Synthesis and Characterization of Functional Cellulose–Ether-Based PCL- and PLA-Grafts-Copolymers

The use of biodegradable materials such as cellulose and polyesters can be extended through the combination, as well as modification, of these biopolymers. By controlling the molecular structure and composition of copolymers of these components, it should also be possible to tailor their material properties. We hereby report on the synthesis and characterization of cellulose-based graft copolymers with a precise molecular composition and copolymer architecture. To prepare such materials, we initially modified cellulose through the regioselective protection of the 6-OH group using trityl chloride. The 6-O protected compound was then alkylated, and deprotection at the 6-OH group provided the desired 2,3-di-O-alkyl cellulose compounds that were used as macroinitiators for ring opening polymerization. Regioselective modification was hereby necessary to obtain compounds with an exact molecular composition. Ring opening polymerization, catalyzed by Sn(Oct)₂, at the primary 6-OH group of the cellulose macroinitiator, using L-lactide or ε-caprolactone, resulted in graft copolymers with the desired functionalization pattern. The materials were characterized using Fourier-transform infrared spectroscopy, ¹H- and ¹³C- nuclear magnetic resonance spectroscopy, size exclusion chromatography as well as X-ray diffraction, and differential scanning calorimetry. PCL-based copolymers exhibited distinct melting point as well as a crystalline phase of up to 47%, while copolymers with PLA segments were highly amorphous, showing a broad amorphous reflex in the XRD spectra, and no melting or crystallization points were discernible using differential scanning calorimetry.