Methods of direct addition of (meth) acrylic acid to bio-based oils

Patent metadata

Field	Value
Publication number	US-9533935-B2
Application number	US-201414778644-A
Country	US
Kind code	B2
Filing date	May 1, 2014
Priority date	May 17, 2013
Publication date	Jan 3, 2017
Grant date	Jan 3, 2017

Abstract

(Meth)acrylates are prepared in a single-step method from a mixture of (meth)acrylic acid and at least one biobased oil and/or its derivative(s), including at least one unsaturation. The (meth)acrylates are made by directly adding the (meth)acrylic acid to the biobased oil by reacting in the presence of an acid catalyst, including an inorganic or organic acid having at least one oxygen atom present thereon and which possesses at least one acid functionality having an ionization constant in water which is not greater than 3.

First claim

What is claimed is:

1. A method comprising reacting (meth)acrylic acid with a biobased oil comprising at least one unsaturation; the reacting occurring in the presence of an acid catalyst comprising an inorganic or organic acid having at least one oxygen atom present thereon and which possesses at least one acid functionality having an ionization constant in water which is not greater than 3.

2. The method of claim 1 wherein the acid catalyst comprises a heterogeneous catalyst.

3. The method of claim 1 wherein the acid catalyst comprises a homogeneous catalyst.

4. The method of claim 2 wherein the acid catalyst comprises a cation exchange resin.

5. The method of claim 1 wherein the acid catalyst comprises a sulfuric acid catalyst, a sulfonic acid catalyst, or a combination thereof.

6. The method of claim 1 wherein the reacting occurs in the presence of water in an amount between 0% and 5% by weight of the total components present.

7. The method of claim 1 wherein the acid catalyst comprises a sulfuric acid functional group, a sulfonic acid functional group, or a combination thereof, bound to a C 1 -C 30 aliphatic group, aromatic group, or heteroalkyl group, a polymer or (co)polymer, or an inorganic group.

8. The method of claim 1 wherein the acid catalyst is selected from the group consisting of methanesulfonic acid, p-toluenesufonic acid, fluorosulfuric acid, trifluoromethanesulfonic acid, a sulfonated styrene divinylbenzene copolymer, a fluorosulfonic acid polymer on amorphous silica support, and mixtures thereof.

9. The method of claim 1 wherein the at least one biobased oil is selected from the group consisting of soybean oil, linseed oil, almond oil, castor oil, coconut oil, rapeseed oil, cottonseed oil, sunflower seed oil, groundnut oil, palm oil, palm kernel oil, sesame oil, maize oil, peanut oil, olive oil, hemp oil, corn oil, mustard oil, flaxseed oil, apricot oil, argan oil, avocado oil, ben oil, cashew oil, grape seed oil, hazelnut oil, neem oil, pumpkin seed oil, rice bran oil, walnut oil, safflower oil, copra oil, tall oil, tung oil, cashew nutshell oil, fish oil, whale oil, and a fatty acid or a fatty acid ester derivative thereof.

10. The method of claim 1 wherein the (meth)acrylic acid comprises acrylic acid or methacrylic acid.

11. The method of claim 1 wherein the biobased oil and the (meth)acrylic acid are provided in a 10:1 to a 1:100 molar ratio.

12. The method of claim 11 wherein the biobased oil and the (meth)acrylic acid are provided in a 10:1 to a 1:25 molar ratio.

13. The method of claim 1 wherein the combination of the biobased oil and the (meth)acrylic acid range from 10% to 100% by weight of the total components present.

14. The method of claim 13 wherein the combination of the biobased oil and the (meth)acrylic acid range from 50% to 100% by weight of the total components present.

15. The method of claim 1 wherein the acid catalyst comprises 0.01% to 50% by weight of the total components present.

16. The method of claim 1 wherein the reacting is performed at a temperature of 40° C. to 150° C.

17. The method of claim 16 wherein the reacting is performed at a temperature of 60° C. to 110° C.

18. The method of claim 1 wherein the reacting is performed at a pressure of 0.5 atm (0.05 MPa) to 100 atm (10.13 MPa).

19. The method of claim 1 wherein 15% to 75% of the unsaturations of the biobased oil are acrylated.

20. The method of claim 1 wherein the reacting occurs in a continuous reactor, a semi-continuous reactor, a batch reactor, or combinations thereof.

Assignees

• 3M Innovative Properties Co

Inventors

• Colby Joshua L
• Chen Lianzhou
• Owusu-Adom Kwame
• Hutt Aaron E

Classifications

• C07C69/73

  of unsaturated acids · CPC title

• C07C67/31 Primary

  by introduction of functional groups containing oxygen only in singly bound form · CPC title

• C07C69/54

  Acrylic acid esters; Methacrylic acid esters · CPC title

• C11C3/00

  Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom (sulfonated fats or oils C07C309/62; factice C08H; drying oils C09F) · CPC title

• C07C67/04 Primary

  by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds · CPC title