Air‐Tolerant Reversible Complexation Mediated Polymerization (RCMP) Using Aldehyde.

An air‐tolerant reversible complexation mediated polymerization (RCMP) technique, which can be carried out without prior deoxygenation, is developed. The system contains a monomer, an alkyl iodide initiating dormant species, air (oxygen), an aldehyde, N‐hydroxyphthalimide (NHPI), and a base. Oxygen is consumed via the NHPI‐catalyzed conversion of the aldehyde (RCHO) to a carboxylic acid (RCOOH). The generated RCOOH is further converted to a carboxylate anion (RCOO−) by the base. The RCOO− generated in situ works as an RCMP catalyst; the polymerization proceeds with the monomer, alkyl iodide dormant species, and RCOO− catalyst. Thus, the system is not only air‐tolerant but also does not require additional RCMP catalysts, which is a notable feature of this system. (NHPI is used as an oxidation catalyst for converting RCHO to RCOOH.) This technique is amenable to methyl methacrylate, butyl methacrylate, benzyl methacrylate, 2‐hydroxyethyl methacrylate, and styrene, yielding polymers with relatively low‐dispersity (Mw/Mn = 1.20−1.49), where Mw and Mn are the weight‐ and number‐average molecular weights, respectively. [ABSTRACT FROM AUTHOR]