RDRP在连续流反应器中同时调节分子量分布和组成：动力学模型

IF 5.2 1区化学 Q1 POLYMER SCIENCE

Macromolecules Pub Date : 2025-01-27 DOI:10.1021/acs.macromol.4c02183

Haiyan Xue, Junpo He

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引用次数: 0

摘要

调节分子量分布和共聚物组成对高分子材料的性能控制具有重要意义。将可逆失活自由基聚合（RDRP）与连续流合成技术相结合，为定制复杂的mwd提供了新的机会。在本工作中，我们提出了一种流动控制策略，以同时设计连续流动条件下原子转移自由基聚合的随钻速度和共聚物组成。该方法的一个独特之处在于其设计的流量曲线，其范围可以从启动器注入流量的分段变化到准连续变化。利用高斯分布数学方程和蒙特卡罗模拟，建立了采油产品的流量分布与随钻率之间的关系。结果表明，该建模方法不仅可以根据给定的流量曲线预测随钻数据，还可以确定能够产生任何复杂目标随钻数据的流量情景。此外，我们提出了一个三泵流聚合系统，能够生产具有定制分布的共聚物，并选择性地将共聚物单元纳入特定的产品馏分。这些概念演示为MWD的新模式和组分调节提供了理论框架，只需调整给定仪器配置的注入流剖面即可实现。这种方法在生产具有理想mwd和定制化学成分分布的聚合物方面具有相当大的潜力。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Simultaneous Regulation of Molecular Weight Distribution and Composition through RDRP in a Continuous-Flow Reactor: A Kinetic Modeling

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Simultaneous Regulation of Molecular Weight Distribution and Composition through RDRP in a Continuous-Flow Reactor: A Kinetic Modeling

Regulating the molecular weight distribution (MWD) and copolymer composition is of great significance for controlling the properties of polymer materials. Combining reversible deactivation radical polymerization (RDRP) with continuous-flow synthesis techniques offers new opportunities to tailor complex MWDs. In the present work, we propose a flow-control strategy to simultaneously engineer the MWD and copolymer composition in atom transfer radical polymerization under continuous-flow conditions. A unique aspect of this approach is the intentionally designed flow rate profile, which can range from staged to quasi-continuous variations of the initiator injection flow rate. The relationship between flow rate profiles and the resulting MWD of the collected products was modeled by using Gaussian distribution mathematical equations and Monte Carlo simulations. The results show that this modeling method can not only predict the MWD from a given flow rate profile but also determine a flow rate scenario capable of producing any complex target MWD. Furthermore, we proposed a three-pump flow polymerization system capable of producing copolymers with tailored distributions and selective incorporation of comonomer units into specific product fractions. These conceptual demonstrations provide a theoretical framework for a new mode of MWD and composition regulation achieved simply by adjusting the injection flow profile of a given instrument configuration. This approach holds considerable potential for producing polymers with the desired MWDs and tailored chemical composition distributions.

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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.