One-Step Synthesis of Triblock Copolymers via Simultaneous Reversible-Addition Fragmentation Chain Transfer (RAFT) and Ring-Opening Polymerization Using a Novel Difunctional Macro-RAFT Agent Based on Polyethylene Glycol

One-step synthesis of the triblock copolymers was carried out by reversible addition-fragmentation chain transfer (RAFT) polymerization of methyl methacrylate (MMA) and ring-opening polymerization (ROP) of beta-butyrolactone (BL) or epsilon-caprolactone (CL) using a novel difunctional macro-RAFT agent. For this purpose, primarily PEG-Br (polyethylene glycol bromine) was obtained by using 3-bromopropanoyl chloride and PEGs (polyethylene glycols) with different molecular weights. Then, macro-RAFT agent was synthesized by the reaction of potassium ethyl xanthogenate and PEG-Br. By using macro-RAFT agent, poly(MMA-b-EG-b-BL), and poly(MMA-b-EG-b-CL) triblock copolymers were synthesized by changing some polymerization conditions such as monomer/initiator concentration, polymerization time. The effect of the reaction conditions on the polydispersity and molecular weights were also investigated. The block lengths of the triblock copolymers were calculated by using H-1-nuclear magnetic resonance (H-1-NMR) spectra. It was observed that the block length could be altered by varying the monomer and initiator concentrations. The characterization of the products were achieved using H-1-NMR, Fourier-transform infrared spectroscopy (FTIR), gel-permeation chromatography (GPC), thermogravimetric analysis (TGA), and fractional precipitation (gamma) techniques.