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High Performance Redox Initiating Systems Based on the Interaction of Silane with Metal Complexes: A Unique Platform for the Preparation of Composites

机译:基于硅烷与金属配合物相互作用的高性能氧化还原引发体系:制备复合材料的独特平台

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摘要

Currently, Redox Initiating Systems (RISs) of Free Radical Polymerization (FRP) are mainly based on the interaction of aromatic amines with peroxides (e.g., dibenzoyl peroxide (BPO)) that can be both toxic and unstable. In the present work, we aim to replace these hazardous substances in new RIS that can be peroxide-free and amine-free. Our redox two components (2K) initiating system is based on diphenylsilane (DPS) as reducing agent combined with different metal complexes (Mn(acac) , Cu(AAEMA) or Fe(acac) ) as oxidizing agents. For the new proposed RIS, an excellent reactivity is found for the polymerization of benchmark methacrylate monomers under mild conditions (redox polymerization done under air and at room temperature); remarkably, it is also possible to finely control the gel time. Different techniques (optical pyrometry, Real-Time FTIR spectroscopy, Cyclic Voltammetry and Electron Spin Resonance (ESR)) were used to follow the polymerization processes but also to shed some light on the new redox chemical mechanisms.
机译:当前,自由基聚合(FRP)的氧化还原引发体系(RIS)主要基于芳族胺与过氧化物(例如,二苯甲酰过氧化物(BPO))的相互作用,该过氧化物既有毒又不稳定。在当前的工作中,我们的目标是在新的RIS中替代这些有害物质,这些RIS可以无过氧化物和无胺。我们的氧化还原两组分(2K)引发体系基于作为还原剂的二苯基硅烷(DPS)与作为氧化剂的不同金属配合物(Mn(acac),Cu(AAEMA)或Fe(acac))结合使用。对于新提出的RIS,在温和条件下(基准空气中和室温下进行的氧化还原聚合反应),对基准甲基丙烯酸酯单体的聚合反应具有出色的反应活性。显着地,还可以精细地控制胶凝时间。使用了不同的技术(光学高温测定法,实时FTIR光谱法,循环伏安法和电子自旋共振(ESR))来跟踪聚合过程,同时也阐明了新的氧化还原化学机理。

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