The grafting of polymeric materials to colloidal surfaces is ubiquitous in materials science, to introduce new reactivities, to achieve improved stability, or to incorporate stimuli responsiveness, amongst other goals. Traditionally, this attachment is achieved either by grafting-to the surface with pre-synthesized polymers or by grafting-from the colloid via a surface-initiated system. Recently, work involving a third method of attachment, grafting-through polymerization, has been employed to functionalize colloidal polysaccharide suspensions. Grafting-through polymerization involves the capture of propagating species via reactive handles covalently bound to the surface. This allows for functionalization with a wide variety of monomeric species, including both hydrophilic and hydrophobic species in either solution or emulsion polymerization schemes, along with unique polymer microstructures on the surface of the substrate. In this talk, the functionalization of cellulose nanofibrils (CNFs) by the grafting-through polymerization of a reactive methacrylate handle is used to probe the fundamental properties of this attachment scheme. The mechanism of functionalization with water-soluble monomers in a solution polymerization system along with hydrophobic monomers in an emulsion polymerization setup is explored via FTIR spectroscopy, dynamic light scattering, and size exclusion chromatography. The effects of varying reaction conditions, such as monomer to reactive handle ratio and handle surface density, will provide insights into the mechanism and kinetics of using a grafting-through approach to functionalize a surface. This improved understanding can then be used to tune the surface properties of the materials to target specific applications. The ramifications of this approach to the use of CNFs as renewable composite reinforcements in PLA are discussed.

Exploring grafting-through polymerization as a method for the surface functionalization of renewable cellulosic nanomaterials

Fall 2022 abstracts, posters, and presentations will launch in mid-September.

ACS Fall 2022

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.