Drive to Asymmetric Lamellar Order by Polymerization-Induced Microphase Separation from the Janus Bottlebrush Architecture

IF 5.1 1区化学 Q1 POLYMER SCIENCE

Macromolecules Pub Date : 2025-03-02 DOI:10.1021/acs.macromol.4c02426

Changsu Yoo, Myungeun Seo

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Abstract

We report growing a polymer chain from the backbone of a bottlebrush polymer in the neat polymerization condition produces nanostructured polymer monoliths with ordered morphologies based on the Janus bottlebrush architecture. We installed a norbornene unit at the end of the polylactide macro-chain transfer agent (PLA-CTA) by single unit monomer insertion. We polymerized the resulting macromonomer via ring-opening metathesis polymerization to produce the PLA bottlebrush polymer, where a trithiocarbonate moiety remains on the backbone per every repeating unit. Neat polymerization of styrene in the presence of the PLA bottlebrush polymer proceeded in a grafting-from manner following the reversible addition–fragmentation chain transfer mechanism, resulting in a monolithic solid containing the doubly grafted PLA and polystyrene (PS) side chains. Polymerization-induced microphase separation (PIMS) spontaneously occurred, driven by the incompatibility between PLA and the growing PS segment. In contrast to the significant disordered fraction in PLA-b-PS produced with the linear PLA-CTA, the PLA/PS Janus bottlebrush polymer showed improved order across the investigated composition range. Formation of the asymmetric lamellae up to >80 vol % of PS indicated a strong preference for the lamellar symmetry of the Janus architecture. The in situ structured monoliths even exhibited narrower scattering peak widths compared to the solution-cast and annealed sample, suggesting the utility of the Janus PIMS process for facile preparation of ordered nanostructured materials with uniform domain size.

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来源期刊

Macromolecules 工程技术-高分子科学

CiteScore

9.30

自引率

16.40%

发文量

942

审稿时长

2 months

期刊介绍： Macromolecules publishes original, fundamental, and impactful research on all aspects of polymer science. Topics of interest include synthesis (e.g., controlled polymerizations, polymerization catalysis, post polymerization modification, new monomer structures and polymer architectures, and polymerization mechanisms/kinetics analysis); phase behavior, thermodynamics, dynamic, and ordering/disordering phenomena (e.g., self-assembly, gelation, crystallization, solution/melt/solid-state characteristics); structure and properties (e.g., mechanical and rheological properties, surface/interfacial characteristics, electronic and transport properties); new state of the art characterization (e.g., spectroscopy, scattering, microscopy, rheology), simulation (e.g., Monte Carlo, molecular dynamics, multi-scale/coarse-grained modeling), and theoretical methods. Renewable/sustainable polymers, polymer networks, responsive polymers, electro-, magneto- and opto-active macromolecules, inorganic polymers, charge-transporting polymers (ion-containing, semiconducting, and conducting), nanostructured polymers, and polymer composites are also of interest. Typical papers published in Macromolecules showcase important and innovative concepts, experimental methods/observations, and theoretical/computational approaches that demonstrate a fundamental advance in the understanding of polymers.