mol), SiO.sub.2 (20 mg) and NaI (20 mg) were stirred in a glass round bottom flask under CO.sub.2 atmospheric pressure (the air inside the flask was displaced by CO.sub.2 with the help of carbon dioxide filled balloons) at 130 C.

(9) 100% conversion into the corresponding cyclic carbonate was observed after 2 h by means of .sup.1H-NMR and IR spectroscopy. No side products were observed.

Comparative Example 4: Reaction Between Polyethyleneglycol Diglycidyl Ether (PEGDE), and LiBr

(10) ##STR00007##

(11) Polyethyleneglycol diglycidyl ether (PEGDE, 1 g, M.sub.n=500 g/mol) and LiBr (20 mg) were stirred in a glass round bottom flask under CO.sub.2 atmospheric pressure (the air inside the flask was displaced by CO.sub.2 with the help of carbon dioxide filled balloons) at 130 C.

(12) 100% conversion into the corresponding cyclic carbonate was observed after 2 h by means of .sup.1H-NMR and IR spectroscopy. No side products were observed.

Example 5: Reaction Between Polyethyleneglycol Diglycidyl Ether (PEGDE), SiO2, and LiBr

(13) ##STR00008##

(14) Polyethyleneglycol diglycidyl ether (PEGDE, 1 g, M.sub.n=500 g/mol), SiO.sub.2 (20 mg) and LiBr (20 mg) were stirred in a glass round bottom flask under CO.sub.2 atmospheric pressure (the air inside the flask was displaced by CO.sub.2 with the help of carbon dioxide filled balloons) at 130 C.

(15) 100% conversion into the corresponding cyclic carbonate was observed after 1 h by means of .sup.1H-NMR and IR spectroscopy. No side products were observed.

Example 6: Reaction Between D.E.R. 736, SiO2, and NaI

(16) ##STR00009##

(17) D.E.R. 736 from The Dow Chemical Company (1 g), SiO.sub.2 (20 mg) and NaI (20 mg) were stirred in a glass round bottom flask under CO.sub.2 atmospheric pressure (the air inside the flask was displaced by CO.sub.2 with the help of carbon dioxide filled balloons) at 130 C.

(18) 100% conversion into the corresponding cyclic carbonate was observed after 8 h by means of .sup.1H-NMR and IR spectroscopy. No side products were observed.

Example 7: Reaction Between D.E.R. 736, SiO2, and LiBr

(19) ##STR00010##

(20) D.E.R. 736 (1 g), SiO.sub.2 (20 mg) and LiBr (20 mg) were stirred in a glass round bottom flask under CO.sub.2 atmospheric pressure (the air inside the flask was displaced by CO.sub.2 with the help of carbon dioxide filled balloons) at 130 C.

(21) 100% conversion into the corresponding cyclic carbonate was observed after 6 h by means of .sup.1H-NMR and IR spectroscopy. Some side products derived from degradation of epoxide moieties were detected.

Example 8: Reaction Between 1,4-butanediol diglycidyl ether, SiO2, and NaI

(22) ##STR00011##

(23) 1,4-butanediol diglycidyl ether (1 g), SiO.sub.2 (20 mg) and NaI (20 mg) were stirred in a glass round bottom flask under CO.sub.2 atmospheric pressure (the air inside the flask was displaced by CO.sub.2 with the help of carbon dioxide filled balloons) at 130 C.

(24) 100% conversion into the corresponding cyclic carbonate was observed after 2 h by means of .sup.1H-NMR and IR spectroscopy. No side products were observed.

Example 9: Reaction Between 1,4-butanediol diglycidyl ether, SiO2, and LiBr

(25) ##STR00012##

(26) 1,4-butanediol diglycidyl ether (1 g), SiO.sub.2 (20 mg) and LiBr (20 mg) were stirred in a glass round bottom flask under CO.sub.2 atmospheric pressure (the air inside the flask was displaced by CO.sub.2 with the help of carbon dioxide filled balloons) at 130 C.

(27) 100% conversion into the corresponding cyclic carbonate was observed after 2 h by means of .sup.1H-NMR and IR spectroscopy. Some side products derived from degradation of epoxide moieties were detected.