Issue 18, 2017

Comparison of photo- and thermally initiated polymerization-induced self-assembly: a lack of end group fidelity drives the formation of higher order morphologies

Abstract

Polymerization-induced self-assembly (PISA) is an emerging industrially relevant technology, which allows the preparation of defined and predictable polymer self-assemblies with a wide range of morphologies. In recent years, interest has turned to photoinitiated PISA processes, which show markedly accelerated reaction kinetics and milder conditions, thereby making it an attractive alternative to thermally initiated PISA. Herein, we attempt to elucidate the differences between these two initiation methods using isothermally derived phase diagrams of a well-documented poly(ethylene glycol)-b-(2-hydroxypropyl methacrylate) (PEG-b-HPMA) PISA system. By studying the influence of the intensity of the light source used, as well as an investigation into the thermodynamically favorable morphologies, the factors dictating differences in the obtained morphologies when comparing photo- and thermally initiated PISA were explored. Our findings indicate that differences in a combination of both reaction kinetics and end group fidelity led to the observed discrepencies between the two techniques. We find that the loss of the end group in photoinitiated PISA drives the formation of higher order structures and that a morphological transition from worms to unilamellar vesicles could be induced by extended periods of light and heat irradiation. Our findings demonstrate that PISA of identical block copolymers by the two different initiation methods can lead to structures that are both chemically and morphologically distinct.

Graphical abstract: Comparison of photo- and thermally initiated polymerization-induced self-assembly: a lack of end group fidelity drives the formation of higher order morphologies

Supplementary files

Article information

Article type
Paper
Submitted
09 Mar 2017
Accepted
07 Apr 2017
First published
19 Apr 2017
This article is Open Access
Creative Commons BY license

Polym. Chem., 2017,8, 2860-2871

Comparison of photo- and thermally initiated polymerization-induced self-assembly: a lack of end group fidelity drives the formation of higher order morphologies

L. D. Blackman, K. E. B. Doncom, M. I. Gibson and R. K. O'Reilly, Polym. Chem., 2017, 8, 2860 DOI: 10.1039/C7PY00407A

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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