Accessing new and scalable high molecular weight branched copolymer structures using transfer-dominated branching radical telomerisation (TBRT)

Abstract

Academic and commercial branched polymer synthesis very commonly relies upon a repeating chemistry derived from a single monomer. Literature reports of branched homopolymers often rely upon chemistries that are difficult to scale. Step-growth polymerisations are widely utilised which also limit the molecular weight of resulting branched macromolecules. The recent reports of Transfer-dominated Branching Radical Telomerisation (TBRT) provide readily accessible routes to a range of previously inaccessible macromolecular architectures utilising free radical reactions but resulting in step-growth-like backbones. Here we show how TBRT may be used to form branched statistical copolymers with step-growth backbone chemistries using facile free radical reaction conditions through three novel synthesis strategies leading to new materials with readily tunable physical properties. The strategies are outlined conceptually, exemplified by experimental examples and determination of glass transition temperatures provides clear evidence of homogeneous statistical copolymer formation.