RAFT (Co)polymerization of 1,1,1,3,3,3-Hexafluoroisopropyl Acrylate as the Synthesis Technique of Amphiphilic Copolymers

The reversible addition-fragmentation chain transfer (RAFT) polymerization of 1,1,1,3,3,3-hexafluoroisopropyl acrylate (HFIPA) in the presence of dibenzyl carbonotrithioate (BTC) was studied. The effect of solvent used in polymerization process on kinetic features and molecular-weight characteristics was shown. It turns out that polymerization of HFIPA proceeds in a control mode at any conditions investigated that is confirmed by linear increase of M-n with the rise of conversion and low values of dispersity (D = 1.09-1.3). The location of trithiocarbonate group was estimated both quantum-chemical calculation and experimental methods. Copolymerization monomer pairs of HFIPA-acrylic acid and HFIPA-tert-butyl acrylate in the presence of low molecular (BTC) and polymeric chain transfer agent were investigated. Reactivity ratios of monomers was determined by Fineman-Ross and Kelen-Tudos models. The use of polymeric RAFT agent leads to instance of preferential solvation effect and formation of copolymer with gradient microstructure at final conversion.