Synthesis of polyols suitable for castor oil replacement

Patent metadata

Field	Value
Publication number	US-2018222829-A1
Application number	US-201615748149-A
Country	US
Kind code	A1
Filing date	Jul 29, 2016
Priority date	Jul 31, 2015
Publication date	Aug 9, 2018
Grant date	—

Abstract

A method for the preparation of polyol from an unsaturated TAG oil that can function similarly to castor oil in certain applications. The method comprises controlled epoxidation of the TAG oil with an acid and an oxidizing agent to obtain a partially epoxidized TAG oil with desired iodine and oxirane values; hydroxylating the partially epoxidized TAG oil using a monoalcohol and a solid acid catalyst to obtain the polyol. The resulting polyols are comprised of a triglyceride structure and hydroxyl values, viscosities, and colors that are similar to castor oil.

First claim

1 . A method for the preparation of polyols from an unsaturated triacylglycerol (TAG) oil, comprising the steps of:
(a) partially epoxidizing the unsaturated TAG oil with an acid and an oxidizing agent to obtain a partially epoxidized TAG oil which is still unsaturated; and (b) hydroxylating the partially epoxidized TAG oil using an alcohol and an acid catalyst to obtain hydroxylated and unsaturated TAG polyols.

2 . The method of claim 1 , wherein the unsaturated TAG oil comprises camelina oil, canola oil, high oleic canola oil, sunflower oil, juvenile canola oil, flaxseed oil, camelina oil, solin oil, yellow mustard oil, brown mustard oil, oriental mustard oil, palm oil olein, or palm oil, soy oil, high erucic acid rapeseed oil, hemp oil, safflower oil, corn oil, olive oil, cottonseed oil, peanut oil, nut oils, algal oils, fish oils, or mixtures thereof.

3 . The method of claim 2 , wherein the unsaturated fatty acid comprises camelina oil or a mixture of camelina oil and flaxseed oil.

4 . The method of claim 1 , wherein the acid comprises formic acid or acetic acid,

5 . The method of claim 1 , wherein the oxidizing agent comprises hydrogen peroxide.

6 . The method of claim 1 , wherein the partially epoxidized TAG oil is extracted using an organic solvent and dried.

7 . The method of claim 1 , wherein the acid catalyst comprises a heterogeneous macroreticular ion exchange resin.

8 . The method of claim 1 , wherein the ratio of the monoalcohol to the partially epoxidized TAG oil ranges from between about 1:0.3 to about 1:1 by weight.

9 . The method of claim 8 , wherein the monoalcohol comprises methanol or ethanol.

10 . The method of claim 1 , wherein hydroxylation is conducted for between about 3.0 hours to about 24 hours, or from 3.0 hours to about 12 hours, or from 3.0 hours to about 5.0 hours.

11 . The method of claim 1 wherein epoxidation of the unsaturated TAG oil is stopped when the partially epoxidated TAG oil has an OOC ranging from about 3.0% to about 6.0%

12 . The method of claim 11 wherein the epoxidation of the unsaturated TAG oil is stopped when the TAG oil has an OOC ranging from about 4.0% to about 5.5%.

13 . The method of claim 1 wherein the TAG oil is mixed with the oxidizing agent at a temperature of between about 20° to about 40°.

14 . The method of claim 13 wherein the acid is added in small portions to the mixture of TAG oil and oxidizing agent, and the temperature is gradually increased to about 40° to about 80°, preferably about 60° C., after or during addition of the acid.

15 . The method of claim 1 wherein the acid catalyst is added to a mixture of the partially epoxidized TAG oil and a monoalcohol at a temperature of about 40° C. to about 80° C.

16 . The method of claim 1 wherein the molar ratio of acid to TAG oil double bonds is less than 1:1 and/or the molar ratio of oxidizing agent to TAG oil double bonds is greater than 1:1.

17 . The method of claim 16 wherein the molar ratio of TAG oil double bonds:oxidizing agent:acid is about 1.0:1.5:0.25.

18 . A composition comprising hydroxylated and unsaturated triacylglycerol polyols have one or more of the following properties:
(a) a hydroxyl value ranging from about 110 mg KOH/g to about 210 mg KOH/g; (b) a viscosity of between about 0.4 Pa·s to about 2.5 Pa·s; (c) an iodine value of between about 55 to about 90; or (d) an acid value of less than about 1.0 mg KOH/g.

19 . The composition of claim 18 , wherein the polyols have one or more of the following properties:
(a) a hydroxyl value of between about 150 mg KOH/g to about 200 mg KOH/g; (b) a viscosity of between about 0.6 Pa·s to about 1.6 Pa·s.; (c) an iodine value of between about 60 to about 80; or (d) an acid value of less than about 0.7 mg KOH/g.

20 . The composition of claim 19 having less than 15% non-monomeric content.

21 . (canceled)

22 . (canceled)

23 . (canceled)

24 . (canceled)

Assignees

• Univ Alberta

Inventors

• Curtis Jonathan M
• Omonov Tolibjon S
• Kharraz Ereddad

Classifications

• C07C2531/04

  containing carboxylic acids or their salts · CPC title

• C07C29/03 Primary

  by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 (by simultaneous introduction of -OH groups and halogens C07C29/64) · CPC title

• C07C33/02

  Acyclic alcohols with carbon-to-carbon double bonds · CPC title

• C11C3/006

  by oxidation · CPC title

• C07C2531/08

  Ion-exchange resins · CPC title