How Do Spherical Diblock Copolymer Nanoparticles Grow during RAFT Alcoholic Dispersion Polymerization?

Macromolecules
Elizabeth R JonesSteven P Armes

Abstract

A poly(2-(dimethylamino)ethyl methacrylate) (PDMA) chain transfer agent (CTA) is used for the reversible addition-fragmentation chain transfer (RAFT) alcoholic dispersion polymerization of benzyl methacrylate (BzMA) in ethanol at 70 °C. THF GPC analysis indicated a well-controlled polymerization with molecular weight increasing linearly with conversion. GPC traces also showed high blocking efficiency with no homopolymer contamination apparent and Mw/Mn values below 1.35 in all cases. 1H NMR studies confirmed greater than 98% BzMA conversion for a target PBzMA degree of polymerization (DP) of up to 600. The PBzMA block becomes insoluble as it grows, leading to the in situ formation of sterically stabilized diblock copolymer nanoparticles via polymerization-induced self-assembly (PISA). Fixing the mean DP of the PDMA stabilizer block at 94 units and systematically varying the DP of the PBzMA block enabled a series of spherical nanoparticles of tunable diameter to be obtained. These nanoparticles were characterized by TEM, DLS, MALLS, and SAXS, with mean diameters ranging from 35 to 100 nm. The latter technique was particularly informative: data fits to a spherical micelle model enabled calculation of the core diameter, surface ar...Continue Reading

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Citations

Mar 29, 2016·Macromolecules·Sarah L CanningSteven P Armes
Jun 25, 2016·Chemical Society Reviews·J JenningsP B Zetterlund
Aug 10, 2018·Macromolecular Rapid Communications·Song Yang KhorThomas P Davis
Jun 22, 2019·Macromolecular Rapid Communications·Dan LiJinying Yuan
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Mar 10, 2018·Biomacromolecules·Umberto Capasso PalmieroDavide Moscatelli
Jun 27, 2018·Langmuir : the ACS Journal of Surfaces and Colloids·Yuki OharaShin-Ichi Yusa
Feb 6, 2020·Langmuir : the ACS Journal of Surfaces and Colloids·James E HallettGregory N Smith

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Methods Mentioned

BETA
PISA
RAFT
transmission electron microscopy
X-ray
light
static light scattering
silica chromatography
light scattering

Software Mentioned

Irena SAS
MALLS
Igor Pro
Nika SAS
ASTRA

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