Reversible Complexation Mediated Living Radical Polymerization (RCMP) Using Organic Catalysts

Abstract

A novel class of living radical polymerization using amines as organic catalysts was developed. It is based on a new reversible activation mechanism, reversible complexation (RC). The polymer molecular weight and its distribution (M w/M n = 1.1–1.4) were well controlled in the polymerizations of methyl methacrylate (MMA), styrene, acrylonitrile, and some functional methacrylates with a fairly high conversion in hours in many cases. The catalysts include such common amines as triethylamine and tetramethylethylenediamine (TMEDA). Their low cost, good environmental safety, and ease of handling may be attractive for possible applications. Kinetic studies supported the RC mechanism. The activation rate constant for the MMA/TMEDA system was large enough to explain why the system provides low-polydispersity polymers from an early stage of polymerization.

Macromolecular Architectures Designed by Living Radical Polymerization with Organic Catalysts

“…RTCP and RCMP can be facile and pervasive methodologies for various applications. We previously reported the use of RTCP and RCMP in preparing well-defined linear polymers including homopolymers, random copolymers, and diblock copolymers [16][17][18][19][20][21][22][23][24][25][26][27]. In this paper, we report new examples of diblock copolymers and summarize the diblock copolymers prepared in previous and current works.…”

“…We developed two mechanistically different systems referred to as reversible chain transfer catalyzed polymerization (RTCP) [16][17][18][19][20][21][22][23] and reversible coordination mediated polymerization (RCMP) [24][25][26][27].…”

Photo-Induced Living Radical Polymerization via Organic Catalysis

“…We recently developed a new family of LRP, reversible complexation-mediated polymerization (RCMP) [20][21][22][23]. RCMP uses iodine as X (capping agent) and organic amines and organic salts as catalysts to drive the reversible activation (Scheme 1b).…”

Living Radical Polymerization via Organic Superbase Catalysis

“…We recently developed new LRP systems using iodine as a capping agent and organic molecules as catalysts. We developed two mechanistically different systems, referred to as reversible chain transfer-catalyzed polymerization (RTCP) [25][26][27][28][29][30][31] and reversible coordination-mediated polymerization (RCMP) [31][32][33][34][35]. These polymerizations are metal-free systems.…”

“…In this work, we focus on the latter system (RCMP). We previously employed amines, such as triethylamine (TEA) [32,34] and organic salts, such as tetrabutylammonium iodide (BNI) [35], as RCMP catalysts. RCMP involves reversible coordination of the catalyst to Polymer-I to generate Polymer We are pursuing more reactive catalysts to widen the scope of RCMP.…”