Synthesis of pH- and thermo-responsive poly (ε-caprolactone-b-4-vinyl benzyl-g-dimethyl amino ethyl methacrylate) brush type graft copolymers via RAFT polymerization

A novel pH- and thermo-responsive poly (ε-caprolactone-b-4-vinyl benzyl-g-2-(dimethyl amino ethyl) methacrylate), poly (CL-b-VB-g-DMAEMA), brush type copolymer has been described. In this study, a reversible addition–fragmentation chain transfer (RAFT) agent, 1,2-propanediol-3-ethyl xanthogenate, was obtained through the reaction of 3-chloro-1,2-propanediol with potassium salt of ethyl xanthogenate. Poly (CL-b-VB) block copolymer was synthesized in one-pot polymerization of ε-caprolactone (CL) and 4-vinyl benzyl chloride (VB) using a new dual macro-RAFT agent. In the second step of the work, chloride side groups of poly-VB in poly (CL-b-VB) block copolymer were reacted with potassium salt of ethyl xanthogenate to obtain another novel macro-RAFT agent, poly (CL-b-VB)-g-xanthate (PCL-PVB-Xa). Controlled free radical living polymerization of 2-(dimethylaminoethyl) methacrylate (DMAEMA) was initiated with this PCL-VB-Xa macro-RAFT agent to obtain new poly (CL-b-VB-g-DMAEMA) comb type pH- and thermo-responsive heterograft copolymer. The homopolymer was soluble in water at pH = 10–11 and not soluble at pH = 12.5. A pH-sensitive feature of the brush type graft copolymer was observed between pH 9.4 and 11.5 in view of their swelling/solution properties depending on the acrylic polymer inclusion. The LCST values of the multiblock brush type copolymers were found to be as low as 42.8 °C, while that of PDMAEMA homopolymer was 46.6 °C. The characterization of the products was achieved using gel-permeation chromatography (GPC), thermal, and spectrometric analysis techniques. pH- and thermo-responsiveness of the copolymers were verified by surface tension and zeta potential measurements.