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

IF 5.1 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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Abstract

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.