Hybrid polyols based on natural oil polyols

Patent metadata

Field	Value
Publication number	US-11098158-B2
Application number	US-201716313216-A
Country	US
Kind code	B2
Filing date	Jun 27, 2017
Priority date	Jun 28, 2016
Publication date	Aug 24, 2021
Grant date	Aug 24, 2021

Abstract

This invention relates to hybrid polyols useful in the manufacture of polyurethane. The hybrid polyols of the present invention is derived by copolymerizing or grafting a traditional polyester polyol onto a natural oil polyol. In the preferred embodiment of the present invention, the traditional polyester polyol grafted onto natural oil polyol contains a high level of bio-renewable content. The hybrid polyols of the present invention with high level of bio-renewable content is useful in the manufacture of polyurethane either alone or in combination with polyester polyol or polyether polyol derived from petrochemical sources.

First claim

What is claimed:

1. A hybrid polyol, comprising, in reacted form:
a functionalized natural oil or natural oil polyol useful in flexible polyurethane foam manufacturing; and
a bio-based polyester polyol comprising, in polyesterified form, a polyfunctional carboxylic acid and a polyhydric alcohol, grafted onto the functionalized natural oil or natural oil polyol,
wherein the functionalized natural oil or natural oil polyol is derived from one or more triglycerides comprising a fatty acid side chain in place of introducing functionality comprising 12 to 22 carbon atoms, and
wherein the hybrid polyol has an average functionality in a range of from 0.2 to 4.0 and a hydroxyl number in a range of from 30 to 250.

2. The hybrid polyol of claim 1 , wherein the functionalized natural oil or natural oil polyol is prepared from a natural oil selected from a group consisting of castor oil, coconut oil, cochin oil, corn oil, cottonseed oil, linseed oil, olive oil, palm oil, palm kernel oil, peanut oil, soybean oil, sunflower oil, tall oils, tallow, lesquerella oil, tung oil, whale oil, tea seed oil, sesame seed oil, safflower oil, rapeseed oil, fish oils, any derivatives thereof, and any combinations thereof,
wherein the polyfunctional carboxylic acid is selected from a group consisting of succinic acid, oxalic acid, malonic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, citraconic acid, sebacic acid, fumaric acid, malic acid, itaconic acid, muconic acid, citric acid, phthalic acid, isophthalic acid, aconitic acid, propane-1,2,3-tricarboxylic acid, trimesic acid, 2-butynedioic acid, 1,4-cyclohexane dicarboxylic acid, hexahydrophthalic acid, hexachloroendomethylenetetrahydrophthalic acid, dichlorophthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, any derivatives thereof, and any combination thereof, and
wherein the polyhydric alcohol is selected from a group consisting of ethylene glycol, propylene glycol, neopentylglycol, butanediol, pentanediol, hexanediol, cyclopentanediol, cyclohexanediol, dimethylol cyclohexane, diethylene glycol, glycerol, trimethylolpropane, butanetriol, pentaerytritol, dipentaeiythritol, cyclohexanetriol, 1,3-propanediol, 1,4-butanediol, any mixture thereof, any derivatives thereof, and any combinations thereof.

3. The hybrid polyol of claim 1 , wherein the polyfunctional carboxylic acid is succinic acid,
wherein the polyhydric alcohol is diethylene glycol,
wherein the functionalized natural oil has a structure (i)

wherein
R 1 and R 2 are independently alkyl chains comprising 9 to 21 carbons, and
n and m are independently one or more.

4. The hybrid polyol of claim 1 , wherein the polyfunctional carboxylic acid is succinic acid,
wherein the polyhydric alcohol is 1,3-propanediol,
wherein the functionalized natural oil has a structure (i)

wherein
R 1 and R 2 are independently alkyl chains comprising 9 to 21 carbons, and
n and m are independently one or more.

5. The hybrid polyol of claim 1 , wherein the polyfunctional carboxylic acid is biobased succinic acid, and
wherein the polyhydric alcohol is biobased 1,3-propanediol.

6. The hybrid polyol of claim 1 , having at least 10 percent biorenewable content.

7. A polyol mixture, comprising:
the hybrid polyol of claim 1 ; and
a petroleum-based polyol,
wherein the hybrid polyol is at least 10 percent of the polyol mixture.

8. The polyol mixture of claim 7 , wherein the petroleum-based polyol is a polyester polyol.

9. The polyol mixture of claim 7 , wherein the petroleum-based polyol is a polyether polyol.

10. A polyol mixture, comprising:
the hybrid polyol of claim 1 ; and
an isosorbide based polyol,
wherein the isosorbide-based polyol is at least 10% of the polyol mixture.

11. The polyol mixture of claim 10 , wherein the isosorbide-based polyol is prepared using bio-based isosorbide.

12. A process for manufacturing the hybrid polyol of claim 1 , which is suitable for flexible polyurethane foam manufacturing, the process comprising:
reacting components comprising (a) a functionalized natural oil or natural oil polyol, (b) a polyfunctional carboxylic acid with at least two carboxylic acid groups, and (c) a polyhydric alcohol with at least two hydroxyl groups in the presence of an esterification catalyst to yield the hybrid polyol.

13. The process of claim 12 , wherein the functionalized natural oil or natural oil polyol is prepared from a natural oil selected from a group consisting of castor oil, coconut oil, cochin oil, corn oil, cottonseed oil, linseed oil, olive oil, palm oil, palm kernel oil, peanut oil, soybean oil, sunflower oil, tall oils, tallow, lesquerella oil, tung oil, whale oil, tea seed oil, sesame seed oil, safflower oil, rapeseed oil, fish oils, any derivatives thereof, and any combinations thereof,
wherein the polyfunctional carboxylic acid is selected from succinic acid, oxalic acid, malonic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, citraconic acid, sebacic acid, fumaric acid, malic acid, itaconic acid, muconic acid, citric acid, phthalic acid, isophthalic acid, aconitic acid, propane-1,2,3-tricarboxylic acid, trimesic acid, 2-butynedioic acid, 1,4-cyclohexane dicarboxylic acid, hexahydrophthalic acid, hexachloroendomethylene tetrahydrophthalic acid, dichlorophthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, any derivatives thereof, and any mixtures thereof, and
wherein the polyhydric alcohol is selected from a group consisting of ethylene glycol, propylene glycol, neopentylglycol, butanediol, pentanediol, hexanediol, cyclopentanediol, cyclohexanediol, dimethylol cyclohexane, diethylene glycol, glycerol, trimethylolpropane, butanetriol, pentaerytritol, dipentaerythritol, cyclohexanetriol, 1,3-propanediol, 1,4-butanediol, any mixture thereof, any derivatives thereof, and any combinations thereof.

14. The hybrid polyol of claim 1 , wherein the functionalized natural oil or natural oil polyol is derived by subjecting an ethylenically unsaturated natural oil to a free radical mediated grafting reaction involving an ethylenically unsaturated monomer.

15. The hybrid polyol of claim 14 wherein the ethylenically unsaturated monomer is a monomer comprising a carboxyl functional group.

16. The hybrid polyol of claim 14 , wherein the ethylenically unsaturated monomer is maleic anhydride.

17. The hybrid polyol of claim 14 , wherein the ethylenically unsaturated monomer is a monomer comprising a hydroxyl functional group.

18. The hybrid polyol of claim 1 , produced by reacting the functionalized natural oil or natural oil polyol with at least one polyfunctional carboxylic acid and at least one polyhydric alcohol,
wherein the functionalized natural oil or natural oil polyol is derived by subjecting an ethylenically unsaturated natural oil to a free radical mediated grafting reaction involving an ethylenically unsaturated monomer.

Assignees

• Ptt Global Chemical Public Co Ltd

Inventors

• Terwillegar Arne Matthew
• Tosukhowong Thidarat
• Denniston Charliss
• Jamonnak Nuttara

Classifications

• C08G63/12

  derived from polycarboxylic acids and polyhydroxy compounds · CPC title

• C08G18/4288 Primary

  modified by higher fatty oils or their acids or by resin acids · CPC title

• C08G18/7621

  being toluene diisocyanate including isomer mixtures · CPC title

• C08G18/1825

  having hydroxy or primary amino groups · CPC title

• C08J2375/06

  from polyesters · CPC title