Chemistry Agnostic and Facile Method for Programming the Molecular Weight Distribution of Polymers

IF 5.1 1区化学 Q1 POLYMER SCIENCE

Macromolecules Pub Date : 2024-11-27 DOI:10.1021/acs.macromol.4c01973

Michael T. Taleff, Antonia Statt, Damien Guironnet

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Abstract

Many of a polymer material’s bulk properties (e.g., tensile strength, viscosity, and self-assembly) are dependent upon its molecular weight distribution. Thus, optimizing the properties of polymers requires systematic tuning of their molecular weight distributions. We developed a simple protocol for the synthesis of polymers with precisely programmed molecular weight distributions, which is applicable across all polymerizations in which molecular weight increases with time. Experimentally, the solution from an active polymerization vessel is transferred to a quenching vessel over time, building a targeted molecular weight distribution. The transfer rate is calculated using a robust and versatile mathematical model. The model includes an interpolation method that predicts the molecular weight distribution at any time during polymerization from a limited set of kinetic data. This interpolation enables the predictive capabilities of our protocol. We demonstrate the method by synthesizing polymers with square or trapezoidal molecular weight distributions using the group transfer polymerization of methyl methacrylate, the ring-opening metathesis polymerization of exo-5-norbornene-2-methylbenzoate, the atom transfer radical polymerization of methyl methacrylate, and the ring-opening polymerization of butylene oxide.

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与化学无关的聚合物分子量分布编程简便方法

聚合物材料的许多基本特性（如拉伸强度、粘度和自组装）都取决于其分子量分布。因此，要优化聚合物的性能，就必须系统地调整其分子量分布。我们开发了一种用于合成具有精确编程分子量分布的聚合物的简单方案，该方案适用于分子量随时间增加的所有聚合过程。实验中，随着时间的推移，活性聚合容器中的溶液被转移到淬火容器中，从而形成目标分子量分布。传输速率是通过一个稳健、通用的数学模型计算得出的。该模型包括一种内插法，可根据一组有限的动力学数据预测聚合过程中任何时间的分子量分布。这种内插法使我们的方案具有预测能力。我们利用甲基丙烯酸甲酯的基团转移聚合、外-5-降冰片烯-2-甲基苯甲酸酯的开环偏析聚合、甲基丙烯酸甲酯的原子转移自由基聚合以及环氧丁烯的开环聚合，合成了分子量分布为正方形或梯形的聚合物，从而演示了该方法。

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.