Polysaccharide derivatives and cross-metathesis processes for preparing them

Patent metadata

Field	Value
Publication number	US-2016376379-A1
Application number	US-201515125787-A
Country	US
Kind code	A1
Filing date	Mar 16, 2015
Priority date	Mar 14, 2014
Publication date	Dec 29, 2016
Grant date	—

Abstract

Methods for the cross-metathesis of polysaccharides with one or more olefin-terminated side chains and cross-metathesized products are described. In an exemplary embodiment, a method for the synthesis of cellulose ω-carboxyesters via olefin cross-metathesis with acrylates is described. Conditions of the reactions were relatively mild and the olefin-substituted polysaccharides and the appropriate acrylate partners appear to follow Grubbs rules as summarized herein. Additionally, a method of hydrogenation of the cross-metathesized product is described. The compounds and methods may be useful for waterborne coating applications, adhesives, lubricants, or any product in need of dispersion in an aqueous media.

First claim

1 . A method for the synthesis of a cross-metathesized polysaccharide derivative, the method comprising:
providing an olefin-substituted polysaccharide which has one or more olefin-terminated side chains; providing a solvent capable of dissolving the olefin-substituted polysaccharide; providing an acrylate as a cross-metathesis partner; providing Hoveyda-Grubbs 2 nd Generation Catalyst; and reacting the acrylate and the olefin-substituted polysaccharide in the solvent for a time and under conditions sufficient to obtain a cross-metathesized polysaccharide derivative.

2 . The method of claim 1 , further comprising hydrogenating the cross-metathesized polysaccharide derivative.

3 . (canceled)

4 . The method of claim 2 , wherein the hydrogenating involves Pd/C as a hydrogenation catalyst.

5 . (canceled)

6 . The method of claim 1 , wherein the acrylate is selected from the group consisting of methyl acrylate, 2-hydroxyethyl acrylate, methyl ether acrylate, poly(ethylene glycol) methyl ether acrylate (PEGMEA), and poly(propylene glycol) acrylate (PPGA).

7 . The method of claim 1 , wherein the olefin-substituted polysaccharide is a linear or branched polysaccharide or oligosaccharide comprising monosaccharide, disaccharide, or trisaccharide repeating units.

8 . The method of claim 1 , wherein the olefin-substituted polysaccharides are chosen from olefin-substituted cellulose, cellulose ester, cellulose ether, amylose, amylopectin, curdlan, pullulan, dextran, chitin, chitosan, alginic acid, xylan, glucuronoxylan, glucomannan, galactoglucomannan, pectin, chondroitin sulfate, dermatan sulfate, hyaluronic acid, heparan sulfate, and heparin.

9 . (canceled)

10 . The method of claim 1 , wherein the olefin-substituted polysaccharide is chosen from a cellulose alkanoate undec-10-enoate derivative, a cellulose pent-4-enoate derivative, a cellulose hept-4-enoate derivative, and ethyl cellulose substituted with allyl chloride, 5-bromo-1-pentene, 7-bromo-1-heptene, or 11-bromo-1-undecene.

11 - 12 . (canceled)

13 . The method of claim 1 , wherein the cross-metathesis partner is provided at a cross-metathesis partner: terminal olefin ratio exceeding 1:1.

14 . The method of claim 1 , wherein the cross-metathesis partner is provided at a cross-metathesis partner: terminal olefin ratio exceeding 20:1.

15 . The method of claim 1 [[or 2]], wherein the Hoveyda-Grubbs 2 nd Generation Catalyst is provided in a range of 0.1 to 20 mol %.

16 - 22 . (canceled)

23 . The method of claim 1 , wherein the one or more olefin-terminated side chains have one or more functional groups chosen from hydroxyl, carboxyl, carbonyl, amine, amide, aldehyde, carboxylate, ester, ether, nitrate, nitroso, sulfide, and sulfydryl.

24 . The method of claim 1 , wherein the one or more olefin-terminated side chains include at least one heteroatom chosen from phosphorus, sulfur, oxygen, nitrogen, boron, chlorine, bromine, iodine, and fluorine.

25 . (canceled)

26 . A compound having the formula:

wherein:
R can be H, ethyl, methyl, acetyl, propionyl and butyryl m=0−8

n=10-10,000

27 . A method for the synthesis of a polysaccharide derivative, the method comprising:
providing an olefin-substituted polysaccharide which has one or more olefin-terminated side chains; providing a solvent capable of dissolving the olefin-substituted polysaccharide; providing a cross-metathesis partner; providing Hoveyda-Grubbs 2nd Generation Catalyst; and reacting the cross-metathesis partner and the olefin-substituted polysaccharide in the solvent for a time and under conditions sufficient to obtain a cross-metathesized polysaccharide derivative; and hydrogenating the cross-metathesized polysaccharide derivative.

28 - 30 . (canceled)

31 . The method of claim 27 , wherein the hydrogenation catalyst is Pd/C.

32 . The method of claim 27 , wherein the cross-metathesis partner is chosen from acrylic acid, acrylates, acrylate esters, methyl acrylate, 2-hydroxyethyl acrylate, poly(ethylene glycol) methyl ether acrylate, acrylamide, and allyl alcohols.

33 . The method of claim 27 , wherein the hydrogenating yields a cellulose ether comprising pendent carboxylic acid functionality.

34 . The method of claim 27 , wherein the hydrogenating yields a cellulose ester comprising pendent carboxylic acid functionality.

35 . The method of claim 27 , wherein the polysaccharide derivative is amphiphilic.

36 - 38 . (canceled)

39 . The method of claim 1 , wherein the cross-metathesized polysaccharide derivative is amphiphilic and dispersible in water.

Assignees

• Edgar Kevin J
• Meng Xiangtao
• Dong Yifan
• Virginia Tech Intellectual Properties Inc

Inventors

• Edgar Kevin J
• Meng Xiangtao
• Dong Yifan

Classifications

• C08B37/00

  Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof (cellulose D21; {microbiological processes C12P}) · CPC title

• C08B3/16 Primary

  Preparation of mixed organic cellulose esters {, e.g. cellulose aceto-formate or cellulose aceto-propionate} · CPC title

• C08B3/02

  Catalysts used for the esterification · CPC title

• C08B11/193

  Mixed ethers, i.e. ethers with two or more different etherifying groups · CPC title

• C08B11/20

  Post-etherification treatments of chemical or physical type, {e.g. mixed etherification in two steps}, including purification · CPC title