Methods for converting glycerol to allyl compounds

Patent metadata

Field	Value
Publication number	US-10633316-B2
Application number	US-201916454954-A
Country	US
Kind code	B2
Filing date	Jun 27, 2019
Priority date	Jun 28, 2018
Publication date	Apr 28, 2020
Grant date	Apr 28, 2020

Abstract

The present disclosure is directed towards methods of converting glycerol to an allyl compound, involving deoxydehydrating glycerol with formic acid and heat to form allyl alcohol; and esterifying the allyl alcohol with formic acid and/or phthalic anhydride and heat to form allyl formate and diallyl phthalate. In some instances, the heat is generated by a microwave. In further instances, the methods involve polymerizing the allyl alcohol, allyl formate and/or diallyl phthalate to form poly(allyl alcohol) or poly(allyl formate) or poly (diallyl phthalate). In some instances, the allyl polymers were used for the consolidation of oil sands tailings.

First claim

What is claimed is:

1. A method of converting glycerol to an allyl compound, comprising:
a) deoxydehydrating glycerol with formic acid and heat to form allyl alcohol; and
b) esterifying the allyl alcohol with formic acid and heat to form allyl formate.

2. The method of claim 1 , wherein the heat of step a) and step b) is generated by a microwave.

3. The method of claim 2 , wherein the allyl alcohol is step a) is formed by distillation and the allyl formate in step b) is formed by reflux.

4. The method of claim 1 , wherein deoxydehydrating the glycerol with the formic acid and heat to form the allyl alcohol comprises heating the glycerol and the formic acid to 195° C., and then heating the glycerol and the formic acid to 240° C.

5. The method of claim 4 , further comprising isolating the allyl alcohol while heating the glycerol and the formic acid to 240° C.

6. The method of claim 5 , further comprising cooling the glycerol and the formic acid to between 95°-100° C., and then adding more of the formic acid.

7. The method of claim 5 , wherein esterifying the allyl alcohol with formic acid and heat to form allyl formate comprises heating the allyl alcohol and formic acid at 60° C.

8. The method of claim 5 , wherein the allyl alcohol formed has a purity of ≥90%.

9. The method of claim 5 , wherein the allyl formate formed has a purity of ≥85%.

10. The method of claim 6 , further comprising polymerizing the allyl formate using α,α′-azoisobutyronitrile, tert-butyl perbenzoate, di-tert-butyl peroxide, tert-butyl hydroperoxide, or benzoyl peroxide and heat to form poly(allyl formate).

11. The method of claim 10 , wherein the poly(allyl formate) has a molecular weight of at least 1000 g/mol.

12. A method of converting glycerol to an allyl polymer, comprising:
a) deoxydehydrating glycerol with formic acid and heat to form allyl alcohol; and
b) polymerizing the allyl alcohol using a radical initiator and heat to form poly(allyl alcohol);
wherein the heat of step (a) and step (b) is generated by a microwave.

13. The method of claim 12 , wherein the allyl alcohol is step a) is formed by distillation and the poly(allyl alcohol) in step b) is formed by reflux.

14. The method of claim 12 , wherein deoxydehydrating the glycerol with the formic acid and heat to form the allyl alcohol comprises heating the glycerol and the formic acid to 195° C., and then heating the glycerol and the formic acid to 260° C.

15. The method of claim 12 , further comprising isolating the allyl alcohol while heating the glycerol and the formic acid to 260° C.

16. The method of claim 15 , further comprising cooling the glycerol and the formic acid to between 95°-100° C., and then adding more of the formic acid.

17. The method of claim 16 , wherein the allyl alcohol formed has a purity of ≥90%.

18. The method of claim 16 , wherein the allyl alcohol formed has a purity of 95%.

19. The method of claim 16 , wherein the poly(allyl alcohol) has a molecular weight of at least 2400 g/mol.

Assignees

• Univ Alberta

Inventors

• Ullah Aman
• Herrero Yanet Rodriguez

Classifications

• C07C33/025

  with only one double bond · CPC title

• C07C67/08

  by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds · CPC title

• C08G6/00

  Condensation polymers of aldehydes or ketones only · CPC title

• C07C29/60 Primary

  by elimination of -OH groups, e.g. by dehydration (C07C29/34 takes precedence) · CPC title

• C08F16/08

  Allyl alcohol · CPC title