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Living Free-Radical Dispersion Polymerization of Styrene

journal contribution
posted on 2023-06-08, 06:22 authored by Laurence I Gabaston, Richard A Jackson, Steven P Armes
Polystyrene latexes were synthesized via living free-radical chemistry with 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) in both alcoholic and aqueous alcoholic media using poly(N-vinylpyrrolidone) (PVP) as a steric stabilizer at 112-130 °C. Genuine dispersion polymerization was only achieved in ethylene glycol or ethylene glycol-water mixtures. In the absence of TEMPO, near-quantitative monomer conversions, high molecular weights, broad molecular weight distributions, and submicrometer-sized latexes were obtained. The addition of TEMPO had a profound effect on the polymerization chemistry: only moderate monomer conversions (as low as 20%, with a maximum conversion of 60% obtained after 71 h) and larger, typically micrometer-sized, latexes were obtained with TEMPO-mediated syntheses. Polydispersities (Mw/Mn's) as low as 1.11 were achieved in the presence of TEMPO, but only relatively low molecular weight polystyrene chains were obtained. All TEMPO-synthesized latexes had spherical particle morphologies and very broad size distributions, as evidenced by scanning electron microscopy (SEM) and disk centrifuge photosedimentometry (DCP), respectively. Surprisingly, high G values were calculated for the adsorbed PVP stabilizer, which suggests that it is not located exclusively on the outside of the polystyrene latex particles.

History

Publication status

  • Published

Journal

Macromolecules

ISSN

0024-9297

Publisher

Journal of the American Chemical Society

Volume

31

Page range

2883-2888

ISBN

0024-9297

Department affiliated with

  • Chemistry Publications

Full text available

  • No

Peer reviewed?

  • Yes

Legacy Posted Date

2012-02-06

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