Synthesis of functional polymers via oxyanion and iodide catalyzed living radical polymerizations in emulsion, solution and bulk systems and their applications

Abstract

Chapter 1 introduced the general concept of living radical polymerization (LRP), three most widely-used LRP methods were introduced, and their advantages and disadvantages were discussed. The mechanism of reversible complexation mediated polymerization (RCMP) was introduced, and its advantages over other LRPs have been discussed. The current catalysts and current limitations of RCMP were also introduced. The motivations and aims for the works in this Thesis were explained.In Chapter 2, oxyanions (carboxylate, nitrate, phosphate, and sulfonate) were systematically studied as new RCMP catalysts. The oxyanion-catalyzed RCMP yielded polymers with relatively high conversion in short reaction times, maintaining low dispersity.The high chain-end iodide livingness of the obtained polymers also enabled the synthesis of block copolymers. Oxyanion compounds are inexpensive, little toxic, and amenable to broad molecular structures. These features are attractive for RCMP catalysis. The development of oxyanions as RCMP catalysts also contributed to development of air-tolerant RCMP in Chapter 3.In Chapter 3, air-tolerant RCMP was developed. The air-tolerant RCMP system employed an aldehyde, N-hydroxyphthalimide (NHPI), and an amine for both oxygen consumption and catalysis. The aldehyde (RCHO) consumed oxygen and was converted to a carboxylic acid (RCOOH) catalyzed by NHPI. The carboxylic acid was subsequently converted to a carboxylate anion (RCOO − ) in the presence of the amine. The generated RCOO − worked as an RCMP catalyst. This system does not require deoxygenation before polymerization and is amenable to methacrylates and styrene. The development of air-tolerant RCMP enhances the practicality of RCMP.In Chapter 4, RCMP was explored in the emulsion system. We systematically studied the effect of emulsifiers, catalysts, and alkyl iodide initiating dormant species in emulsion