Issue 37, 2022

Polymerization-induced self-assembly of random bottlebrush copolymers

Abstract

Bottlebrush polymers have shown unique self-assembly behaviors, providing access to hierarchical nanoparticles with a precise structure and tailorable function. However, the self-assembly pattern of random bottlebrush copolymers (random BBCPs) is still unclear due to the complexity of their synthesis and the kinetic barriers of the conventional solution self-assembly methods. Herein, RAFT-mediated polymerization-induced self-assembly (PISA) was exploited to evaluate the self-assembly behavior of amphiphilic random BBCPs. P[PEGMA-co-(HEMA-g-PS)] random BBCPs with tailored lengths of backbone and side-chains were synthesized via RAFT dispersion polymerization using a hydrophilic bottlebrush as the chain-transfer agent (CTA). The structural characteristic of the as-formed amphiphilic random BBCPs was confirmed by 1H NMR, and the assemblies were examined by DLS and TEM. PISA of these random BBCPs resulted in spherical micelles, whose hydrodynamic size increases with the growth of the hydrophobic PS side-chains. Furthermore, the micellar core size was correlated with the chain length of PS via a scaling law, which revealed that the hydrophobic side-chains become increasingly stretched, and the segregation strength between PPEGMA and PS side-chains increases with the backbone length of random BBCPs.

Graphical abstract: Polymerization-induced self-assembly of random bottlebrush copolymers

Supplementary files

Article information

Article type
Paper
Submitted
04 Jul 2022
Accepted
30 Aug 2022
First published
31 Aug 2022

Polym. Chem., 2022,13, 5389-5396

Polymerization-induced self-assembly of random bottlebrush copolymers

G. Mei, Y. Zheng, Y. Fu and M. Huo, Polym. Chem., 2022, 13, 5389 DOI: 10.1039/D2PY00858K

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