Controlled Synthesis of Block Copolymers by Mechanistic Transformation from Atom Transfer Radical Polymerization to Iniferter Process

Abstract

A straightforward transformation protocol combining two distinct living polymerization methods for the controlled synthesis of block copolymers is described. In the first step, bromo‐terminated poly(methyl methacrylate) is prepared by atom transfer radical polymerization (ATRP). Then, a bromide end group is substituted with a triphenylmethyl (trityl) functionality under visible light irradiation using dimanganese decacarbonyl (Mn2(CO)10) photochemistry. The resulting polymers with trityl end groups are used as macroiniferter for the polymerization of styrene and tert‐butyl acrylate (tBA) to yield desired block copolymers with narrow molecular weight distribution. Moreover, the amphiphilic copolymers with acrylic acid functionalities are obtained by the hydrolyzation of poly(tert‐butyl acrylate) containing block copolymers with trifluoroacetic acid.

Combination of the Photoinduced Atom Transfer Radical Addition Reaction and Living Cationic Polymerization: A Latent Initiator Strategy toward Tailoring Polymer Molecular Weight Distributions

“…In addition, the observation of the peaks assigned to PS and PIBVE in the 1 H NMR spectra (Figure S4) provided further evidence for the preparation of the block copolymers. This result also proved an efficient and novel method for mechanism transformation polymerization from controlled radical polymerization to living cationic polymerization to prepare polymer materials with complex structures. − …”

Visible Light Induced Degradation of Poly(methyl methacrylate‐co‐methyl α‐chloro acrylate) Copolymer at Ambient Temperature

“…Generated radical species can be either directly used in radical polymerizations or oxidized to the corresponding carbocations to initiate radical-promoted cationic polymerizations (Scheme 1). [58][59][60][61][62] Table 1. Synthesis of P(MMA-co-CHPM) and photodegradable P(MMA-co-MCA) by RAFT polymerization.…”

Synthesis of Block Copolymers by Mechanistic Transformation from Reversible Complexation Mediated Living Radical Polymerization to the Photoinduced Radical Oxidation/Addition/Deactivation Process

“…Poly(tert-butyl acrylate)-based block copolymers are essentially converted to poly(acrylic acid), resulting in the formation of amphiphilic copolymers with a facile hydrolization protocol. 57 The current work was designed to combine RCMP with PROAD processes both proceeding in a controlled manner to produce block copolymers with welldefined structures by a mechanistic transformation pathway. The presented approach is particularly useful as the type of the monomers used are structurally different and cannot be combined by either mechanism.…”

“…The obtained polymers bearing trityl end groups acted as macroiniferters which enabled the polymerization of vinyl monomers to yield desired block copolymers in a controlled fashion. Poly­( tert- butyl acrylate)-based block copolymers are essentially converted to poly­(acrylic acid), resulting in the formation of amphiphilic copolymers with a facile hydrolization protocol . The current work was designed to combine RCMP with PROAD processes both proceeding in a controlled manner to produce block copolymers with well-defined structures by a mechanistic transformation pathway.…”