Solvent-less preparation of polyols by ozonolysis

• US 8,624,047 B2
• Filed: 12/31/2009
• Issued: 01/07/2014
• Est. Priority Date: 04/26/2005
• Status: Active Grant

• Current Assignee: Battelle Memorial Institute
• Original Assignee: Battelle Memorial Institute
• Inventors: Garbark, Daniel B., Benecke, Herman Paul
• Primary Examiner(s): Carr, Deborah D
• Application Number:
  US13/142,657
• Publication Number:
  US 20110269978A1
• Time in Patent Office: 1,468 Days
• Field of Search: 554/69, 554/121, 554/133, 554/172
• US Class Current: 554/133
• 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

Solvent-less methods to convert oil derivatives, and modified oils 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 comprising:

A. reacting an oil derivative, or a modified oil with ozone and a co-solubilizing reactive alcohol in the absence of a solvent selected from the group consisting of ester solvents, ketone solvents, chlorinated solvents, amide solvents, and combinations thereof at a temperature between about −

80°

C. to about 80°

C. to produce intermediate products, wherein the co-solubilizing reactive alcohol is a polyol; 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 acids are transesterified to esters at the fatty acid sites.

2. The method of claim 1 wherein the oil derivative, or modified oil is reacted in the presence of an ozonolysis catalyst.

3. The method of claim 2 wherein the ozonolysis catalyst is selected from Lewis acids and Bronsted acids.

4. The method of claim 1 further comprising reacting a second alcohol with the oil derivative, or a modified oil, ozone, and co-solubilizing reactive alcohol.

5. The method of claim 4 wherein the second alcohol is a primary polyol, and wherein the ester is an ester alcohol.

6. The method of claim 5 wherein the primary polyol is selected from glycerin, trimethylolpropane, pentaerythritol, 1,2-propylene glycol, 1,3-propylene glycol, ethylene glycol, sorbitol, glucitol, fructose, glucose, sucrose, aldoses, ketoses, alditols, or combinations thereof.

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

8. The method of claim 7 wherein amidifying the esters to form amides takes place in the presence of an amidifying catalyst.

19. The method of claim 1 wherein the polyol is selected from 2-methyl-1,3-propylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, or combinations thereof.

9. A method for producing amides comprising:

A. amidifying an oil derivative or a modified oil so that substantially all of the fatty acids are amidified at the fatty acid sites;

B. reacting the amidified oil derivative or modified oil with ozone, and a co-solubilizing reactive alcohol in the absence of a solvent selected from the group consisting of ester solvents, ketone solvents, chlorinated solvents, amide solvents, and combinations thereof at a temperature between about −

80°

C. to about 80°

C. to produce intermediate products, wherein the co-solubilizing reactive alcohol is a polyol;

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

10. The method of claim 9 wherein amidifying the oil derivative or modified oil takes place in the presence of an amidifying catalyst.

11. The method of claim 9 wherein the oil derivative or modified oil is reacted in the presence of an ozonolysis catalyst.

12. The method of claim 9 further comprising reacting a second alcohol with the amidified oil derivative, or modified oil, ozone, and co-solubilizing reactive alcohol.

13. The method of claim 12 wherein the second alcohol is a primary polyol, and wherein the ester is an ester alcohol.

14. The method of claim 13 wherein the primary polyol is selected from glycerin, trimethylolpropane, pentaerythritol, 1,2-propylene glycol, 1,3-propylene glycol, ethylene glycol, sorbitol, glucitol, fructose, glucose, sucrose, aldoses, ketoses, alditols, or combinations thereof.

15. The method of claim 9 further comprising amidifying the esters to form amides.

16. The method of claim 15 wherein amidifying the esters to form amides comprises reacting an amine alcohol with the esters to form the amide alcohols.

17. The method of claim 15 wherein amidifying the esters to form amides takes place in the presence of an amidifying catalyst.

18. The method of claim 15 wherein the amide formed at the glyceride site is different from the amide formed from the ester so that a hybrid diamide alcohol is produced.

20. The method of claim 9 wherein the polyol is selected from 2-methyl-1,3-propylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, or combinations thereof.