Synergistic Radical Taming by Concurrent Degenerative Transfer and Atom Transfer Radical Polymerization in Emulsion

IF 5.2 1区化学 Q1 POLYMER SCIENCE

Macromolecules Pub Date : 2024-10-15 DOI:10.1021/acs.macromol.4c01812

Francesco De Bon, Teresa J. Lourenço Bernardino, Arménio Coimbra Serra, Marco Fantin, Krzysztof Matyjaszewski, Jorge Fernando Jordao Coelho

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Abstract

Atom transfer radical polymerization (ATRP) and reversible addition–fragmentation chain transfer polymerization (RAFT) are two independent polymer synthesis methods. Here, we show that the synergy between the ATRP and RAFT degenerative transfer mechanisms under emulsion conditions is a promising and attractive option for scalable and efficient polymerization processes, offering significant advantages over stand-alone procedures. They work synergistically, reinforcing each other and relaxing the stringent conditions required for controlled radical polymerization in emulsion. This drastically reduces the metal loading and environmental impact. Stable, well-defined latexes of poly(n-butyl methacrylate) with predetermined molecular weights and Đ < 1.5 were obtained with only 50 μM Cu (18.3 ppm) on a 1 L scale and even below this concentration on a 20 mL scale. The latex color imparted by the RAFT chain transfer agent was catalytically decolorized by a one-pot, nondisruptive method using an ATRP Cu catalyst via the oxygen reduction reaction (ORR).

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通过乳液中同时发生的退化转移和原子转移自由基聚合作用协同驯化自由基

原子转移自由基聚合（ATRP）和可逆加成-碎片链转移聚合（RAFT）是两种独立的聚合物合成方法。在这里，我们展示了在乳液条件下，ATRP 和 RAFT 退化转移机制之间的协同作用是可扩展的高效聚合工艺的一种有前景、有吸引力的选择，与独立的程序相比具有显著优势。它们协同工作，相互促进，放宽了在乳液中进行受控自由基聚合所需的严格条件。这大大降低了金属负荷和对环境的影响。在 1 升规模的聚甲基丙烯酸正丁酯乳液中，只需 50 μM 铜（18.3 ppm）就能获得具有预定分子量和 Đ < 1.5 的稳定、明确的聚甲基丙烯酸正丁酯乳液，在 20 mL 规模的聚甲基丙烯酸正丁酯乳液中甚至低于这一浓度。使用 ATRP Cu 催化剂，通过氧还原反应 (ORR) 以单锅、无干扰的方法对 RAFT 链转移剂赋予的胶乳颜色进行催化脱色。

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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.