Organocatalyzed ring opening polymerization of lactide from the surface of cellulose nanofibrils

The surface initiated ring opening polymerization (SI-ROP) of cellulose nanofibers (CNF) with rac-Lactide under mild conditions using N,N-dimethyl aminopyridine (DMAP) was investigated. The influence of catalyst amount, monomer-to-initiator (cellulose surface -OH groups) ratio, temperature, and cellulose preconditioning (lyophi-lization vs solvent exchange) were studied to determine the best SI-ROP conditions, and to understand the effect of the parameters on grafting efficiency. The fibers modified after lyophilization had a PLA content comparable to those obtained with traditional metal catalysts (e.g. tin-(II)ethylhexanoate). Starting from a stable dispersion of CNF in dichloromethane obtained through solvent-exchange showed better results at low catalyst amounts. Furthermore, DMAP was readily removed from the products whereas metal catalysts can be hard to remove from the final material, potentially shortening the material lifespan and making it unfit for some applications. Therefore, the use of an easily removable and more efficient organocatalyst can be considered a good alternative to metal catalysts.