title: Revival of the R-group approach: a "CTA-shuttled" grafting from approach for well-defined cylindrical polymer brushes via RAFT polymerization.
abstract: The synthesis of well-defined cylindrical polymer brushes (CPBs) from a linear polymer backbone with a high density of RAFT functionalities ("grafting from" approach) is challenging when the chain transfer agent (CTA) is attached to the backbone via its R-group. It is proposed that the difficulties of the R-group approach in controlling the grafting polymerization are induced by the "entrapment" of active free radicals within individual growing CPBs. A facile "CTA-shuttled" R-group approach overcoming this entrapment effect is developed, and used to synthesize well-defined CPBs with polystyrene or poly(tert-butyl acrylate) branches and core-shell CPBs with polystyrene-block-poly(N-isopropylacrylamide) branches. The polydispersity index (PDI = 1.23) of the obtained CPBs with polystyrene branches is much lower than that from the conventional R-group approach (PDI = 2.18). Monte Carlo simulations confirm that the advantage of the "CTA-shuttled" R-group approach consists in the release of the active radicals from the trapping CPB systems.
authors.affiliation: Makromolekulare Chemie II, Universität Bayreuth, 95440, Bayreuth, Germany.
authors.forename: Zhicheng
authors.initials: Z
authors.lastname: Zheng
authors.affiliation: Makromolekulare Chemie II, Universität Bayreuth, 95440, Bayreuth, Germany.|MOE Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou, 310027, China.
authors.forename: Jun
authors.initials: J
authors.lastname: Ling
authors.affiliation: Makromolekulare Chemie II, Universität Bayreuth, 95440, Bayreuth, Germany.
authors.forename: Axel H E
authors.initials: AHE
authors.lastname: Müller
mesh_terms: D058105:Polymerization; D011108:Polymers / Q000737:chemistry*
chemical_list: D011108:Polymers
keywords: R-group approach; cylindrical polymer brushes; entrapment of active radicals; graft copolymers; reversible addition-fragmentation chain transfer (RAFT)