Process for producing (meth)acrylates from glycerol carbonate

Abstract

A process for preparing an ester of (meth)acrylic acid or a derivative thereof comprises reacting (meth)acrylic acid or a derivative thereof with glycerol carbonate at a reaction temperature of 10 to 150 C. without a solvent in the presence of at least one enzyme catalyzing the esterification reaction.

Claims

1. The process for preparing an ester of (meth)acrylic acid or a derivative thereof by reaction of (meth)acrylic acid or an ester thereof with glycerol carbonate at a reaction temperature of 10 to 150 C. without a solvent in the presence of at least one enzyme catalyzing the esterification reaction.

2. The process according to claim 1 wherein the reaction temperature is in the range from 10 to 100 C.

3. The process according to claim 1, wherein the enzyme used is a lipase from Candida antarctica.

4. The process according to claim 1, wherein the at least one enzyme is present on a carrier material.

5. The process according to claim 1, wherein the (meth)acrylic acid ester used is a C.sub.1-12-alkylester.

6. The process according to claim 1, in the presence of a drier.

7. The process according to claim 1, in the presence of at least one stabilizer.

8. The process according to claim 1, wherein water, alcohols or mixtures thereof are removed during the reaction by distillation.

9. The process according to claim 1, wherein the molar ratio of (meth)acrylic acid or an ester thereof to glycerol carbonate is in the range from 2:1 to 30:1.

10. The process according to claim 1, wherein the resulting glycerol carbonate (meth)acrylate is converted into glycerol mono(meth)acrylate after the reaction.

11. The process according to claim 1, wherein the reaction temperature is in the range from 20 to 90 C.

12. The process according to claim 1, wherein the reaction temperature is in the range from 40 to 60 C.

13. The process according to claim 1, wherein the (meth)acrylic acid ester used is a methyl, ethyl or propyl ester.

Description

EXAMPLES

(1) Novozym 435 enzyme is used in all runs. It is a lipase from Candida antarctica on a macroporous, divinylbenzene-crosslinked methacrylate-based polymer in spherical bead form. The carrier material has a particle size (D.sub.80) of 0.315 to 1.0 mm and an effective size of 0.32 to 0.45 mm. The density is 1.06 g/ml; the water content is 55 to 65 wt %. The BET surface area of the carrier material is 130 m.sup.2/g. The pore volume of the carrier material is 0.5 cm.sup.3/g. The pore diameter of the pores present in the carrier material is 15 nm.

Example 1 (without Molecular Sieve)

(2) Glycerol carbonate (4.0 g, 0.034 mol), methyl acrylate (15.0 g, 0.174 mol), MeHQ (ca. 400 ppm), Novozym 435 (0.4 g, 10 wt %) were weighed into a 50 ml Schott flask. The batch was shaken in a water bath shaker at 40 C. Conversion was policed by GC. The results after 2 h, 4 h and 8 h are shown in Table 1:

(3) TABLE-US-00001 TABLE 1 2 h 4 h 8 h [area %] [area %] [area %] glycerol carbonate 50.50 45.50 44.50 glycerol carbonate acrylate 49.50 54.50 55.50

Example 2 (with Molecular Sieve)

(4) Glycerol carbonate (4.0 g, 0.034 mol), methyl acrylate (15.0 g, 0.174 mol), MeHQ (ca. 400 ppm), Novozym 435 (0.4 g, 10 wt %) and 5 A molecular sieve (9 g) were weighed into a 50 ml Schott flask. The batch was shaken in a water bath shaker at 40 C. Conversion was policed by GC. The results after 2 h, 4 h and 8 h are shown in Table 2:

(5) TABLE-US-00002 TABLE 2 2 h 4 h 8 h [area %] [area %] [area %] glycerol carbonate 58.50 17.10 <1 glycerol carbonate acrylate 41.50 82.90 >99

Example 3 (Scaled-Up Experiment)

(6) Glycerol carbonate (1000 g, 8.46 mol), methyl acrylate (3645 g, 42.34 mol), MeHQ (400 mg) and Novozym 435 (75 g, 7.5 wt %) were weighed into a 10 L HWS Miniplant reactor. This was followed by stirring at 40 C., 195 mbar and 140 rpm. Methanol was continuously removed from the methanol/methyl acrylate azeotrope by distillation. Conversion was policed by GC. The results after certain times are shown in Table 3:

(7) TABLE-US-00003 TABLE 3 Time Time Reactant Product [h] [min] [area %, RT time: 6.048] [area %, RT time: 6.867] 0 0 94.1 0 2.00 120 40.99 59 4.00 240 27.87 72.12 6.00 360 18.97 81.02 9.00 540 13.73 86.26 11.00 660 11.54 88.45 14.00 840 9.18 90.81 16.00 960 8.21 91.78 18.00 1080 6.41 93.58 20.00 1200 6.05 93.94 23.00 1380 4.27 95.72 25.00 1500 3.63 96.36

Example 4 (Scaled-Up Experiment)

(8) Glycerol carbonate (600 g, 5.08 mol), methyl acrylate (4374 g, 50.81 mol), MeHQ (250 mg) and Novozym 435 (45 g, 7.6 wt %) were weighed as fixed bed into a 10 L HWS Miniplant reactor. The reaction mixture was continuously pumped through this fixed bed until the reaction had ended. The conditions were 50 C., 195 mbar and 140 rpm. Methanol was continuously removed from the methanol/methyl acrylate azeotrope by distillation. Conversion was policed by GC. The results after certain times are shown in Table 4: Table 4:

(9) TABLE-US-00004 TABLE 4 Time Time Reactant Product [h] [min] [area %, RT time: 6.048] [area %, RT time: 6.867] 0.00 0 96.34 0 1.00 60 32.91 67.08 2.00 120 24.2 75.79 4.00 240 13.61 86.38 5.00 300 13.69 86.3 6.00 360 8.85 91.14 8.00 480 6.01 93.98 10.00 600 3.67 96.32 12.00 720 3.30 96.69 14.00 840 2.81 97.48 15.00 900 1.42 98.57