Functionalized cellulose nanocrystal materials and methods of preparation

Patent metadata

Field	Value
Publication number	US-10669404-B2
Application number	US-201716081446-A
Country	US
Kind code	B2
Filing date	Feb 27, 2017
Priority date	Mar 2, 2016
Publication date	Jun 2, 2020
Grant date	Jun 2, 2020

Abstract

The surface hydrophobization of cellulose nanocrystals (CNCs) by carboxylic acids, biodiesel, or plant oils was conducted via there herein disclosed green process using an one-pot synthetic method. In the process, an aqueous lactic acid syrup served as a solvent to provide a stable and well-dispersed water suspension of CNCs and participated in esterification reactions to produce an intermediate product of polylactic acid (PLA) oligomer grafted CNCs (CNC-g-PLA). This solvent and intermediate product system allows for an in situ solvent exchange from water to lactic acid without prior drying of the CNCs and a subsequent efficient esterification reaction of CNCs with carboxylic acids or esters having a long hydrocarbon chain (FAs). Another advantage of the disclosed process is the ability to reuse the reagents in the subsequent reaction in order to reduce the production cost. Grafting of renewable materials on the surface of CNCs was developed by polyesterification that is capable of being environmentally friendly and mass-produced without any organic solvents or toxic reagents.

First claim

The invention claimed is:

1. A method of making a composition of cellulose nanoparticles, wherein the chemical structure of the cellulose nanoparticles comprising a glucose unit of formula I, wherein the method comprises:
a) contacting cellulose nanoparticles with water, a catalyst suitable for esterification, and a carboxylic acid with the formula of HOOC—X—OH, and heating the formed mixture, wherein said carboxylic acid is used as both a reactant and a co-solvent with water, wherein said formed mixture is substantially free of other organic solvent;
b) removing water to facilitate the esterification reaction; and
c) adding a carboxylic acid with the formula of HOOCR 2 , wherein the formula I is:

wherein R 1 is H or

wherein each R 1 in formula I may be the same or different, and at least one R 1 is not H;
X is C1-C8 straight or branched carbon linker, wherein X is optionally substituted with C1-C4 alkyl, F, Cl, —OMe, or OEt;
R 2 is a C5-C10 hetero or carbon aryl wherein the hetero aryl comprising N, O or S; a C11-17 straight or branched alkyl or alkenyl, wherein the C11-17 straight or branched alkyl or alkenyl is optionally substituted with a C5-C10 hetero or carbon aryl wherein the hetero aryl comprising N, O or S, a C1-C4 alkyl, F, Cl, —OMe, or OEt; and
n is 10-20,000, p is 1-12.

2. The method of claim 1 , wherein the step c) of adding a carboxylic acid with the formula of HOOCR 2 is carried out in step a) prior to the heating.

3. The method of claim 1 , wherein X is —CH(CH3)—, and wherein R 2 is C11-C17 straight or branched alkyl or alkenyl.

Assignees

• Purdue Research Foundation

Inventors

• Youngblood Jeffrey Paul
• Yoo Youngman

Classifications

• C08B3/02

  Catalysts used for the esterification · CPC title

• Y02P20/582

  Recycling of unreacted starting or intermediate materials · CPC title

• C08B3/00

  Preparation of cellulose esters of organic acids {(rendering cellulose suitable for esterification C08B1/02)} · CPC title

• C08L2205/16

  Fibres; Fibrils · CPC title

• C08B1/02

  Rendering cellulose suitable for esterification {(esterification per se, C08B3/00, C08B5/00, C08B7/00 or C08B9/00)} · CPC title