Exploring the Removal of Thiocarbonylthio Chain Ends from Poly(styrene-alt-maleic anhydride) Copolymers

IF 5.2 1区化学 Q1 POLYMER SCIENCE

Macromolecules Pub Date : 2025-09-03 DOI:10.1021/acs.macromol.5c01887

Michael-Phillip Smith, , , Lauren E. Ball, , , Ilanie Wessels, , and , Bert Klumperman*,

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Abstract

Poly(styrene-alt-maleic anhydride) (SMAnh), an alternating copolymer composed of electron-rich styrene (STY) and electron-deficient maleic anhydride (MAnh) comonomers, was synthesized via reversible addition–fragmentation chain transfer (RAFT)-mediated polymerization, using either a trithiocarbonate, dithiobenzoate, or dithiocarbamate chain transfer agent (CTA). SMAnh copolymers with different terminal repeat units (MAnh vs STY) were subjected to either radical-induced reduction or thermolysis to facilitate the transformation of the thiocarbonylthio functional chain end. The chemical composition of the ω-chain end and the solvency conditions employed during each end-group removal process were found to significantly influence the rate and extent of removal/transformation of the thiocarbonylthio functional group. MAnh-functional ω-chain ends enhanced the lability of the thiocarbonylthio group for all end-group removal strategies assessed, suggesting that electron-deficient chain ends facilitate higher efficiency removal of thiocarbonylthio functional groups. Additionally, 3,5-dimethyl pyrazole dithiocarbamate chain ends were reduced or thermolyzed faster and to a higher degree than trithiocarbonate- or dithiobenzoate-functional chain ends.

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探讨从聚苯乙烯-马来酸酐共聚物中去除硫代羰基硫代链端

摘要以三硫代碳酸酯、二硫代苯甲酸酯和二硫代氨基甲酸酯为转移剂，通过可逆加成-断裂链转移（RAFT）催化聚合，合成了富电子苯乙烯（STY）和缺电子马来酸酐（MAnh）共聚物。具有不同末端重复单元（MAnh vs STY）的SMAnh共聚物进行自由基诱导还原或热裂解以促进硫代羰基硫代官能链末端的转化。ω链末端的化学组成和每个端基去除过程中所采用的溶解条件对硫代羰基硫代官能团的去除/转化速率和程度有显著影响。高官能团的ω-链末端增强了硫代碳基硫基对所有端基去除策略的稳定性，这表明缺电子的链末端有助于更高效率地去除硫代碳基硫基。此外，3,5-二甲基吡唑二硫代氨基甲酸酯链端比三硫代碳酸酯或二硫代苯甲酸酯官能团链端还原或热解速度更快，程度更高。

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.