A novel class of living radical polymerizations using germanium, phosphorus, nitrogen, oxygen, and carbon-centered compounds as catalysts. The catalysts include such common compounds as phosphites (P), imides (N), alcohols (O) and diens (C). They may be attractive for their low cost, low toxcity, and ease of handling.
In this work, inventors develop a novel initiating system for RTCP(reversible chain transfer(RT) catalyzed polymerization ), i.e., we use alcohols as the initiating dormant species instead of isolated alkyl iodides used in our previous works. (The work concerns the dormant species but not the catalyst.) In LRP(living radical polymerization), a number of works have used alcohols (alcohol-based molecules and substrates) as the initiating moieties by attaching LRP dormant species to them via, e.g., esterification and amidation. In most cases, the product was purified and isolated, and then subjected to the polymerization. This is a two-step process consisting of the attachment and the polymerization as independent steps.
A striking advantage of the invention is that, in principle, all sorts of non-conjugated alcohols can be used. Without prior chemical modification (attachment of the LRP dormant species), from molecules and substrates with hydroxy group(s), we may easily obtain, e.g., end-functional polymers, block copolymers, star and comb-shaped branched polymers, and graft polymers on surfaces. The method is also in principle applicable to any monomer, since the product RO-Mm-I possesses the same monomer unit as that for the polymerization and thus should be one of the most efficient dormant species. Such universality in alcohol and monomer can eliminate the tasks for the tedious design and synthesis of the initiating species, which is indispensable so far. In this paper, we present the proof of the principle on this method. As a model system, we studied the polymerization of methyl methacrylate (MMA) from benzyl alcohol (or its derivatives) . 

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