Investigations into CTA-differentiation-involving polymerization of fluorous monomers: exploitation of experimental variances in fine-tuning of molecular weights

Accessing well-defined ultra-high-molecular-weight (UHMW) polymers has long been one of the paramount challenges in polymer synthesis. Apart from the existing strategies, the CTA-differentiation-involving polymerization implemented facile generation of UHMW fluoropolymers with narrow polydispersities. Herein, aiming at achieving logical control of the differentiation process and accurate regulation of the molecular weight, we investigated the impact of different conditions and substrates on the reaction outputs. Moreover, the M n effects on the thermal and mechanical performances of the derived materials were also examined. The results revealed that the obtained M n can be easily directed upon alteration of the polymerization rate and the substrate structure (6.13 × 10 5 -3.52 × 10 6 Da, = 1.06-1.28), improving the efficiency and practicability of this approach for producing UHMW fluorinated materials to tailor for diverse applications. Condition and substrate effects on CTA-differentiation-involving polymerization were explored for logical control of molecular weight.