Because of facile implementation, quantitative conversions, and an insensitivity to oxygen, water, and most organic functional groups, radical-mediated thiol–ene coupling (TEC) reactions have emerged as a valuable tool in macromolecule synthesis. It was recently demonstrated that the kinetics and conversions of thiyl radical-mediated reactions are adversely affected in the presence of basic amines by the formation of retardive thiolate anions. Herein, the performance of TEC polymerizations is evaluated under a variety of reaction environments with the intention to aid in the optimal formulation design of TEC reactions in the presence of amines. Results from both bulk and aqueous-phase network photopolymerizations established that sensitivity to amine basicity and pH is dependent on the thiol acidity, although norbornene-type alkenes exhibit a unique ability to achieve high conversions, where allyl ethers, vinyl ether, and vinyl siloxanes are highly inhibited. Additionally, the protic solvents such as alcohols and acetic acid are established as ideal solvents or additives to suppress or eliminate amine-induced retardation.

中文翻译：

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在胺和硫醇盐阴离子存在下，反应环境对自由基硫醇-烯聚合动力学的影响

由于易于实施、定量转换以及对氧、水和大多数有机官能团的不敏感性，自由基介导的硫醇-烯偶联 (TEC) 反应已成为大分子合成中的一种有价值的工具。最近证明，硫自由基介导的反应的动力学和转化在碱性胺的存在下会因形成阻滞硫醇根阴离子而受到不利影响。在此，TEC 聚合的性能在各种反应环境下进行评估，旨在帮助在胺存在下优化 TEC 反应的配方设计。本体和水相网络光聚合的结果表明，对胺碱度和 pH 值的敏感性取决于硫醇酸度，尽管降冰片烯型烯烃表现出实现高转化率的独特能力，其中烯丙基醚、乙烯基醚和乙烯基硅氧烷受到高度抑制。此外，质子溶剂如醇和乙酸被确立为理想的溶剂或添加剂，以抑制或消除胺诱导的延迟。