Thermoreversible Crystallization-driven Aggregation of Diblock Copolymer Nanoparticles in Mineral Oil

Overview

Journal Chem Sci

Publisher Royal Society of Chemistry

Specialty Chemistry

Date 2018 May 22

PMID 29780536

Citations 5

Authors

Matthew J Derry

Oleksandr O Mykhaylyk

Anthony J Ryan

Steven P Armes

Affiliations

Soon will be listed here.

Abstract

A poly(behenyl methacrylate) (PBeMA) macromolecular chain transfer agent is utilized for the reversible addition-fragmentation chain transfer (RAFT) dispersion polymerization of benzyl methacrylate (BzMA) directly in mineral oil at 90 °C. Polymerization-induced self-assembly (PISA) occurs under these conditions, yielding a series of sterically-stabilized PBeMA-PBzMA diblock copolymer spheres of tunable diameter as confirmed by dynamic light scattering (DLS) and transmission electron microscopy (TEM) studies. Rheological studies indicate that a relatively transparent, free-flowing, concentrated dispersion of non-interacting 32 nm PBeMA-PBzMA spheres at 50 °C forms a turbid, paste-like dispersion on cooling to 20 °C. Turbidimetry and differential scanning calorimetry (DSC) studies conducted on solutions of PBeMA homopolymer in mineral oil suggest that this switchable colloidal stability is linked to crystallization-induced phase separation exhibited by this stabilizer block. Indeed, variable-temperature small-angle X-ray scattering (SAXS) indicates that a loose mass fractal network of strongly interacting spheres is formed on cooling to 20 °C, which accounts for this thermoreversible sol-gel transition. Moreover, SAXS, DSC and wide-angle X-ray scattering (WAXS) analyses indicate that the behenyl (CH) side-chains first form crystalline domains comprising adjacent stabilizer chains within individual spherical nanoparticles, with subsequent crystallization between neighboring nanoparticles leading to the formation of the mass fractal aggregates.

Citing Articles

Recent Advances in Polymerization-Induced Self-Assembly (PISA) Syntheses in Non-Polar Media.

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PMID: 37409380 PMC: 10952376. DOI: 10.1002/anie.202308372.

RAFT-mediated polymerization-induced self-assembly (RAFT-PISA): current status and future directions.

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PMID: 35509470 PMC: 9006902. DOI: 10.1039/d2sc00762b.

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Parker B, Derry M, Ning Y, Armes S Langmuir. 2020; 36(14):3730-3736.

PMID: 32216260 PMC: 7161081. DOI: 10.1021/acs.langmuir.0c00211.

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