Acid-functionalized polyolefin materials and their use in acid-promoted chemical reactions

Patent metadata

Field	Value
Publication number	US-9359320-B2
Application number	US-201314032727-A
Country	US
Kind code	B2
Filing date	Sep 20, 2013
Priority date	Sep 20, 2013
Publication date	Jun 7, 2016
Grant date	Jun 7, 2016

Abstract

An acid-functionalized polyolefin material that can be used as an acid catalyst in a wide range of acid-promoted chemical reactions, wherein the acid-functionalized polyolefin material includes a polyolefin backbone on which acid groups are appended. Also described is a method for the preparation of the acid catalyst in which a precursor polyolefin is subjected to ionizing radiation (e.g., electron beam irradiation) of sufficient power and the irradiated precursor polyolefin reacted with at least one vinyl monomer having an acid group thereon. Further described is a method for conducting an acid-promoted chemical reaction, wherein an acid-reactive organic precursor is contacted in liquid form with a solid heterogeneous acid catalyst comprising a polyolefin backbone of at least 1 micron in one dimension and having carboxylic acid groups and either sulfonic acid or phosphonic acid groups appended thereto.

First claim

What is claimed is:

1. A method for conducting an acid-promoted chemical reaction, the method comprising contacting an acid-reactive organic precursor in liquid form with a solid heterogeneous acid catalyst comprising a polyolefin structure of a macroscopic size of at least 1 micron in at least one dimension, wherein surfaces of the polyolefin structure have carboxylic acid groups and either sulfonic acid or phosphonic acid groups appended thereto, wherein the solid heterogeneous acid catalyst possesses an acid density of at least 6 mmol H + /g, and wherein said acid-promoted chemical reaction is selected from dehydration, esterification, etherification, aldol condensation, enolization, oxidation, dehydrogenation, acetalization, and alkene hydration reactions, and wherein said solid heterogeneous acid catalyst is re-used in a subsequent acid-promoted chemical reaction.

2. The method of claim 1 , wherein said polyolefin structure is selected from the group consisting of polyethylene, polypropylene, halogenated polyolefins, polystyrene, copolymers thereof, and mixtures thereof.

3. The method of claim 1 , wherein said solid heterogeneous acid catalyst is in the form of fibers.

4. The method of claim 1 , wherein said solid heterogeneous acid catalyst is in the form of a mesh, foam, sponge, or fabric.

5. The method of claim 1 , wherein said solid heterogeneous acid catalyst comprises a plurality of acid-functionalized polyolefin macroscopic objects of at least 1 micron in one dimension.

6. The method of claim 1 , wherein said solid heterogeneous acid catalyst comprises a single acid-functionalized polyolefin macroscopic object of at least 1 mm in one dimension.

7. The method of claim 1 , wherein, following completion of said acid-promoted chemical reaction, said solid heterogeneous acid catalyst is separated from the acid-reactive organic precursor by a process not requiring filtration.

8. The method of claim 1 , wherein grafts containing said carboxylic acid and sulfonic acid or phosphonic acid groups are appended to said surfaces of said polyolefin structure of macroscopic size, wherein said grafts have the formula:

wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 are independently selected from hydrogen atom; hydrocarbon groups R having at least 1 and up to 6 carbon atoms; acid groups selected from sulfonic acid groups, phosphonic acid groups, and carboxylic acid groups; acid precursor groups; halide atoms; and non-acid hydrophilic groups; wherein said hydrocarbon group R is unsubstituted or substituted with one or more heteroatom linkers and/or one or more heteroatom-containing groups comprising at least one heteroatom selected from nitrogen, oxygen, sulfur, and phosphorus; and the subscripts n, m, and p are independently selected from 0 or an integer of at least 1, provided that the sum of n, m, and p is an integer of at least 2;
provided that at least one of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 is a sulfonic acid or phosphonic acid group, and at least one of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 is a carboxylic acid group, and wherein the one of the bonds ending in an asterisk in the grafts depicted in Formula (1) is attached to the surface of said polyolefin structure of macroscopic size, and one of the bonds ending in an asterisk is attached to a terminating group selected from any of the groups provided above for groups R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , and R 12 .

9. The method of claim 1 , wherein said acid-reactive organic precursor is within a polar solvent.

10. The method of claim 9 , wherein said polar solvent is selected from water and water-soluble organic solvents.

11. The method of claim 9 , wherein said polar solvent is water in the absence of an organic solvent.

12. The method of claim 1 , wherein said acid-promoted chemical reaction is a dehydration reaction.

13. The method of claim 12 , wherein said dehydration reaction converts a hexose into a furfural derivative.

14. The method of claim 13 , wherein said hexose comprises fructose.

15. The method of claim 13 , wherein said furfural derivative is 5-hydroxymethylfurfural.

16. The method of claim 13 , wherein said dehydration reaction is conducted in water as the polar solvent in the absence of an organic solvent.

17. The method of claim 15 , wherein said 5-hydroxymethylfurfural is produced in a yield of at least 20%.

18. The method of claim 15 , wherein said 5-hydroxymethylfurfural is produced with a selectivity of at least 25%.

19. The method of claim 15 , wherein said 5-hydroxymethylfurfural is produced in a yield of at least 20% with a selectivity of at least 25%.

20. The method of claim 13 , wherein said hexose is derived from biomass.

Assignees

• Ut Battelle Llc
• Univ Tennessee Res Foundation

Inventors

• Oyola Yatsandra
• Tian Chengcheng
• Bauer John Christopher
• Dai Sheng

Classifications

• C07D307/48 Primary

  Furfural · CPC title