Continuous Synthesis of Main-Chain-type Fluorinated Graft Copolymers via Successive Flow START Polymerization and Cu(0)-Mediated RDRP

Fluorinated polymers are receiving more and more attention worldwide due to their unique chemical properties,and modified fluorinated polymers with different topologies are persued for enriching and enhancing their performance in a variety of application fields.In this work,main-chain-type semifluorinated graft copolymers are produced steadily in continuous tube reactors via photocontrolled step transferaddition and radical-termination(START)polymerization and Cu(0)-mediated reversible deactivation radical polymerization(Cu(0)-RDRP)at room temperature for the first time.Specifically,semifluorinated alternating copolymer(AB)n B is prepared by START polymerization of 1,6-diiodoperfluorohexane(A)and 1,7-octadiene(B)in the first quartz pipeline under irradiation with purple LED light at 20℃.The(AB)nB with periodic C―I bonds is then flowed into the second copper pipeline directly and acts as the macroinitiators for Cu(0)-RDRP of methyl acrylate(MA)to obtain corresponding graft copolymer(AB)n B-g-PMA.This work provides a new strategy for continuous synthesis of fluorinated graft copolymer materials.