Synthesis of Cellulose-graft-Poly(N,N-dimethylamino-2-ethyl methacrylate) Copolymers via Homogeneous ATRP and Their Aggregates in Aqueous Media

Cellulose-graft-poly(N,N-dimethylamino-2-ethyl methacrylate) (cellulose-g-PDMAEMA) copolymers were prepared by homogeneous atom transfer radical polymerization (ATRP) under mild conditions. Cellulose macroinitiator was successfully synthesized by direct acylation of cellulose with 2-bromopropionyl bromide in a room temperature ionic liquid (RTIL), 1-allyl-3-methylimidazolium chloride. Copolymers were obtained via ATRP of N,N-dimethylamino-2-ethyl methacrylate (DMAEMA) with CuBr/pentamethyldiethylenetriamine (PMDETA) as catalyst and N,N-dimethylformamide (DMF) as solvent without homopolymer byproduct. The grafting copolymers were characterized by H-1 NMR, FT-IR, and TGA measurements. The results confirmed that PDMAEMA had been covalently bonded to cellulose backbone. Furthermore, the assemblies or aggregates formed by cellulose-g-PDMAEMA copolymers in water were studied at various concentrations, temperatures, and pH values by means of UV, DLS, TEM, and AFM. The results indicate that the copolymers had the pH- and temperature-responsive properties similar to the expected stimuli-responses by PDMAEMA. The synthetic strategy presented here could be employed in the preparation of other novel biomaterials from a variety of polysaccharides.