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Rational synthesis of low-polydispersity block copolymer vesicles in concentrated solution via polymerization-induced self-assembly

DOI: 10.1021/ja505406s DOI Help

Authors: Carlo Gonzato (The University of Sheffield) , Mona Semsarilar (The University of Sheffield) , Elizabeth R. Jones (The University of Sheffield) , Feng Li (DSM ChemTech Center) , Gerard J. P. Krooshof (DSM ChemTech Center) , Paul Wyman (DSM Ahead) , Oleksandr Mykhaylyk (The University of Sheffield) , Remco Tuinier (DSM ChemTech Center; Utrecht University) , Steven P. Armes (The University of Sheffield)
Co-authored by industrial partner: Yes

Type: Journal Paper
Journal: Journal Of The American Chemical Society , VOL 136 (31) , PAGES 11100 - 11106

State: Published (Approved)
Published: August 2014
Diamond Proposal Number(s): 8001

Open Access Open Access

Abstract: Block copolymer self-assembly is normally conducted via post-polymerization processing at high dilution. In the case of block copolymer vesicles (or “polymersomes”), this approach normally leads to relatively broad size distributions, which is problematic for many potential applications. Herein we report the rational synthesis of low-polydispersity diblock copolymer vesicles in concentrated solution via polymerization-induced self-assembly using reversible addition–fragmentation chain transfer (RAFT) polymerization of benzyl methacrylate. Our strategy utilizes a binary mixture of a relatively long and a relatively short poly(methacrylic acid) stabilizer block, which become preferentially expressed at the outer and inner poly(benzyl methacrylate) membrane surface, respectively. Dynamic light scattering was utilized to construct phase diagrams to identify suitable conditions for the synthesis of relatively small, low-polydispersity vesicles. Small-angle X-ray scattering (SAXS) was used to verify that this binary mixture approach produced vesicles with significantly narrower size distributions compared to conventional vesicles prepared using a single (short) stabilizer block. Calculations performed using self-consistent mean field theory (SCMFT) account for the preferred self-assembled structures of the block copolymer binary mixtures and are in reasonable agreement with experiment. Finally, both SAXS and SCMFT indicate a significant degree of solvent plasticization for the membrane-forming poly(benzyl methacrylate) chains.

Journal Keywords: Binary mixtures; Copolymers; Membranes; Vesicles; X-ray scattering

Subject Areas: Chemistry, Materials

Instruments: I22-Small angle scattering & Diffraction

Other Facilities: ID02 at ESRF

Added On: 06/02/2015 17:05


Discipline Tags:

Chemistry Materials Science Polymer Science

Technical Tags:

Scattering Small Angle X-ray Scattering (SAXS)