Process for producing glycerol carbonate methacrylate

Abstract

A process for preparing glycerol carbonate methacrylate, wherein glycidyl methacrylate is reacted with carbon dioxide in the presence of a catalyst and a solvent, wherein the catalyst is potassium iodide, the solvent is acetonitrile, one or more monoalcohols, or any desired mixture of acetonitrile and one or more monoalcohols, and the reaction of glycidyl methacrylate with carbon dioxide is carried out at a pressure from 0.5 to 5 bar.

Claims

1. A process for preparing glycerol carbonate methacrylate comprising reacting glycidyl methacrylate with carbon dioxide in the presence of a catalyst and a solvent, wherein the catalyst is potassium iodide, the solvent is acetonitrile, one or more monoalcohols, or any desired mixture of acetonitrile and one or more monoalcohols, and the reaction of glycidyl methacrylate with carbon dioxide is carried out at a pressure from 0.5 to 1.5 bar.

2. The process according to claim 1, wherein the reaction temperature is 50 to 100° C.

3. The process according to claim 1, wherein the pressure is 0.8 to 1.5 bar.

4. The process according to claim 1, wherein the process is a batchwise process.

5. The process according to claim 1, wherein the monoalcohol is ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol or tert-butanol.

6. The process according to claim 1, wherein the total amount of solvent used is 0.1 to 50 percent by weight based on the total amount of glycidyl methacrylate used.

7. The process according to claim 1, wherein the solvent is acetonitrile and the total amount of solvent used is 2 to 40 percent by weight based on the total amount of glycidyl methacrylate used.

8. The process according to claim 1, wherein the molar ratio between the total amount of catalyst used and the total amount of glycidyl methacrylate used is 0.005:1 to 0.5:1.

9. The process according to claim 1, wherein carbon dioxide as the carbon dioxide-containing gas is fed into the reaction mixture comprising the catalyst, the solvent, GMA that has not yet reacted, and optionally any GCMA already formed, and/or into the gas space above the reaction mixture.

10. The process according to claim 9, wherein the carbon dioxide-containing gas is fed in continuously.

11. The process according to claim 1, wherein an oxygen-containing gas is fed into the reaction mixture comprising the catalyst, the solvent, GMA that has not yet reacted, and optionally any GCMA already formed, and/or into the gas space above the reaction mixture.

12. The process according to claim 1, wherein the reaction of glycidyl methacrylate to glycerol carbonate methacrylate takes place in the presence of a stabilizer and the stabilizer is phenothiazine, one or more phenolic compounds, one or more N-oxyls or any desired mixture of the abovementioned stabilizers.

13. The process according to claim 1, wherein the reaction mixture resulting from conversion of most of the glycidyl methacrylate used into glycerol carbonate methacrylate is worked up and the workup comprises one or more extraction steps and/or one or more distillation steps.

14. The process according to claim 13, wherein the workup includes, in addition to one or more extraction steps and/or distillation steps, the addition of one or more acids.

15. The process according to claim 14, wherein the acid is phosphinic acid and/or phosphoric acid.

16. A process for preparing glycerol carbonate methacrylate comprising reacting glycidyl methacrylate with carbon dioxide in the presence of a catalyst and a solvent, wherein the solvent is acetonitrile, one or more monoalcohols, or any desired mixture of acetonitrile and one or more monoalcohols, and the catalyst consists of potassium iodide, and the reaction of glycidyl methacrylate with carbon dioxide is carried out at a pressure from 0.5 to 5 bar.

Description

INVENTIVE EXAMPLES

Example 1

(1) A round-bottomed flask equipped with jacketed coil condenser, magnetic stirrer, thermometer, CO.sub.2 inlet and with pressure equalization is charged with 7 mg of PTZ and 4.15 g of acetonitrile. To this is added 41.5 g of GMA and 4.75 g of Kl. CO.sub.2 (approx. 2 L/h) and 0.5 L/h of air are fed into the reaction mixture. The reaction mixture is heated to an internal temperature from 80 to 85° C. Samples are collected at regular intervals and analyzed by gas chromatography. After 6 h, the conversion of GMA into GCMA is 80.25%. The mixture comprises (excluding the solvent acetonitrile and disregarding components that do not pass through the GC) 79.38 area % of GCMA and 19.53 area % of GMA. The sum of the by-products is 1.09 area %. The selectivity is 98.6%. The reaction solution is colorless.

Example 2

(2) A round-bottomed flask equipped with jacketed coil condenser, magnetic stirrer, thermometer, CO.sub.2 inlet and with pressure equalization is charged with 7 mg of PTZ and 0.42 g of n-butanol. To this is added 41.5 g of GMA and 4.75 g of Kl. CO.sub.2 (approx. 2 L/h) and 0.5 L/h of air are fed into the reaction mixture. The reaction mixture is heated to an internal temperature from 80 to 85° C. Samples are collected at regular intervals and analyzed by gas chromatography. After 6 h, the conversion of GMA into GCMA is 82.7%. The mixture comprises (disregarding components that do not pass through the GC) 81.63 area % of GCMA and 17.04 area % of GMA. The sum of the by-products is 0.9 area %. The amount of n-butanol is 0.43 area %. The selectivity is 98.9%. The reaction solution is colorless.

Example 3

(3) A round-bottomed flask equipped with jacketed coil condenser, magnetic stirrer, thermometer, CO.sub.2 inlet and with pressure equalization is charged with 7 mg of PTZ and 2.08 g of sec-butanol. To this is added 41.5 g of GMA and 4.75 g of Kl. CO.sub.2 (approx. 2 L/h) and 0.5 L/h of air are fed into the reaction mixture. The reaction mixture is heated to an internal temperature from 80 to 85° C. Samples are collected at regular intervals and analyzed by gas chromatography. After 6 h, the conversion of GMA into GCMA is 84.3%. The mixture comprises (disregarding components that do not pass through the GC) 80.59 area % of GCMA and 15.04 area % of GMA. The sum of the by-products is 1.72 area %. The amount of sec-butanol is 2.65 area %. The selectivity is 97.9%. The reaction solution is colorless.

Example 4

(4) A round-bottomed flask equipped with jacketed coil condenser, magnetic stirrer, thermometer, CO.sub.2 inlet, and with pressure equalization is charged with 7 mg of PTZ and 2.08 g of acetonitrile. To this is added 41.5 g of GMA and 4.75 g of Kl. CO.sub.2 (approx. 2 L/h) and 0.5 L/h of air are fed into the reaction mixture. The reaction mixture is heated to an internal temperature from 80 to 85° C. Samples are collected at regular intervals and analyzed by gas chromatography. After 6 h, the conversion of GMA into GCMA is 80.9%. The mixture comprises (excluding the solvent acetonitrile and disregarding components that do not pass through the GC) 80.03 area % of GCMA and 18.85 area % of GMA. The sum of the by-products is 1.12 area %. The selectivity is 98.6%. The reaction solution is colorless.

Example 5

(5) A round-bottomed flask equipped with jacketed coil condenser, magnetic stirrer, thermometer, CO.sub.2 inlet, and with pressure equalization is charged with 7 mg of PTZ and 2.08 g of isopropanol. To this is added 41.5 g of GMA and 2.37 g of Kl. CO.sub.2 (approx. 2 L/h) and 0.5 L/h of air are fed into the reaction mixture. The reaction mixture is heated to an internal temperature from 80 to 85° C. Samples are collected at regular intervals and analyzed by gas chromatography. After 8 h, the conversion of GMA into GCMA is 98.1%. The mixture comprises (excluding the solvent isopropanol and disregarding components that do not pass through the GC) 96.68 area % of GCMA and 1.91 area % of GMA. The sum of the by-products is 1.41 area %. The selectivity is 98.1%. The reaction solution is slightly yellowish.

Example 6

(6) A round-bottomed flask equipped with jacketed coil condenser, magnetic stirrer, thermometer, CO.sub.2 inlet, and with pressure equalization is charged with 7 mg of PTZ and 2.08 g of acetonitrile. To this is added 41.5 g of GMA and 4.75 g of finely ground Kl. CO.sub.2 (approx. 2 L/h) and 0.5 L/h of air are fed into the reaction mixture. The reaction mixture is heated to an internal temperature from 80 to 85° C. Samples are collected at regular intervals and analyzed by gas chromatography. After 6 h, the conversion of GMA into GCMA is 80.3%. The mixture comprises (excluding the solvent acetonitrile and disregarding components that do not pass through the GC) 79.5 area % of GCMA and 19.56 area % of GMA. The sum of the by-products is 0.94 area %. The selectivity is 98.8%. The reaction solution is colorless.

Example 7

(7) A round-bottomed flask equipped with jacketed coil condenser, magnetic stirrer, thermometer, CO.sub.2 inlet, and with pressure equalization is charged with 7 mg of PTZ and 0.42 g of n-butanol. To this is added 41.5 g of GMA and 4.75 g of Kl. CO.sub.2 (approx. 2 L/h) and 0.5 L/h of air are fed into the reaction mixture. The reaction mixture is heated to an internal temperature from 80 to 85° C. Samples are collected at regular intervals and analyzed by gas chromatography. After 6 h, the conversion of GMA into GCMA is 81.5%. The mixture comprises (disregarding components that do not pass through the GC) 80.45 area % of GCMA and 18.24 area % of GMA. The sum of the by-products is 0.99 area %. The amount of n-butanol is 0.32 area %. The selectivity is 98.8%. The reaction solution is colorless.

Example 8

(8) A round-bottomed flask equipped with jacketed coil condenser, stirrer, thermometer, CO.sub.2 inlet, and with pressure equalization is charged with 540 mg of MeHQ, 11 mg of PTZ, 72.9 g of Kl, and 238 g of acetonitrile. To this is added 425 g of GMA. CO.sub.2 (approx. 5 L/h) and 1 L/h of air are fed into the reaction mixture. The reaction mixture is heated to an internal temperature from 80 to 85° C. Samples are collected at regular intervals and analyzed by gas chromatography. After 27 h, the conversion of GMA into GCMA is 99.4%. The reaction solution still contains 0.56 area % of GMA. After cooling, the reaction mixture is concentrated under reduced pressure and twice extracted with 50 ml of water, with phase separation. The organic phase is dried over sodium sulfate, filtered, and the filtrate is concentrated again under reduced pressure. 530 g (98.2% yield) of a light-colored liquid is obtained in a purity of 97.2 area %. The residual GMA content is 1.6 area %. The selectivity is 98.8%. The Hazen color value is 88.

Example 9

(9) A round-bottomed flask equipped with jacketed coil condenser, stirrer, thermometer, CO.sub.2 inlet, and with pressure equalization is charged with 1.14 g of MeHQ, 23 mg of PTZ, 103 g of Kl, and 504 g of acetonitrile. To this is added 900 g of GMA. CO.sub.2 (approx. 30 L/h) and 1 L/h of air are fed into the reaction mixture. The reaction mixture is heated to an internal temperature from 80 to 85° C. Samples are collected at regular intervals and analyzed by gas chromatography. After 7 h, the feed rate is reduced to approx. 10 L/h. After 15 h, the conversion of GMA into GCMA is 99.11%. The reaction solution still contains 0.64 area % of GMA.

Example 10

(10) 2 g of a reaction mixture prepared in analogous manner to example 9 that has a conversion of GMA into GCMA of 99.41% and still contains 0.42 area % of GMA (0.5 area % without integration of the solvent acetonitrile) is mixed with 0.2 g of phosphinic acid (50% by weight) and the mixture is stirred at room temperature for 1.5 h. A sample is collected and analyzed by gas chromatography. There is still 0.07 area % of GMA remaining (without integration of the solvent).

Example 11

(11) 2 g of a reaction mixture prepared in analogous manner to example 9 that has a conversion of GMA into GCMA of 99.41% and still contains 0.42 area % of GMA (0.5 area % without integration of the solvent acetonitrile) is mixed with 0.2 g of phosphoric acid (85% by weight) and the mixture is stirred at room temperature for 1.5 h. There is still 0.11 area % of GMA remaining (without integration of the solvent).

Example 12

(12) 2 g of a reaction mixture prepared in analogous manner to example 9 that has a conversion of GMA into GCMA of 99.41% and still contains 0.42 area % of GMA (0.5 area % without integration of the solvent acetonitrile) is mixed with 0.2 g of acetic acid (99%) and the mixture is stirred at room temperature for 1.5 h. There is still 0.2 area % of GMA remaining (without integration of the solvent and of the acetic acid).

Example 13

(13) 2 g of a reaction mixture prepared in analogous manner to example 9 that has a conversion of GMA into GCMA of 99.41% and still contains 0.42 area % of GMA (0.5 area % without integration of the solvent acetonitrile) is mixed with 0.2 g of formic acid (98%) and the mixture is stirred at room temperature for 1.5 h. There is still 0.14 area % of GMA remaining (without integration of the solvent and the formic acid).

Example 14

(14) A reaction mixture analogous to example 9 is cooled and then mixed with 12 g of phosphinic acid (50% by weight), stirred for 30 min, and filtered. The solution is concentrated under reduced pressure and twice extracted with 150 ml of water, with phase separation. It is then neutralized with aqueous Na.sub.2CO.sub.3 solution. After phase separation, the organic phase is concentrated again under reduced pressure. 1153 g of a light-colored liquid is obtained in a purity of 98.3 area %. The residual GMA content is <20 ppm (UPLC) The Hazen color value is 100.

Example 15

(15) A heatable jacketed reactor equipped with jacketed coil condenser, disk stirrer, thermometer, CO.sub.2 inlet, and with pressure equalization is charged with 2.8 g of MeHQ, 56 mg of PTZ, 252 g of Kl, and 1233 g of acetonitrile. To this is added 2200 g of GMA. CO.sub.2 (approx. 40 L/h) and 1 L/h of air are fed into the reaction mixture. The reaction mixture is heated to an internal temperature from 85 to 90° C. Samples are collected at regular intervals and analyzed by gas chromatography. After 13 h, the conversion of GMA into GCMA is 99.46%. The reaction solution still contains 0.36 area % of GMA. Acetonitrile is distilled off under reduced pressure and the mixture is then cooled to 50° C. 500 ml of water is added and the mixture is extracted. The aqueous phase is removed. The reaction mixture is mixed with 36 g of phosphinic acid (50% by weight) and extracted twice with 500 ml of water at room temperature. The organic phase is neutralized with aqueous Na.sub.2CO.sub.3 solution and the aqueous phase is separated and concentrated under reduced pressure. 2798 g of a light-colored liquid is obtained in a purity of 98.7 area %. The residual GMA content is <20 ppm (UPLC) The Hazen color value is 32.

Example 16

(16) A heatable jacketed reactor equipped with jacketed coil condenser, disk stirrer, thermometer, CO.sub.2 inlet, and with pressure equalization is charged with 3.05 g of MeHQ, 348 mg of PTZ, 275 g of Kl, and 24 g of tert-butanol. To this is added 2400 g of GMA. CO.sub.2 (approx. 35 L/h) and 1 L/h of air are fed into the reaction mixture. The reaction mixture is heated to an internal temperature from 90 to 95° C. Samples are collected at regular intervals and analyzed by gas chromatography. After 13 h, the conversion of GMA into GCMA is 99.65%. 871 g of CO.sub.2 was used. The reaction solution still contains 0.34 area % of GMA. After cooling to 40° C., 500 ml of water is added and the mixture is extracted. The aqueous phase is removed. The reaction mixture is mixed with 31 g of phosphinic acid (50% by weight) and extracted two more times with 500 ml of water. The organic phase is neutralized with aqueous Na.sub.2CO.sub.3 solution and the aqueous phase is separated and concentrated under reduced pressure. A further 15 g of phosphinic acid (50% by weight) is added. 3059 g of a light-colored liquid is obtained in a purity of 98 area %. The residual GMA content is <20 ppm (UPLC) The Hazen color value is 34.

Example 17

(17) A heatable jacketed reactor equipped with jacketed coil condenser, disk stirrer, thermometer, CO.sub.2 inlet, and with pressure equalization is charged with 4.3 g of MeHQ, 86 mg of PTZ, 387 g of Kl, and 169 g of acetonitrile. To this is added 3386 g of GMA. CO.sub.2 (approx. 40 L/h) and 1 L/h of air are fed into the reaction mixture. The reaction mixture is heated to an internal temperature from 90 to 95° C. Samples are collected at regular intervals and analyzed by gas chromatography. After 16 h, the conversion of GMA into GCMA is 99.44%. The reaction solution still contains 0.53 area % of GMA. After cooling to 60° C., 500 ml of water is added and the mixture is extracted. The aqueous phase is removed. The reaction mixture is mixed with 31 g of phosphinic acid (50% by weight) and extracted two more times with 500 ml of water at 40 to 50° C. The organic phase is neutralized with aqueous Na.sub.2CO.sub.3 solution and the aqueous phase is separated and concentrated under reduced pressure. 4299 g of a light-colored liquid is obtained in a purity of 98.3 area %. The residual GMA content is <20 ppm (UPLC) The Hazen color value is 193.

Example 18

(18) A heatable jacketed reactor equipped with jacketed coil condenser, disk stirrer, thermometer, CO.sub.2 inlet, and with pressure equalization is charged with 2.92 g of MeHQ, 58 mg of PTZ, 263 g of Kl, and 115 g of acetonitrile. To this is added 2300 g of GMA. CO.sub.2 (approx. 50 to 70 L/h) is fed into the reaction mixture. The reaction mixture is heated to an internal temperature from 95 to 98° C. Samples are collected at regular intervals and analyzed by gas chromatography. After 7 h, the conversion of GMA into GCMA is 99.04%. 815 g of CO.sub.2 was used. The reaction mixture is cooled and then mixed with 31 g of phosphinic acid (50% by weight), stirred for 30 min, and filtered. The solution is twice extracted with 500 ml of water at 40° C., with phase separation. The mixture is then neutralized with aqueous Na.sub.2CO.sub.3 solution and extracted again with 500 ml of water. After phase separation, 9 g of phosphinic acid (50% by weight) is added. After 20 min, the mixture is neutralized again with aqueous Na.sub.2CO.sub.3 solution, the phases are separated, and the organic phase is concentrated under reduced pressure. 2864 g of a light-colored liquid is obtained, which is filtered again. The purity is 98.5 area %. The residual GMA content is <20 ppm (UPLC) The Hazen color value is 20.

COMPARATIVE EXAMPLES

Example C1

(19) A round-bottomed flask equipped with jacketed coil condenser, magnetic stirrer, thermometer, CO.sub.2 inlet, and with pressure equalization is charged with 7 mg of PTZ. To this is added 41.5 g of GMA and 4.75 g of Kl. CO.sub.2 (approx. 2 L/h) and 0.5 L/h of air are fed into the reaction mixture. The reaction mixture is heated to an internal temperature from 80 to 85° C. Samples are collected at regular intervals and analyzed by gas chromatography. After 6 h, the conversion of GMA into GCMA is 68.9%. The mixture comprises (disregarding components that do not pass through the GC) 68.41 area % of GCMA and 30.9 area % of GMA. The sum of the by-products is 0.69 area %. The selectivity is 99%. The reaction solution is colorless. The conversion of GMA into GCMA can be seen to occur considerably more slowly at ambient pressure in the absence of a suitable solvent.

Example C2

(20) A round-bottomed flask equipped with jacketed coil condenser, magnetic stirrer, thermometer, CO.sub.2 inlet, and with pressure equalization is charged with 7 mg of PTZ and 2.08 g of triethylamine. To this is added 41.5 g of GMA and 4.75 g of Kl. CO.sub.2 (approx. 2 L/h) and 0.5 L/h of air are fed into the reaction mixture. The reaction mixture is heated to an internal temperature from 70 to 74° C.

(21) Samples are collected at regular intervals and analyzed by gas chromatography. After 7 h, the conversion of GMA into GCMA is 84.4%. The mixture comprises (disregarding components that do not pass through the GC) 79.21 area % of GCMA and 14.7 area % of GMA. The sum of the by-products is 5.97 area %. The selectivity is 93%. The reaction solution is orange.

Example C3

(22) A round-bottomed flask equipped with jacketed coil condenser, magnetic stirrer, thermometer, CO.sub.2 inlet, and with pressure equalization is charged with 17 mg of PTZ and 4.35 g of triethylamine. To this is added 42 g of GMA and 7.2 g of Kl. CO.sub.2 (approx. 2 L/h) is fed into the reaction mixture. The reaction mixture is heated to an internal temperature from 71 to 72° C. Samples are collected at regular intervals and analyzed by gas chromatography. After 28 h, the conversion of GMA into GCMA is 99.26%. The mixture comprises (disregarding components that do not pass through the GC) 91.07 area % of GCMA and 0.68 area % of GMA. The sum of the by-products is 8.14 area %. The selectivity is 91.8%.

(23) The reaction mixture is worked up. The flask contents are mixed with 10 ml of ethyl acetate, transferred to a separating funnel, and extracted with 30×30 ml of water. The combined aqueous phases are extracted with 20 ml of ethyl acetate. The combined organic phases are then extracted again with 20 ml of saturated NaCl solution. After phase separation, the organic phase is dried over sodium sulfate, filtered, and washed with dichloromethane. The filtrate is concentrated under reduced pressure. 50.4 g of a brown solution is obtained in a purity of 93.9%. The yield is 94.5%. The Hazen color value was no longer measurable. The iodine color value is 23.