Polysaccharide-based copolymers with brush-like, graft architectures have been prepared by many investigators. In contrast, it is challenging to prepare linear polysaccharide-based block copolymers. Only a few approaches have been reported for preparation of such architectures, despite the clear application potential of renewable-based, linear block copolymers. The challenging nature of regioselective polysaccharide end-group functionalization has impeded their preparation. Herein we report a different, flexible approach to linear block copolymers, demonstrated for derivatives of renewable, natural cellulose. To illustrate this approach, trimethyl cellulose-b-poly(ethylene glycol), trimethyl cellulose-b-poly(tetrahydrofuran) and trimethyl cellulose-b-poly(lactic acid) were synthesized by a coupling strategy. Trimethyl cellulose was functionalized regiospecifically at the reducing end anomeric carbon to create an ω-unsaturated alkyl acetal by solvolysis of trimethyl cellulose with an ω-unsaturated alcohol. Subsequently, mild and versatile olefin cross-metathesis was used to couple efficiently (100% conversion) the trimethyl cellulose block with a series of acrylate derivatives, including acrylated polymer blocks. The targeted block co-polymeric structures were confirmed by nuclear magnetic resonance (NMR) spectroscopy, and the degree of polymerization was relatively well-preserved during the coupling step, as shown by size exclusion chromatography (SEC). The results confirm that this new solvolysis/cross-metathesis method is a promising approach to polysaccharide-based linear AB, and likely ABC, block copolymers.
Keywords: Block copolymer; Cellulose; Cross-metathesis; Methyl cellulose; Regioselective; Solvolysis.
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