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Synthesis and characterization of all-acrylic tetrablock copolymer nanoparticles: waterborne thermoplastic elastomers via one-pot RAFT aqueous emulsion polymerization
DOI:
10.1021/acs.chemmater.3c03115
Authors:
Oliver J.
Deane
(University of Sheffield)
,
Pierre
Mandrelier
(University of Sheffield)
,
Osama M.
Musa
(Ashland Specialty Ingredients)
,
Mohammed
Jamali
(The University of Manchester)
,
Lee A.
Fielding
(The University of Manchester)
,
Steven P.
Armes
(University of Sheffield)
Co-authored by industrial partner:
No
Type:
Journal Paper
Journal:
Chemistry Of Materials
State:
Published (Approved)
Published:
February 2024
Diamond Proposal Number(s):
21776
Abstract: Reversible addition–fragmentation chain transfer (RAFT) aqueous emulsion polymerization is used to prepare well-defined ABCB tetrablock copolymer nanoparticles via sequential monomer addition at 30 °C. The A block comprises water-soluble poly(2-(N-acryloyloxy)ethyl pyrrolidone) (PNAEP), while the B and C blocks comprise poly(t-butyl acrylate) (PtBA) and poly(n-butyl acrylate) (PnBA), respectively. High conversions are achieved at each stage, and the final sterically stabilized spherical nanoparticles can be obtained at 20% w/w solids at pH 3 and at up to 40% w/w solids at pH 7. A relatively long PnBA block is targeted to ensure that the final tetrablock copolymer nanoparticles form highly transparent films on drying such aqueous dispersions at ambient temperature. The kinetics of polymerization and particle growth are studied using 1H nuclear magnetic resonance spectroscopy, dynamic light scattering, and transmission electron microscopy, while gel permeation chromatography analysis confirmed a high blocking efficiency for each stage of the polymerization. Differential scanning calorimetry and small-angle X-ray scattering studies confirm microphase separation between the hard PtBA and soft PnBA blocks, and preliminary mechanical property measurements indicate that such tetrablock copolymer films exhibit promising thermoplastic elastomeric behavior. Finally, it is emphasized that targeting an overall degree of polymerization of more than 1000 for such tetrablock copolymers mitigates the cost, color, and malodor conferred by the RAFT agent.
Subject Areas:
Materials,
Chemistry
Instruments:
I22-Small angle scattering & Diffraction
Added On:
19/02/2024 08:40
Discipline Tags:
Chemistry
Materials Science
Organic Chemistry
Nanoscience/Nanotechnology
Polymer Science
Technical Tags:
Scattering
Small Angle X-ray Scattering (SAXS)