Surface modification of cellulose nanocrystals

Patent metadata

Field	Value
Publication number	US-9815910-B2
Application number	US-201514745929-A
Country	US
Kind code	B2
Filing date	Jun 22, 2015
Priority date	Jun 20, 2014
Publication date	Nov 14, 2017
Grant date	Nov 14, 2017

Abstract

Hydrophobic CNCs were successfully prepared by grafting amine- and thiol terminated hydrocarbons to CNCs that have been previously coated with plant polyphenols. Hydrocarbons of various chain lengths can be used to tune the hydrophobicity of the modified CNCs. After the surface modification process, CNCs can be easily redispersed in nonpolar solvents highlighting the potential of the hydrophobic CNCs in, for example, CNC reinforced nanocomposites and non-aqueous formulations.

First claim

The invention claimed is:

1. A method of preparing hydrophobic cellulose nanocrystals (CNCs) comprising:
a) coating CNCs with one or more plant polyphenols in an aqueous suspension to provide polyphenol-coated CNCs;
b) grafting one or more hydrocarbons selected from an amine-terminated hydrocarbon and a thiol-terminated hydrocarbon to the polyphenol-coated CNCs to provide hydrophobic CNCs; and
c) optionally, isolating the hydrophobic CNCs.

2. The method of claim 1 , wherein the plant polyphenol is selected from one or more of tannic acid, aepigallocatechin gallate (EGCG), epicatechin gallate (ECG), epigallocatechin (EGC), gallic acid (GA) and pyrogallol (PG).

3. The method of claim 1 , comprising one or more of:
(a) an amount of CNCs in the aqueous suspension of about 0.5 wt % to about 5 wt %;
(b) adjusting the ionic strength of the aqueous CNC suspension using a buffer;
(c) a weight ratio of CNCs:polyphenol of about 5:1 to about 50:1;
(d) coating the CNCs with one or more plant polyphenols by combining the CNCs with the one or more plant polyphenols at about room temperature and stirring for about 1 hour to about 24 hours; and
(e) adjusting the pH of the suspension after addition of the one or more plant polyphenols to about 7 to about 9 using a base.

4. The method of claim 3 , wherein the amount of CNCs in the aqueous suspension is about 1 wt % to about 3 wt %.

5. The method of claim 3 , wherein the weight ratio of CNCs:polyphenol is about 10:1 to about 30:1.

6. The method of claim 3 , wherein the CNCs are combined with the one or more plant polyphenols at about room temperature and stirred for about 3 hour to about 16 hours.

7. The method of claim 3 , wherein the pH of the suspension after addition of the one or more plant polyphenols is adjusted to about 7.5 to about 8.5.

8. The method of claim 3 , wherein the base is sodium hydroxide.

9. The method of claim 1 , comprising one or more of:
(a) a weight ratio of CNCs:hydrocarbon of about 0.5:1 to about 10:1; and
(b) grafting the one or more hydrocarbons to the polyphenol-coated CNCs by combining the one or more hydrocarbons with the aqueous suspension comprising the polyphenol-coated CNCs at about room temperature and stirring for about 1 minute to about 24 hours.

10. The method of claim 9 , wherein the weight ratio of CNCs:hydrocarbon is about 1:1 to about 5:1.

11. The method of claim 9 , wherein the one or more hydrocarbons are combined with the aqueous suspension comprising the polyphenol-coated CNCs at about room temperature and stirring for about 5 minutes to about 12 hours.

12. The method of claim 1 , comprising one or more of:
(a) adding a first organic, hydrophobic solvent to the aqueous suspension comprising the polyphenol-coated CNCs at about room temperature to provide a biphasic system comprising an organic phase and an aqueous phase;
(b) a weight ratio of CNCs:hydrocarbon of about 0.5:1 to about 10:1; and
(c) grafting the one or more hydrocarbons to the polyphenol-coated CNCs by combining the one or more hydrocarbons with the biphasic system at about room temperature and stirring for about 1 minute to about 24 hours.

13. The method of claim 1 , wherein isolating the hydrophobic CNCs is performed using centrifugation or filtration.

14. The method of claim 13 , wherein isolating the hydrophobic CNCs is performed by separating the organic phase from the aqueous phase, washing the organic phase with an aqueous solvent, adding a second organic hydrophobic solvent to the organic phase, separating solids and collecting the organic phase.

15. The method of claim 14 , wherein the first and second organic hydrophobic solvents are selected from one or more of hexanes, heptane, toluene, chloroform, ethanol and methyl ethyl ketone.

16. The method of claim 1 , wherein the one or more hydrocarbons are selected from one or more of amine-terminated alkyl, thiol-terminated alkyl, amine-terminated aryl and thiol-terminated aryl.

17. The method of claim 1 , wherein the one or more hydrocarbons are selected from one or more of amine-terminated C 9-17 alkyl, thiol-terminated C 9-17 alkyl, amine-terminated C 6-20 aryl and thiol-terminated C 6-20 aryl.

18. The method of claim 1 , wherein the one or more hydrocarbons are selected from one or more of amine-terminated C 9-13 alkyl, thiol-terminated C 9-13 alkyl, amine-terminated C 6-14 aryl and thiol-terminated C 6-14 aryl.

19. The method of claim 1 , wherein one or more hydrocarbons are selected from one or more of decylamine, undecylamine, dodecylamine, decylthiol, undecylthiol, dodecylthiol, benzylamine and benzylthiol.

20. Hydrophobic CNCs prepared using the method of claim 1 .

Assignees

• Univ Mcmaster

Inventors

• Hu Zhen
• Cranston Emily

Classifications

• C08B15/00 Primary

  Preparation of other cellulose derivatives or modified cellulose {, e.g. complexes} · CPC title

• C08J7/12

  Chemical modification · CPC title

• C08B15/08

  Fractionation of cellulose, e.g. separation of cellulose crystallites · CPC title

• C08K9/04

  Ingredients treated with organic substances {(treated with macromolecular compounds C08K9/08)} · CPC title

• C08K9/08

  Ingredients agglomerated by treatment with a binding agent · CPC title