Atom Transfer Radical Polymerization (ATRP) has been a powerful tool to synthesize well-defined functional polymers, which are widely used in biology, drug/gene delivery and antibacterial materials, etc. However, the potential toxic residues in polymer reduced its service life and limited its applications. In order to overcome the problem, in this work, a novel polymerization system of activators generated by electron transfer for atom transfer radical polymerization (AGET ATRP) for synchronous separation of the metal catalyst and byproduct of reducing agent was developed, using thiol-grafted cellulose paper (Cell-SH) as a solid reducing agent. The polymerization kinetics were investigated in detail, and the “living” features of the novel polymerization system were confirmed by chain-end analysis and chain extension experiment for the resultant polymethyl methacrylate (PMMA). It is noted that the copper residual in obtained PMMA was less than 20 ppm, just by filtering the sheet-like byproduct of the reducing agent.

The preparation of well-defined block copolymers from both non-conjugated and conjugated monomers is still challenging. In this work, a typical block copolymer poly(vinyl acetate) (PVAc)-b-polystyrene (PS) was successfully synthesized by using a successive iniferter strategy. Herein, PVAc was first obtained in the presence of an iniferter agent (e.g., 1-cyano-1-methylethyldiethyldithiocarbamate (MANDC), 2-(N,N-diethyldithiocarbamyl)-isobutyric acid ethyl ester (EMADC) or 2-(ethoxycarbonothioyl)sulfanyl propanoate (EXEP)). Then the resultant PVAc with high end-group functionalities could be used as an effective macroiniferter agent for the polymerization of styrene (St). The kinetic studies of the chain extension experiment with St indicated the “living” features of the polymerization system. In addition, the obtained PVAc-b-PS copolymers could be easily converted into PVA-b-PS amphiphiles by methanolysis of the poly(vinyl acetate) block. Importantly, the synthesis of the copolymers just uses a single simple and metal-free catalyzed polymerization method, which may be of great potential for industrial production.