Issue 47, 2020

RAFT dispersion polymerization of benzyl methacrylate in non-polar media using hydrogenated polybutadiene as a steric stabilizer block

Abstract

A monohydroxy-capped hydrogenated polybutadiene (PhBD) is converted into a macromolecular chain transfer agent via esterification using a carboxylic acid-functionalized trithiocarbonate. 1H NMR and UV spectroscopy studies indicated a mean degree of esterification of at least 95%. The resulting precursor is used for the reversible addition–fragmentation chain transfer (RAFT) dispersion polymerization of benzyl methacrylate (BzMA) in n-dodecane at 90 °C. In principle, systematic variation of the mean degree of polymerization (DP) of the insoluble structure-directing PBzMA block should enable the formation of PhBD–PBzMA spheres, worms or vesicles via polymerization-induced self-assembly (PISA). In practice, only kinetically-trapped spheres are obtained when targeting DPs of up to 300 at 25% w/w solids. However, increasing the copolymer concentration up to 40% or 45% w/w provides access to well-defined worms or vesicles, respectively. Gel permeation chromatography and 1H NMR spectroscopy studies confirmed relatively narrow molecular weight distributions (Mw/Mn < 1.20) and high final BzMA conversions (≥99%), respectively. These diblock copolymer nano-objects were characterized in terms of their particle size and morphology using TEM and DLS and a phase diagram was constructed. According to rheology studies, the free-standing worm gels that are formed at ambient temperature have a critical gelation concentration of approximately 5.0% w/w.

Graphical abstract: RAFT dispersion polymerization of benzyl methacrylate in non-polar media using hydrogenated polybutadiene as a steric stabilizer block

Supplementary files

Article information

Article type
Paper
Submitted
24 Sep 2020
Accepted
06 Nov 2020
First published
09 Nov 2020
This article is Open Access
Creative Commons BY license

Polym. Chem., 2020,11, 7533-7541

RAFT dispersion polymerization of benzyl methacrylate in non-polar media using hydrogenated polybutadiene as a steric stabilizer block

B. Darmau, M. J. Rymaruk, N. J. Warren, R. Bening and S. P. Armes, Polym. Chem., 2020, 11, 7533 DOI: 10.1039/D0PY01371D

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