Highly Syndioselective Coordination (Co)Polymerization of ortho-Fluorostyrene

Coordination (co)polymerization of polar vinyl monomers is a theoretical challenge of polymer science, of which monomers bearing a polar group close to the reaction double bond are rather difficult. Herein, we report the first coordination–insertion polymerization of the cheap and commercially available ortho -fluorostyrene ( o FS) by using rare-earth metal-based catalytic systems. Under mild conditions, high activity (2.3 × 10 6 g polymer mol Sc –1 h –1 ) and perfect syndioselectivity (rrrr > 99%) as well as high conversion (99%) are obtained to give poly( o FS)s with high molecular weights and narrow molecular weight distributions. In addition, the copolymerization of o FS and styrene (St) performs fluently, and the insertion of polar o FS can be facilely tuned in a full range of 0–100% simply by changing the o FS-to-St ratio. Competitive reactivity ratios of r o FS = 0.295 and r St = 0.289 indicate the unprecedented random microstructure of the resultant copolymers.