One‐step synthesis of block‐graft copolymers by reversible addition‐fragmentation chain transfer (RAFT) and ring‐opening polymerization (ROP) by using a novel initiator was reported. Block‐graft copolymers were synthesized in one‐step by simultaneous RAFT polymerization of n‐butylmethacrylate (nBMA) and ROP of ε‐caprolacton (CL) in the presence of a novel macroinitiator (RAFT‐ROP agent). For this purpose, first epichlorohydrin (EPCH) was polymerized by using H2SO4 via cationic ring‐opening mechanism. And then a novel RAFT‐ROP agent was synthesized by the reaction of potassium ethyl xanthogenate and polyepichlorohydrin (poly‐EPCH). By using the RAFT‐ROP agent, poly[CL‐b‐EPCH‐b‐CL‐(g‐nBMA)] block‐graft copolymers were synthesized. The principal parameters such as monomer concentration, initiator concentration, and polymerization time that affect the one‐step polymerization reaction were evaluated. The block lengths of the block‐graft copolymers were calculated by using 1H‐nuclear magnetic resonance (1H NMR) spectrum. The block length could be adjusted by varying the monomer and initiator concentrations. The characterization of the products was achieved using 1H NMR, Fourier‐transform infrared spectroscopy, gel‐permeation chromatography, thermogravimetric analysis, differential scanning calorimetry, elemental analysis, and fractional precipitation (γ) techniques. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2651–2659

Synthesis of poly(vinyl chloride-graft-2-vinylpyridine) graft copolymers was carried out by reversible addition-fragmentation chain transfer (RAFT) polymerization of 2-vinylpyridine using a novel macroinitiator (RAFT macroinitiator). For this purpose, RAFT macroinitiator was obtained from the potassium salt of ethyl xanthogenate and poly(vinyl chloride) (PVC). Then the graft copolymers were synthesized by using RAFT macroinitiator and 2-vinylpyridine. The principal parameters such as monomer concentration, initiator concentration, and polymerization time that affect the polymerization reaction were studied. The effect of the reaction conditions on the heterogeneity index and molecular weight was also investigated. The block lengths of the graft copolymers were calculated by using 1 H nuclear magnetic resonance ( 1 H NMR) spectra. The block lengths of the copolymers could be adjusted by varying the monomer and initiator concentrations. The characterizations of the samples were carried out by using 1 H NMR, Fourier-transform infrared spectroscopy, gel-permeation chromatography, thermogravimetric analysis, differential scanning calorimetry, and fractional precipitation (γ value) techniques. RAFT polymerization is used to control the polymerization of 2-vinylpyridine over a broad range of molecular weights.

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