Poly(pentafluorobenzyl 2‐ylidene‐acetate): Polymerization and Postpolymerization Modification

The polymerization of 2,3,4,5,6-pentafluorobenzyl 2-diazoacetate is conducted at ambient temperature and catalyzed by [(l-prolinate)RhI(1,5-dimethyl-1,5-cyclooctadiene)] or [(l-prolinate)RhI(1,5-cyclooctadiene)] yielding C1 polymers with molecular weights of 3000–4000 g mol−1 and dispersity between 1.1 and 1.3. Incorporation of the pentafluorobenzyl group into the C1 polymer results in a different solubility when compare to its C2 analog poly(2,3,4,5,6-pentafluorobenzyl methacrylate). Efficient postmodifications via para-fluoro-thiol reaction with different thiols are conducted with this C1 polymethylene.