Use of fatty acids as feed material in polyol process

• US 8,859,794 B2
• Filed: 12/31/2009
• Issued: 10/14/2014
• Est. Priority Date: 04/26/2005
• Status: Active Grant

• Current Assignee: Battelle Memorial Institute
• Original Assignee: Battelle Memorial Institute
• Inventors: Benecke, Herman Paul, Garbark, Daniel B., Vijayendran, Bhima Rao
• Primary Examiner(s): Carr, Deborah D
• Application Number:
  US13/142,663
• Publication Number:
  US 20110269982A1
• Time in Patent Office: 1,748 Days
• Field of Search: 554/69, 554/133, 554/169, 554/170
• US Class Current: 554/69
• 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 convert fatty acids to highly functionalized esters, ester polyols, amides, and amide polyols. The products can be used to make polyurethane and polyester films and foams.

Claims

1. A method for producing an ester of a free fatty acid comprising:

A. reacting the free fatty acid with ozone and an alcohol at a temperature between about −

80°

C. to about 80°

C. to produce intermediate products; and

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

substantially all of the fatty acid carboxylic acid groups are esterified to esters.

2. The method of claim 1 wherein the free fatty acid is derived from vegetable oil or animal fat.

3. The method of claim 1 wherein the free fatty acid comprises tall oil.

4. The method of claim 1 wherein the free fatty acid is reacted in the presence of an ozonolysis catalyst.

5. The method of claim 4 wherein the ozonolysis catalyst is selected from Lewis acids and Bronsted acids.

6. The method of claim 1 wherein the free fatty acid is reacted in the presence of a solvent.

7. The method of claim 6 wherein the solvent is selected from ester solvents, ketone solvents, chlorinated solvents, amide solvents, or combinations thereof.

8. The method of claim 1 wherein the alcohol is a primary polyol, and wherein the ester is an ester alcohol.

9. The method of claim 8 wherein the primary polyol is selected from glycerin, trimethylolpropane, pentaerythritol, 1,2-propylene glycol, 1,3-propylene glycol, ethylene glycol, glucose, sorbitol, fructose, reduced fructose, sucrose, aldoses, alditols, ketoses, reduced ketoses, disaccharides, or combinations thereof.

10. The method of claim 1 further comprising amidifying the esters to form amides.

11. The method of claim 10 wherein amidifying the esters to form amides takes place in the presence of an amidifying catalyst.

12. The method of claim 1 further comprising reacting one or more of a biobased oil, oil derivative, or modified oil, a primary polyol, a pre-esterified primary polyol, or a pre-esterified monoalcohol with the fatty acid, ozone, and alcohol.

13. A method for producing amides from a free fatty acid comprising:

A. amidifying the free fatty acid so that substantially all of the fatty acids are amidified;

B. reacting the amidified free fatty acid with ozone and alcohol at a temperature between about −

80°

C. to about 80°

C. to produce intermediate products;

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

14. The method of claim 13 wherein the free fatty acid is derived from vegetable oil or animal fat.

15. The method of claim 13 wherein the free fatty acid comprises tall oil.

16. The method of claim 13 wherein amidifying the free fatty acid comprises reacting an amine alcohol with a fatty acid ester.

17. The method of claim 13 wherein amidifying the free fatty acid takes place in the presence of an amidifying catalyst.

18. The method of claim 13 wherein the free fatty acid is reacted in the presence of an ozonolysis catalyst.

19. The method of claim 18 wherein the ozonolysis catalyst is selected from Lewis acids and Bronsted acids.

20. The method of claim 13 wherein the free fatty acid is reacted in the presence of a solvent.

21. The method of claim 20 wherein the solvent is selected from ester solvents, ketone solvents, chlorinated solvents, amide solvents, or combinations thereof.

22. The method of claim 13 wherein the alcohol is a polyol, and wherein the ester is an ester alcohol.

23. The method of claim 22 wherein the polyol is selected from glycerin, trimethylolpropane, pentaerythritol, 1,2-propylene glycol, 1,3-propylene glycol, ethylene glycol, glucose, sorbitol, fructose, reduced fructose, sucrose, aldoses, alditols, ketoses, reduced ketoses, disaccharides, or combinations thereof.

24. The method of claim 13 further comprising amidifying the esters in the hybrid ester/amide to form amides.

25. The method of claim 24 wherein amidifying the esters in the hybrid ester/amide to form amides comprises reacting an amine alcohol with the esters to form the amide alcohols.

26. The method of claim 24 wherein amidifying the esters in the hydrid ester/amide to form amides takes place in the presence of an amidifying catalyst.

27. The method of claim 13 further comprising reacting a biobased oil, oil derivative, or modified oil, a primary polyol, or a pre-esterified primary polyol, with the free fatty acid, ozone, and alcohol.