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The self-assembly and thermoresponsivity of poly(isoprene-b-methyl methacrylate) copolymers in non-polar solvents

Day, Daniel M. and Hutchings, Lian R. (2021) 'The self-assembly and thermoresponsivity of poly(isoprene-b-methyl methacrylate) copolymers in non-polar solvents.', European polymer journal., 156 . p. 110631.


The self-assembly of a series of polyisoprene-block-poly(methyl methacrylate) (PI-b-PMMA) block copolymers, in aliphatic hydrocarbon solvents is reported for the first time. The block copolymers were prepared by a change of mechanism polymerisation (CHOMP) whereby living anionic polymerisation was used to prepare polyisoprene macroinitiators for ATRP (PI-Br), which was in turn used to polymerize MMA. The use of anionic polymerisation ensured optimal control over the molar mass and dispersity of the polyisoprene block, in a synthesis that is readily scaled-up, to enable the production of homologous series of block copolymers by varying only the molar mass of the PMMA block. The block copolymers were subsequently dispersed in n-decane or n-hexane, a selective solvent for the PI block, at high solids content of up to 30 wt%. Analysis of the resulting self-assembled nanostructures using DLS and TEM revealed that the block copolymers self-assemble into varying morphologies (spherical micelles, wormlike micelles or vesicles), dependent upon the molar mass and composition of the block copolymer, enabling the construction of a series of “phase-diagrams”. The resultant self-assembled structures were also found to be thermally responsive and, in some cases, underwent a change in morphology upon heating.

Item Type:Article
Full text:Publisher-imposed embargo until 03 July 2023.
(AM) Accepted Manuscript
Available under License - Creative Commons Attribution Non-commercial No Derivatives 4.0.
File format - PDF
Publisher Web site:
Publisher statement:© 2021 This manuscript version is made available under the CC-BY-NC-ND 4.0 license
Date accepted:30 June 2021
Date deposited:02 August 2021
Date of first online publication:03 July 2021
Date first made open access:03 July 2023

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