Phase Behavior of Frustrated ABC Bottlebrush Block Terpolymers

IF 5.2 1区化学 Q1 POLYMER SCIENCE

Macromolecules Pub Date : 2025-07-08 DOI:10.1021/acs.macromol.5c01090

Subrata Santra, Shuquan Cui, Frank S. Bates* and Timothy P. Lodge*,

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引用次数: 0

Abstract

We investigated the microphase separated morphological behavior of 35 ABC bottlebrush block terpolymers, poly(ethylene-alt-propylene)-b-poly(D,L-lactide)-b-polystyrene (PEP-b-PLA-b-PS), synthesized by ring-opening metathesis polymerization (ROMP) of low dispersity (Đ ∼ 1.1–1.2) norbornene end-capped macromonomers (M_n ∼ 1.5 kg/mol). In PEP-b-PLA-b-PS bottlebrushes, the PEP/PS interface has lower interfacial energy than the mandatory PEP/PLA and PLA/PS interfaces, imparting frustration to the molecular packing. Systematic morphological characterization by small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM) revealed an intriguing 2D rectangular centered cylinders-in-undulating-lamellae (RCCUL) morphology with c2mm symmetry over a significant window of the composition triangle. The data also revealed an unusual trend of a decreasing lamellar domain spacing with increasing total backbone degree of polymerization, which can be attributed to the presentation of the short PS blocks at the PEP/PLA interface, prior to the transition from “two-color” to “three-color” lamellae. The relative ease of norbornene end-capped macromonomer synthesis and subsequent ROMP and the novel morphological behavior of frustrated ABC bottlebrush block terpolymers offer attractive opportunities for the fabrication of functional materials for diverse applications.

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受挫ABC瓶刷嵌段共聚物的相行为

我们研究了35个ABC瓶刷嵌段共聚物的微相分离形态行为，聚（乙烯-丙烯）-b-聚（D， l -丙交酯）-b-聚苯乙烯（PEP-b-PLA-b-PS），低分散性（Đ ~ 1.1-1.2）降冰片烯端封大单体（Mn ~ 1.5 kg/mol）通过开环分解聚合（ROMP）合成。在PEP-b-PLA-b-PS瓶刷中，PEP/PS界面具有比强制性PEP/PLA和PLA/PS界面更低的界面能，给分子包装带来挫折。通过小角x射线散射（SAXS）和透射电子显微镜（TEM）进行系统形态学表征，揭示了一个有趣的二维矩形中心圆柱体-起伏-片层（rcul）形态，在组成三角形的一个重要窗口上具有c2mm的对称性。数据还显示，随着总主链聚合度的增加，层状域间距减小，这可能是由于在PEP/PLA界面上出现了短PS块，在从“双色”层状过渡到“三色”层状之前。降冰片烯端盖大单体的相对容易合成和随后的ROMP以及受挫的ABC瓶刷嵌段三元聚合物的新形态行为为制造各种应用的功能材料提供了有吸引力的机会。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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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.