Cross-linking polymerization-induced self-assembly to produce branched core cross-linked star block polymer micelles

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We report polymerization-induced self-assemblyviacontrolled cross-linking copolymerization to produce robust block copolymer micelles with spherical, elongated, and branched shapes. Reversible addition-fragmentation chain transfer (RAFT) copolymerization of styrene and divinylbenzene (DVB) or 1,2-bismaleimidoethane (BMI) as a cross-linker in the presence of a polylactide macro-chain transfer agent (PLA-CTA) was performed in acetonitrile, which is a non-solvent to polystyrene (PS). The addition of the cross-linker accelerates the copolymerization compared to styrene homopolymerization, which leads to the formation of block polymer micelles within a shorter time frame, followed byin situinter-chain cross-linking. The micelles are virtually identical to the core cross-linked star polymer consisting of a cross-linked polystyrenic core surrounded by a PLA corona. Molecular weights up to more than 1000 kg mol(-1)could be obtained with relatively narrow dispersity values (1.1-1.4). In the case of copolymerization with DVB, the micellar morphology changes from spherical to elongated and branched shapes with increasing conversion. The size and morphology of the micelles are retained in a good solvent to PS, suggesting that thein situcross-linking effectively stabilizes the micellar core. BMI undergoes alternating copolymerization with styrene in the early stage of polymerization and yields spherical micelles exclusively, because the densely cross-linked core seems to prevent further morphological transition.
Publisher
ROYAL SOC CHEMISTRY
Issue Date
2020-07
Language
English
Article Type
Article
Citation

POLYMER CHEMISTRY, v.11, no.26, pp.4335 - 4343

ISSN
1759-9954
DOI
10.1039/d0py00515k
URI
http://hdl.handle.net/10203/275718
Appears in Collection
CH-Journal Papers(저널논문)
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