Phase Behavior of Reversibly Bonding Polymer Blends

IF 5.1 1区化学 Q1 POLYMER SCIENCE

Macromolecules Pub Date : 2025-06-18 DOI:10.1021/acs.macromol.5c01173

Christopher Balzer, Puck Springintveld, Glenn H. Fredrickson

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Abstract

Blending polymers is a versatile strategy for creating materials with tailored properties, but controlling the phase behavior of polymer blends remains a central challenge. Functionalization with sparse, associative chemical groups is a powerful way to shift phase behavior without changing individual component properties. We develop a field-theoretic model for heteroassociating polymer blends using the coherent states formalism, enabling an exact treatment of reversible bonding while avoiding explicit enumeration of polymer topologies. This framework captures the full distribution of supramolecular species, including higher-order branching and large clusters, and reveals how correlations between association sites of multifunctional polymers govern thermodynamic behavior across length scales. Using the random phase approximation, we identify conditions for macrophase separation and microphase ordering, and uncover a new motif for microphase separation in which bond density, rather than species density, exhibits spatial variations. These results unify and extend existing theories of reversibly bonding polymers, including phenomena such as gelation, and establish a foundation for designing compatibilizers through polymer architecture and sequence-level control of reversible interactions.

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可逆键合聚合物共混物的相行为

共混聚合物是一种创造具有定制性能的材料的通用策略，但控制聚合物共混物的相行为仍然是一个核心挑战。用稀疏的、结合的化学基团进行功能化是一种不改变单个组分性质而改变相行为的有力方法。我们开发了异质缔合聚合物共混物的场理论模型，使用相干态形式，使可逆键的精确处理，同时避免了聚合物拓扑的显式枚举。该框架捕获了超分子物种的完整分布，包括高阶分支和大簇，并揭示了多功能聚合物缔合位点之间的相关性如何在长度尺度上控制热力学行为。利用随机相位近似，我们确定了大相分离和微相排序的条件，并揭示了微相分离的新基序，其中键密度而不是物种密度表现出空间变化。这些结果统一和扩展了现有的可逆键合聚合物理论，包括凝胶现象，并为通过聚合物结构和可逆相互作用的序列级控制来设计相容剂奠定了基础。

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.