Pre-Esterification Of Primary Polyols To Improve Solubility In Solvents Used In The Polyol Process

• US 20110269981A1
• Filed: 12/31/2009
• Published: 11/03/2011
• Est. Priority Date: 04/26/2005
• Status: Active Grant

• Current Assignee: Battelle Memorial Institute
• Original Assignee: Battelle Memorial Institute
• Inventors: Garbark, Daniel B., Vijayendran, Bhima Rao, Benecke, Herman Paul
• Granted Patent: US 8,877,952 B2
• Time in Patent Office: Days
• US Class Current: 554/170
• CPC Class Codes: C11C 3/003 by esterification of fatty acids with alcohols C11C3/02 takes precedence
• CPC Class Codes: C11C 3/04 by esterification of fats or fatty oils
• CPC Class Codes: C11C 3/06 with glycerol
• CPC Class Codes: C11C 3/10 Ester interchange

Abstract

Methods to pre-esterify primary polyols used in converting biobased oils, oil derivatives, and modified oils to highly functionalized esters, ester polyols, amides, and amide polyols.

Claims

1. A method for producing an ester comprising:

A. pre-esterifying a primary polyol;

B. reacting the pre-esterified primary polyol with ozone, and optionally a biobased oil, oil derivative, or modified oil, in the presence of a solvent at a temperature between about −

80°

C. to about 80°

C. to produce intermediate products; and

C. refluxing the intermediate products or further reacting at lower than reflux temperature, wherein esters are produced from the intermediate products at double bond sites; and

substantially all of the fatty acids are transesterified to esters at the fatty acid sites.

2. The method of claim 1 wherein the solvent is selected from ester solvents, ketone solvents, chlorinated solvents, amide solvents, or combinations thereof.

3. The method of claim 1 wherein the solvent is selected from ethyl acetate, methyl acetate, ethyl propionate, methyl propionate, ethyl butyrate, methyl butyrate, isobutyl acetate, and isobutyl isobutyrate

4. The method of any of claims 1-3 wherein the ester is an ester alcohol and further comprising reacting a hydroxyl group on the ester alcohol with an ester solvent to reduce a hydroxyl value of the ester alcohol.

5. The method of any of claims 1-4 wherein the primary polyol is selected from glycerin, trimethylolpropane, pentaerythritol, 1,2-propylene glycol, 1,3-propylene glycol, ethylene glycols, glucoses, sorbitol, fructoses, reduced fructoses, sucroses, aldoses, alditols, ketoses, reduced ketoses, disaccharides, or combinations thereof.

6. The method of any of claims 1-5 wherein the biobased oil, oil derivative, or modified oil is reacted in the presence of an ozonolysis catalyst.

7. The method of claim 6 wherein the ozonolysis catalyst is selected from Lewis acids and Bronsted acids.

8. The method of any of claims 1-7 further comprising amidifying the esters to form amides.

9. The method of claim 8 wherein amidifying the esters to form amides takes place in the presence of an amidifying catalyst.

10. The method of any of claims 1-9 further comprising reacting a second primary polyol or a monoalcohol with the pre-esterified primary polyol, the ozone, and the optional biobased oil, oil derivative, or modified oil, in the presence of the solvent.

11. The method of any of claims 1-10 wherein the primary polyol is pre-esterified with a carboxylic acid.

12. The method of claim 11 wherein the carboxylic acid is a fatty acid.

13. A method for producing amides comprising:

A. pre-esterifying a primary polyol;

B. amidifying a biobased oil, or oil derivative so that substantially all of the fatty acids are amidified at the fatty acid sites;

C. reacting the amidified biobased oil, or oil derivative with ozone and the pre-esterified primary polyol in the presence of a solvent at a temperature between about −

80°

C. to about 80°

C. to produce intermediate products;

D. refluxing the intermediate products or further reacting at lower than reflux temperature, wherein ester alcohols are produced from the intermediate products at double bond sites to produce a hybrid ester/amide.

14. The method of claim 13 wherein the solvent is selected from ester solvents, ketone solvents, chlorinated solvents, amide solvents, or combinations thereof.

15. The method of claim 13 wherein the solvent is selected from ethyl acetate, methyl acetate, ethyl propionate, methyl propionate, ethyl butyrate, methyl butyrate, isobutyl acetate and isobutyl isobutyrate.

16. The method of any of claims 13-15 wherein the ester is an ester alcohol and further comprising reacting a hydroxyl group on the ester alcohol with an ester solvent to reduce a hydroxyl value of the ester alcohol.

17. The method of any of claims 13-16 wherein the primary polyol is selected from glycerin, trimethylolpropane, pentaerythritol, 1,2-propylene glycol, 1,3-propylene glycol, ethylene glycols, glucoses, sorbitol, fructoses, reduced fructoses, sucroses, aldoses, alditols, ketoses, reduced ketoses, disaccharides, or combinations thereof.

18. The method any of claims 13-17 wherein amidifying the biobased oil, or oil derivative takes place in the presence of an amidifying catalyst.

19. The method of any of claims 13-18 wherein the biobased oil, or oil derivative is reacted in the presence of an ozonolysis catalyst.

20. The method of any of claims 13-19 further comprising amidifying the esters to form amides.

21. The method of claim 20 wherein amidifying the esters to form amides comprises reacting an amine alcohol with the esters to form the amide alcohols.

22. The method of any of claims 20-21 wherein amidifying the esters to form amides takes place in the presence of an amidifying catalyst.

23. The method of any of claims 20-22 wherein the amide formed at the fatty acid site is different from the amide formed from the ester so that a hybrid diamide alcohol is produced.

24. The method of any of claims 13-23 further comprising reacting a second primary polyol or a monoalcohol with the amidified biobased oil, or oil derivative, ozone, and the pre-esterified primary polyol in the presence of the solvent.

25. The method of any of claims 13-24 wherein the primary polyol is pre-esterified with a carboxylic acid.

26. The method of claim 25 wherein the carboxylic acid is a fatty acid.