A self-crosslinking monomer, a-pinene methacrylate: understanding and exploiting hydrogen abstraction
A self-crosslinking monomer, a-pinene methacrylate: understanding and exploiting hydrogen abstraction
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自交联单体α-蒎烯甲基丙烯酸酯：理解和利用氢提取
DOI：
10.1039/d2py00878e
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发表时间：
2022
影响因子：
4.6
通讯作者：
Monaghan O
中科院分区：
文献类型：
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作者：
Monaghan O
交联是创造新聚合物材料的一种有价值的途径，通常涉及引入交联剂或某种形式的二次加工。本文报道了一种自交联可持续萜烯衍生单体α-蒎烯甲基丙烯酸酯（αPMA）的发现和分析。该单体在自由基均聚过程中与共聚单体如甲基丙烯酸甲酯（MMA）发生交联。α - pma似乎不包含任何明显的功能，可以诱导交联，如乙烯基键，但我们假设它可能会从悬垂基团中偶然抽取一个氢原子。本文采用计算与实验相结合的方法对其进行了研究。此外，我们使用DFT分析来预测相关单体β -甲基丙烯酸蒎烯（βPMA）的行为。据我们所知，这是第一次在甲基丙烯酸酯自由基聚合中观察到自交联，这是通过链转移从垂基团中抽氢而实现的。我们已经利用这种交联来生产新的、可再生的多聚高内相乳剂（polyHIPEs），它可以与那些从化石基苯乙烯中提取的乳液相媲美，而且我们在不需要任何额外交联剂的情况下完成了这一过程。
Crosslinking is a valuable route to creating new polymeric materials and normally involves introduction of a cross linker or some form of secondary processing. Here we report the discovery and analysis of a self-crosslinking sustainable terpene derived monomer, α-pinene methacrylate (αPMA). This monomer undergoes crosslinking during free radical homopolymerisation and with comonomers e.g. methyl methacrylate (MMA). αPMA does not appear to contain any obvious functionality that would induce crosslinking such as vinyl bonds, but we postulate that it may undergo a fortuitous abstraction of a hydrogen atom from the pendant group. A combined computational (DFT) and experimental approach has been applied to investigate this. Further, we used DFT analysis to predict the behaviour of a related monomer, beta-pinene methacrylate (βPMA). To the best of our knowledge this is the first-time that self-crosslinking has been observed in free radical polymerisation of methacrylates via chain transfer through hydrogen abstraction from a pendant group. We have exploited this crosslinking to generate new, renewable poly high internal phase emulsions (polyHIPEs) that could rival those derived from fossil-based styrene- polyHIPEs and we have done this in a process which does not require any additional cross-linking agent.