Monitoring morphology evolution within block copolymer microparticles during dispersion polymerisation in supercritical carbon dioxide: a high pressure SAXS study

Alauhdin, Mohammad; Bennett, Thomas M.; He, Guping; Bassett, Simon P.; Portale, Giuseppe; Bras, Wim; Hermida-Merino, Daniel; Howdle, Steven M.

doi:10.1039/c8py01578c

Monitoring morphology evolution within block copolymer microparticles during dispersion polymerisation in supercritical carbon dioxide: a high pressure SAXS study

Journal Article · Mon Dec 31 23:00:00 EST 2018 · Polymer Chemistry

DOI:https://doi.org/10.1039/c8py01578c· OSTI ID:1494887

Alauhdin, Mohammad ^[1]; ^[1]; He, Guping ^[1]; Bassett, Simon P. ^[1]; ^[2]; ^[3]; Hermida-Merino, Daniel ^[4]; ^[1]

Univ. of Nottingham (United Kingdom). School of Chemistry
Univ. of Groningen (The Netherlands). Zernike Inst. for Advanced Materials
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
Netherlands Organisation for Scientific Research (N.W.O), Grenoble (France)

Reversible addition-fragmentation chain transfer (RAFT) dispersion polymerisation in supercritical carbon dioxide is an effective process for creating block copolymer microparticles with internal nanostructures. Here we report an alternative synthesis route involving completely independent steps by exploiting the livingness of RAFT-terminated PMMA microparticles and their unique ability to be redispersed in scCO₂. This not only enables a series of block copolymers to be created from a single RAFT dispersion synthesised PMMA homopolymer batch, thus improving reproducibility, but also adds flexibility by allowing the time and concentration requirements for each stage to be decoupled. The internal morphology development and evolution for a series of poly(methyl methacrylate-block-styrene) (PMMA-b-PS) block copolymer microparticles synthesised via this route was monitored via in situ small-angle X-ray scattering (SAXS) using an autoclave with diamond windows. Together with offline kinetics experiments and post-mortem transmission electron microscopy imaging, this study provides remarkably detailed insights into block copolymer self-organisation phenomena in scCO₂. Specifically, the time period over which this block copolymer undergoes phase separation before progressing from an arrangement of spheres to lamellae via the hexagonal cylinder phase is elucidated, and the data are used to plot a detailed empirical phase diagram for this block copolymer system in scCO₂.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1494887

Journal Information:: Polymer Chemistry, Journal Name: Polymer Chemistry Journal Issue: 7 Vol. 10; ISSN PCOHC2; ISSN 1759-9954

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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