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Influence of an ionic comonomer on polymerization-induced self-assembly of diblock copolymers in non-polar media

DOI: 10.1039/D0PY00101E DOI Help

Authors: Gregory N. Smith (University of Sheffield; University of Copenhagen) , Sarah L. Canning (University of Sheffield) , Matthew J. Derry (University of Sheffield) , Oleksandr O. Mykhaylyk (University of Sheffield) , Sarah E. Norman (Queen's University Belfast) , Steven P. Armes (University of Sheffield)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Polymer Chemistry , VOL 11 , PAGES 2605 - 2614

State: Published (Approved)
Published: April 2020
Diamond Proposal Number(s): 17255

Abstract: A series of poly(stearyl methacrylate)–poly(benzyl methacrylate) (PSMA–PBzMA) diblock copolymer nano-objects has been synthesized via reversible addition–fragmentation chain-transfer (RAFT) dispersion polymerization in n-dodecane at 20 wt%. This polymerization-induced self-assembly (PISA) formulation was modified by the incorporation of an anionic monomer, tetradodecylammonium 3-sulfopropyl methacrylate ([NDod4]+[SPMA]−) into the oil-insoluble PBzMA block. According to the literature (M. J. Derry, et al., Chem. Sci., 2016, 7, 5078–5090), PSMA18–PBzMA diblock copolymers only form spheres using this formulation for any core degree of polymerization. Unexpectedly, incorporating just a small fraction (<6 mol%) of [NDod4]+[SPMA]− comonomer into the structure-directing block resulted in the formation of non-spherical diblock copolymer nano-objects, including pure worm-like and vesicular morphologies. However, only spherical micelles could be formed using a longer PSMA34 stabilizer. These diblock copolymer nano-objects were characterized by transmission electron microscopy, small-angle X-ray scattering, and dynamic light scattering. The bulky nature of the ionic comonomer appears to make it possible to avoid the kinetically-trapped sphere morphology. This study reveals a new approach for tuning the morphology of diblock copolymer nano-objects in non-polar media.

Subject Areas: Chemistry


Instruments: I22-Small angle scattering & Diffraction

Other Facilities: ID02 at ESRF

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