Bio-based epoxy resins, compositions, and methods thereof

Patent metadata

Field	Value
Publication number	US-11802176-B2
Application number	US-202017085016-A
Country	US
Kind code	B2
Filing date	Oct 30, 2020
Priority date	Nov 8, 2019
Publication date	Oct 31, 2023
Grant date	Oct 31, 2023

Abstract

A bio-based epoxy resin obtained from a reaction mixture comprising a glycidyl ether component and a bio-based component comprising a fatty acid and a rosin acid, wherein the glycidyl ether component comprises at least two epoxide groups.

First claim

What is claimed is:

1. A curable composition comprising a functionalized oligomer epoxy resin and an auxiliary epoxy resin at a ratio of functionalized oligomer epoxy resin to auxiliary epoxy resin of about 10:90 to about 90:10,
wherein the functionalized oligomer epoxy resin is obtained by reacting (i) a glycidyl ether component comprising at least two epoxide groups and (ii) a bio-based component comprising a fatty acid and a rosin acid at a molar ratio of the glycidyl ether component to the bio-based component of about 0.5:1 to about 1.5:1, thereby forming the functionalized oligomer epoxy resin.

2. The curable composition according to claim 1 , wherein:
the fatty acid is derived from at least one soybean oil, canola oil, tall oil, safflower oil, linseed oil, castor oil, corn oil, sunflower oil, olive oil, sesame oil, cottonseed oil, palm-based oils, rapeseed oil, tung oil, peanut oil, jatropha oil, or a combination thereof;
the rosin acid comprises at least one gum rosin acid, wood rosin acid, tall oil rosin acid, or a combination thereof;
the functionalized epoxy resin has an acid number of less than or equal to about 5 milligrams of KOH per gram according to ASTM D664;
the functionalized epoxy resin has an epoxide equivalent weight of about 200 to about 800 grams per equivalent; or
a combination thereof.

3. The curable composition according to claim 1 , wherein the glycidyl ether component comprises a bisphenol epoxy resin, a novolac epoxy resin, a diglycidyl ether, triglycidyl ether, tetraglycidyl ether, or a combination thereof.

4. The curable composition according to claim 3 , wherein the bisphenol epoxy resin comprises bisphenol A epoxy resin, bisphenol F epoxy resin, or a combination thereof.

5. The curable composition according to claim 3 , wherein the diglycidyl ether comprises a diglycidyl ether of neopentyl glycol, a diglycidyl ether of 1,4-butanediol, or diglycidyl ether of resorcinol; the triglycidyl ether comprises trimethylolpropane triglycidyl ether; and the tetraglycidyl ether comprises pentaerythritol tetraglycidyl ether.

6. The curable composition according to claim 3 , wherein the novolac epoxy resin comprises epoxy phenol novolac, epoxy cresol novolac, or a combination thereof, and wherein the novolac epoxy resin has an epoxy functionality of 3-6.

7. The curable composition according to claim 1 , wherein the bio-based component further comprises fatty acid derivatives, rosin acid derivatives, or a combination thereof.

8. The curable composition according to claim 7 , wherein the fatty acid derivatives comprise dimer fatty acids, acrylic acid modified fatty acids, maleic anhydride modified fatty acids, or a combination thereof.

9. The curable composition according to claim 7 , wherein the rosin acid derivatives comprise hydrogenated rosins, disproportionated rosins, maleic anhydride modified rosins, fumaric acid modified rosins, or a combination thereof.

10. The curable composition according to claim 1 , wherein the bio-based component comprises
1-99 wt % of fatty acids; and
1-99 wt % of rosin acids.

11. The curable composition according to claim 1 , wherein the molar ratio of the glycidyl ether component to the bio-based component is about 0.9:1 to about 1.1:1.

12. The curable composition according to claim 1 , wherein the glycidyl ether component is bisphenol A epoxy resin, and the bio-based component is a distilled tall oil comprising up to about 50 wt % rosin acids, based on the total weight of the distilled tall oil.

13. The curable composition according to claim 1 , wherein the glycidyl ether component is a bisphenol A epoxy resin and a novolac epoxy resin, and the bio-based component is a distilled tall oil comprising up to about 50 wt % rosin acids, based on the total weight of the distilled tall oil.

14. The curable composition according to claim 1 , wherein the glycidyl ether component is triglycidyl ether and novolac epoxy resin, and the bio-based component is a distilled tall oil comprising up to about 50 wt % rosin acids, based on the total weight of distilled tall oil.

15. The curable composition according to claim 1 , wherein the glycidyl ether component is trimethylolpropane triglycidyl ether, and bio-based component is a distilled tall oil comprising from about 50 wt % to about 70 wt % rosin acid, based on the total weight of the bio-based component.

16. The curable composition of claim 1 , wherein the ratio of functionalized oligomer epoxy resin to auxiliary epoxy resin is about 25:75 to about 75:25.

17. The curable composition of claim 1 , wherein
the glycidyl ether component is bisphenol A epoxy resin, and the bio-based component is a distilled tall oil comprising up to about 50 wt % rosin acids; or
the glycidyl ether component is a mixture of bisphenol A epoxy resin and a novolac epoxy resin, and the bio-based component is a distilled tall oil comprising up to about 50 wt % rosin acids; or
the glycidyl ether component is a mixture of triglycidyl ether and novolac epoxy resin, and the bio-based component is a distilled tall oil comprising up to about 50 wt % rosin acids, each based on the total weight of the bio-based component.

18. A method of preparing the curable composition of claim 1 , the method comprising the steps of
a. admixing (i) the glycidyl ether component comprising at least two epoxide groups and (ii) the bio-based component comprising the fatty acid and the rosin acid to form a reaction mixture;
b. heating the reaction mixture;
c. adding a catalyst to the reaction mixture;
d. allowing the reaction to proceed until the reaction mixture has an acid number of less than or equal to about 1 mg KOH/g according to ASTM D664;
e. adding the reaction mixture from step (d) to an auxiliary epoxy resin to form a mixture;
f. adding a curing agent to the mixture from step (e).

19. The curable composition of claim 1 , wherein the functionalized oligomer epoxy resin is a liquid.

20. The curable composition of claim 1 , wherein the ratio of functionalized oligomer epoxy resin to auxiliary epoxy resin is about 25:75 to about 75:25, or about 50:50.

Assignees

• Ingevity South Carolina Llc

Inventors

• Liu Yongning
• Yu Wumin
• Chen Zhigang

Classifications

• C08G59/1472 Primary

  Fatty acids · CPC title

• C08G59/186

  with acids · CPC title

• C08L63/04

  Epoxynovolacs · CPC title

• C08G59/38 Primary

  together with di-epoxy compounds · CPC title

• C08G59/32

  Epoxy compounds containing three or more epoxy groups · CPC title