Formaldehyde-free phenolic resins, downstream products, their synthesis and use

Patent metadata

Field	Value
Publication number	US-2016355631-A1
Application number	US-201515119030-A
Country	US
Kind code	A1
Filing date	Feb 20, 2015
Priority date	Feb 20, 2014
Publication date	Dec 8, 2016
Grant date	—

Abstract

A resin composition containing the reaction product of a 5-hydroxymethyl furfural (HMF) produced in-situ from e.g., glucose and a phenolic compound. Phenolic compounds include phenol, cardanol and bio-phenol. The resin is heat-curable using cross-linking agents such as tetraethylammonium chloride or lignin, etc.

First claim

1 . A method for preparing a cross-linkable resin, the method comprising the step of:
(i) converting a hexose to 5-hydroxymethyl furfural (HMF) in the presence of a phenolic compound and a catalyst that promotes formation of covalent bonds between a carbon atom of the aromatic ring of the phenolic compound and the carbon of the formyl group of the HMF to form the resin.

2 . The method of claim 1 , wherein the catalyst comprises a Friedel-Crafts alkylation catalyst.

3 . The method of claim 2 , wherein the catalyst comprises a mixture of YCl 2 , YCl 3 and quaternary ammonium salt, wherein Y is Cr or Cu.

4 . The method of claim 3 , wherein the quaternary ammonium salt is tetraethylammonium chloride (TEAC) or tetramethylammonium chloride.

5 . The method of claim 1 , wherein the catalyst comprises a Lewis acid.

6 . The method of claim 1 , wherein said catalyst further catalyzes the conversion of the hexose to HMF.

7 . The method of claim 1 , wherein the hexose comprises glucose.

8 . The method of claim 1 , wherein said phenolic compound is selected from unsubstituted phenol, cardanol and combinations thereof.

9 . The method of claim 1 , wherein the phenolic compound is obtained from a lignocellulosic biomass.

10 . The method of claim 9 , wherein said biomass is one or more of pyrolysis oil, liquefied biomass, lignin, de-polymerized lignin, phenolated de-polymerized lignin, and liquefied lignin.

11 . The method of claim 1 , wherein step (i) includes heating a mixture comprising the hexose, the phenolic compound and the catalyst to a temperature sufficient to form a liquid mixture.

12 . The method of claim 11 , wherein said temperature is at least between 80° C. and 120° C.

13 - 15 . (canceled)

16 . The method of claim 11 , wherein the molar ratio of hexose:phenolic rings of the phenolic compound is between 0.5:1 and 3:1.

17 . The method of claim 16 , wherein said molar ratio is at least 1, and said mixture further comprises water.

18 . The method of claim 17 , wherein said water is present in an amount of between 2 and 20 weight percent of the mixture.

19 - 22 . (canceled)

23 . The method of claim 1 , wherein step (i) is conducted for a period of between 1 hour and 12 hours.

24 . (canceled)

25 . The method of claim 1 , further comprising the step of:
(ii) removing unreacted phenolic compound from the resin formed in step (i).

26 . (canceled)

27 . The method of claim 25 , wherein step (ii) comprises steam distillation.

28 . A method for producing a reaction product comprising a plurality of furyl and phenyl rings, neighboring furyl and phenyl rings being covalently linked to each other by a —CH 2 — or a —CHOH— group, the method comprising:
(a) converting a hexose to 5-hydroxymethyl furfural (HMF) in the presence of phenol and a catalyst that promotes formation of said —CH 2 — and said —CHOH— groups between the phenol and the HMF.

29 . A phenolic resin prepared according to claim 1 .

30 - 60 . (canceled)

Assignees

• Univ Western Ontario

Inventors

• Xu Chunbao
• Zhang Yongsheng
• Yuan Zhongshun

Classifications

• C08J3/24 Primary

  Crosslinking, e.g. vulcanising, of macromolecules (mechanical aspects B29C35/00; crosslinking agents C08K) · CPC title

• C08G8/04 Primary

  of aldehydes · CPC title

• C08J2361/06

  of aldehydes with phenols · CPC title

• C08G8/06

  of furfural · CPC title

• C09J161/06

  of aldehydes with phenols · CPC title