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Issue 41, 2015
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Exploring the homogeneous controlled radical polymerisation of hydrophobic monomers in anti-solvents for their polymers: RAFT and ATRP of various alkyl methacrylates in anhydrous methanol to high conversion and low dispersity

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Abstract

In previous reports, the use of anhydrous methanol in the homogeneous ATRP polymerisation of n-butyl methacrylate (nBuMA) was shown to yield polymers with dispersities as low as Đ = 1.02, despite methanol being widely regarded as an anti-solvent for p(nBuMA). Herein, we describe the homogeneous methanolic controlled radical polymerisation of three hydrophobic alkyl methacrylate monomers (methyl, t-butyl and n-butyl methacrylate) using both ATRP and RAFT to generate a range of homopolymers, statistical copolymers, amphiliphilic block copolymers and branched polymers. Methanolic ATRP and RAFT are compared, with RAFT able to target high degrees of polymerisation (800 monomer units) with very low dispersities (Đ = 1.06) in shorter reaction times (44 h) under these conditions. Poly(ethylene glycol)-derived macroinitiators were shown to generate well defined A–B and A–B–A block copolymers (Đ = 1.02–1.18) whilst branched A–B block copolymers with weight average molecular weights up to Mw = 2.33 × 106 g mol−1 were readily synthesised. The role of methanol within the polymerisations is discussed.

Graphical abstract: Exploring the homogeneous controlled radical polymerisation of hydrophobic monomers in anti-solvents for their polymers: RAFT and ATRP of various alkyl methacrylates in anhydrous methanol to high conversion and low dispersity

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Supplementary files

Article information


Submitted
25 May 2015
Accepted
01 Jul 2015
First published
03 Jul 2015

Polym. Chem., 2015,6, 7286-7296
Article type
Paper
Author version available

Exploring the homogeneous controlled radical polymerisation of hydrophobic monomers in anti-solvents for their polymers: RAFT and ATRP of various alkyl methacrylates in anhydrous methanol to high conversion and low dispersity

A. B. Dwyer, P. Chambon, A. Town, F. L. Hatton, J. Ford and S. P. Rannard, Polym. Chem., 2015, 6, 7286
DOI: 10.1039/C5PY00791G

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