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丙烯腈在浓硫氰化钠溶液中应用过氧化氢物(第三丁基过氧化氢,TBH)与胺(三乙醇胺,TEA)作为氧化还原引发体系成功地进行聚合,已有报导。并且初步提出了这个引发体系的反应机构,当时未能肯定醇胺的反应产物,随后我们又研究了TBH与各种胺组成的引发体系对丙烯腈水溶液聚合的影响,并发现胺的结构对聚合反应的关系很大,以聚合速度而言,则胺的碱性强(pK_b小),诱导期短,聚合速度快;以转化率而言,则TEA最大,(C_2H_5)_3N最小。关于过氧化物与胺的引发体系,只有过氢化苯甲酰(BPO)与N,N-二甲基苯胺(DMA)这一体系,由Horner、井本及O’Driscoll
The successful polymerization of acrylonitrile with hydrogen peroxide (TBH) and amine (triethanolamine, TEA) as a redox initiator in concentrated sodium thiocyanate solution has been reported. The reaction mechanism of this initiation system was initially proposed. At that time, the reaction products of the alkanolamines were not confirmed. Then we studied the influence of the initiator system composed of TBH and various amines on the polymerization of acrylonitrile in aqueous solutions. The reaction has a great relationship. For the polymerization rate, amine has strong basicity (pK_b), short induction period and high polymerization rate. TEA is the largest and (C_2H_5) _3N is the smallest with conversion rate. For peroxide and amine initiation systems, only the system of hydroperoxy benzoyl (BPO) and N, N-dimethylaniline (DMA) was developed by Horner, Iwamoto and O’Driscoll