Over the past 10 years, the grafting of polymers from the surface of cellulose nanocrystals (CNCs) has gained substantial interest in both academia and industry due to the rapidly growing number of potential applications of surface-modified CNCs, which range from building blocks in nanocomposites and responsive nanomaterials to antimicrobial agents. CNCs are rod-like nanoparticles that can be isolated from renewable biosources and which exhibit high crystallinity, tunable aspect ratio, high stiffness, and strength. Upon drying, the abundance of surface hydroxyl groups often leads to a degree of irreversible aggregation, as a result of strong hydrogen bonding. Moreover, their relatively hydrophilic character renders CNCs incompatible with hydrophobic media, e.g., nonpolar solvents and polyolefin matrices. By grafting macromolecules from their surface, CNCs can be imparted with surface characteristics and other physicochemical properties that are reminiscent of the grafted polymer. This has allowed the design of nanoscale building blocks whose readily tunable properties are useful for the formation of both colloidal dispersions and solid state materials. In this Perspective, we provide an overview of the morphology and surface chemistry of CNCs and detail various techniques to manipulate their surface chemistry via polymer grafting from approaches. Moreover, we explore the most common polymerization techniques that are used to graft polymers from the surface and reducing end groups of CNCs, including surface-initiated ring-opening polymerization (SI-ROP), surface-initiated free (SI-FRP), and controlled (SI-CRP) radical polymerization. Finally, we provide insights into some of the emerging applications and conclude with an outlook of future work that would benefit the field.
The demand for industrially produced cellulose nanocrystals (CNCs) has been growing since 2012, when CelluForce Inc. opened its inaugural demonstration plant with a production capacity of 1 tonne per day. Currently, there are 10 industrial CNC producers worldwide, each producing a unique material. Thus, academic researchers and commercial users alike must consider the properties of all available CNCs and carefully select the material which will optimize the performance of their desired application. To support these efforts, this article presents a thorough characterization of four new industrially produced CNCs including sulfated CNCs from NORAM Engineering and Constructors Ltd. (in cooperation with InnoTech Alberta and Alberta-Pacific Forest Industries Inc.) and Melodea Ltd., as well as carboxylated CNCs from Anomera Inc. and Blue Goose Biorefineries Inc. These materials were benchmarked against typical lab-made, sulfated CNCs. While all CNCs were similar in size, shape, crystallinity, and suspension quality, the sulfated CNCs had a higher surface charge density than their carboxylated counterparts, leading to higher colloidal stability. Additionally, significant differences in the rheological profiles of aqueous CNC suspensions, as well as CNC thermal stability and self-assembly behavior, were observed. As such, this article highlights both the subtle and significant differences between five CNC types and acts as a guide for end-users looking to optimize the performance of CNC-based materials.
A thermally "switchable" liquid-crystalline (LC) phase is observed in aqueous suspensions of cellulose nanocrystals (CNCs) featuring patchy grafts of the thermoresponsive polymer poly(N-isopropylacrylamide) (PNIPAM). "Patchy" polymer decoration of the CNCs is achieved by preferential attachment of an atom transfer radical polymerization (ATRP) initiator to the ends of the rods and subsequent surface-initiated ATRP. The patchy PNIPAM-grafted CNCs display a higher colloidal stability above the lower critical solution temperature (LCST) of PNIPAM than CNCs decorated with PNIPAM in a brush-like manner. A 10 wt% suspension of the "patchy" PNIPAM-modified CNCs displays birefringence at room temperature, indicating the presence of an LC phase. When heated above the LCST of PNIPAM, the birefringence disappears, indicating the transition to an isotropic phase. This switching is reversible and appears to be driven by the collapse of the PNIPAM chains above the LCST, causing a reduction of the rods' packing density and an increase in translational and rotational freedom. Suspensions of the "brush" PNIPAM-modified CNCs display a different behavior. Heating above the LCST causes phase separation, likely because the chain collapse renders the particles more hydrophobic. The thermal switching observed for the "patchy" PNIPAM-modified CNCs is unprecedented and possibly useful for sensing and smart packaging applications.
(Finland) and works as apart of the FinnCEREScommunity (Aalto University and VTT,F inland) in the group of Eero Kontturi. She received her PhD in 2017 from TU Dresden (Germany) under the direction of Prof. S. Fischer.H er current research lies at the interface between nanocellulose materials science and organic synthesis. Gwendoline Delepierre has aM aster's degree in chemistry from KU Leuven (Belgium), where she was involved in various research projects on cellulose nanocrystals. She started her PhD at the Adolphe Merkle Institute in 2017 under the supervision of Prof. Christoph Weder and Dr.Justin Zoppe. She is currently on an exchange at the University of British Columbia in Vancouver (Canada) under the supervision of Prof.
Cellulose nanocrystals (CNCs) are bio-based rod-like nanoparticles with a quickly expanding market. Despite the fact that a variety of production routes and starting cellulose sources are employed, all industrially produced...
The hydrophilic polymer poly[2-(2-(2-methoxy ethoxy)ethoxy)ethylacrylate] (POEG 3 A) was grafted onto the reducing end-groups (REGs) of cellulose nanocrystal (CNC) allomorphs, and their liquid crystalline properties were investigated. The REGs on CNCs extracted from cellulose I (CNC-I) are exclusively located at one end of the crystallite, whereas CNCs extracted from cellulose II (CNC-II) feature REGs at both ends of the crystallite, so that grafting from the REGs affords asymmetrically and symmetrically decorated CNCs, respectively. To confirm the REG modification, several complementary analytical techniques were applied. The grafting of POEG 3 A onto the CNC REGs was evidenced by Fourier transform infrared spectroscopy, atomic force microscopy, and the coil−globule conformational transition of this polymer above 60 °C, i.e., its lower critical solution temperature. Furthermore, we investigated the self-assembly of endtethered CNC-hybrids into chiral nematic liquid crystalline phases. Above a critical concentration, both end-grafted CNC allomorphs form chiral nematic tactoids. The introduction of POEG 3 A to CNC-I does not disturb the surface of the CNCs along the rods, allowing the modified CNCs to approach each other and form helicoidal textures. End-grafted CNC-II formed chiral nematic tactoids with a pitch observable by polarized optical microscopy. This is likely due to their increase in hydrodynamic radius or the introduced steric stabilization of the end-grafted polymer.
When cellulose nanocrystals (CNCs) are isolated from cellulose microfibrils, the parallel arrangement of the cellulose chains in the crystalline domains is retained so that all reducing end-groups (REGs) point to one crystallite end. This permits the selective chemical modification of one end of the CNCs. In this study, two reaction pathways are compared to selectively attach atom-transfer radical polymerization (ATRP) initiators to the REGs of CNCs, using reductive amination. This modification further enabled the site-specific grafting of the anionic polyelectrolyte poly(sodium 4-styrenesulfonate) (PSS) from the CNCs. Different analytical methods, including colorimetry and solution-state NMR analysis, were combined to confirm the REG-modification with ATRP-initiators and PSS. The achieved grafting yield was low due to either a limited conversion of the CNC REGs or side reactions on the polymerization initiator during the reductive amination. The end-tethered CNCs were easy to redisperse in water after freeze-drying, and the shear birefringence of colloidal suspensions is maintained after this process.
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