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RAFT Emulsion Polymerization: MacroRAFT Agent Self-Assembly Investigated Using a Solvachromatic Dye.
Biomacromolecules ( IF 5.5 ) Pub Date : 2020-06-19 , DOI: 10.1021/acs.biomac.0c00685
Steven W Thompson 1 , Thiago R Guimarães 1 , Per B Zetterlund 1
Affiliation  

Polymerization-induced self-assembly (PISA) and amphiphilic-macroRAFT-mediated emulsion polymerization are commonly used approaches for synthesis of well-defined polymers and sophisticated particle morphologies. One aspect of these systems that remains relatively unexplored is the conformational state of macroRAFT agents in aqueous solution. To redress this deficiency, we have used fluorescence spectrometry experiments to conduct detailed investigations of the coil conformation across a wide range of pH values for a series of poly(acrylic acid) (PAA) and poly(methacrylic acid) (PMAA) macroRAFT agents with different Z-groups (-S-(CH2)2-COOH, -S-(CH2)3-CH3, and -S-(CH2)11-CH3), as well as amphiphilic macroRAFT agents (PMAA-b-poly(methyl methacrylate)(PMMA) and PAA-b-polystyrene(PS)). The critical aggregate concentrations (CAC) or critical micelle concentrations (CMC) for all systems ranged from 7.48 × 10–7 to 2.57 × 10–3 mol L–1. Overall, an extensive library of CAC/CMC values has been compiled for PAA- and PMAA-based macroRAFT agents at different pH conditions, providing important information related to the mechanistic understanding and optimization of macroRAFT-assisted emulsion polymerization.

中文翻译:

RAFT乳液聚合:使用溶剂型染料对MacroRAFT剂的自组装进行了研究。

聚合诱导的自组装(PISA)和两亲性的macroRAFT介导的乳液聚合是合成定义明确的聚合物和复杂颗粒形态的常用方法。这些系统中尚未得到充分研究的一个方面是macroRAFT剂在水溶液中的构象状态。为了解决这一缺陷,我们使用荧光光谱实验对一系列带有聚丙烯酸(PAA)和聚(甲基丙烯酸)(PMAA)macroRAFT试剂的pH值进行了广泛的线圈构象的详细研究。不同的Z-基(-S-(CH 22 -COOH,-S-(CH 23 -CH 3和-S-(CH 211-CH 3),以及两亲的macroRAFT剂(PMAA- b-聚(甲基丙烯酸甲酯)(PMMA)和PAA- b-聚苯乙烯(PS))。所有系统的临界聚集体浓度(CAC)或临界胶束浓度(CMC)范围从7.48×10 –7到2.57×10 –3 mol L –1。总体而言,已经为基于PAA和PMAA的macroRAFT试剂在不同pH条件下编译了广泛的CAC / CMC值库,提供了有关macroRAFT辅助乳液聚合的机理理解和优化的重要信息。
更新日期:2020-06-19
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