Reversible Chain Transfer Catalyzed Polymerizations (RTCPs) of Styrene and Methyl Methacrylate with Phosphorus Catalysts

Abstract

Phosphorus compounds were employed as catalysts in Reversible Chain Transfer Catalyzed Polymerization (RTCP), a novel class of living radical polymerization (LRP) which we had recently developed. Low-polydispersity polystyrene and poly(methyl methacrylate) with predicted molecular weights were obtained with a fairly high conversion in a fairly short time. These catalysts are particularly featured by their high reactivity hence small amounts being required, low toxicity, and low cost. Some phosphorus catalysts used in this work are among the least expensive catalysts/mediators of LRP developed so far.

Reversible chain transfer catalyzed polymerization (RTCP): A new class of living radical polymerization

“…This means that RT plays a main role in the GeI 4 system, with a small contribution of DT. Besides GeI 4 , another Ge catalyst GeI 2 [5,6], Sn catalysts SnI 4 and SnI 2 [5,6], a P catalyst PI 3 [6,7], and a N catalyst N-iodosuccinimide (NIS: Fig. 1) [8] were also effective for St (entries 3-7 in Table 2 and Fig.…”

“…We recently developed a new class of LRP using a tin (Sn) [5,6], germanium (Ge) [5,6], phosphorus (P) [6,7], or nitrogen (N) [8] compound as a catalyst for the reversible activation and have proposed to term the polymerization reversible chain transfer catalyzed polymerization (RTCP) [6] for its new reversible activation mechanism. This is also the first LRP using compounds of typical elements (non-transition metals) as effective catalysts.…”

Simulation of reversible chain transfer catalyzed polymerization (RTCP): effect of different iodide based catalysts

“…In the former called pre-equilibrium reversible chain transfer (reactions i and j), iodine exchange occurs reversibly between PhE-I and A* (radical obtained from AI) and in the latter, reversible chain transfer, a radical transfer takes place by iodine transmission among the catalyst and macroradicals (reactions k and l). Finally, in reaction m the activator radical reacts with propagating macroradicals and causes a cross termination resulting in depletion of the catalyst [1,[14][15][16][17][18][19]. The kinetic parameters of each reaction are demonstrated in Table 1.…”

“…In the presence of AI catalyst (GeI 3 -I, etc.) another reversible reaction mechanism called the reversible chain transfer (RT) coexists which results in a low polydispersity by activating Polymer-I frequently [1,[14][15][16][17][18][19][20]. RT equilibriums are sensitive to the catalyst activity and concentration, therefore various polymer architectures could be attained by employing different catalysts at several concentrations [19].…”

Iodine transfer dispersion polymerization with CHI3 and reversible chain transfer-catalyzed dispersion polymerization with N-iodosuccinimide of methyl methacrylate in supercritical carbon dioxide

“…However, because of the low exchange frequency (k ex ), the preparation of polymers with narrow MWDs by ITP is more difficult than with other CLRP techniques. Goto and colleagues developed the reversible chain transfer-catalyzed polymerization (RTCP) technique (Scheme 1) 24 in which a very small amount of nontransition metal catalyst (such as a compound containing germanium, 25,26 tin, 25,26 phosphorus [25][26][27] or nitrogen 24,28 ) was added to an ITP system. In RTCP, the catalyst induces reversible chain transfer reactions that are faster than the degenerative chain transfer of iodine; the MWDs of polymers prepared by RTCP are narrower than for polymers prepared by ITP.…”