Thermoreversible crystallization-driven aggregation of diblock copolymer nanoparticles in mineral oil

Chemical Science
Matthew J DerrySteven P Armes

Abstract

A poly(behenyl methacrylate)37 (PBeMA37) 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 PBeMA37-PBzMA x 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 PBeMA37-PBzMA100 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 PBeMA37 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,...Continue Reading

References

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Citations

Jul 12, 2019·Proceedings. Mathematical, Physical, and Engineering Sciences·Gregory N SmithSteven P Armes
Oct 24, 2019·Journal of Materials Chemistry. B, Materials for Biology and Medicine·Tomoki NishimuraKazunari Akiyoshi
May 29, 2021·Physical Review Letters·Darren J BateySilvia Cipiccia
Jan 11, 2019·Langmuir : the ACS Journal of Surfaces and Colloids·Sagar Biswas, Apurba K Das

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Methods Mentioned

BETA
X-ray
PISA
differential
rheology
nuclear magnetic resonance
light scattering

Software Mentioned

Foxtrot
SAS
Dispersion Technology
Irena

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