烷基硼-鎓盐Metal-free体系应用于环氧丙烷/乙烷活性阴离子可控聚合反应
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Well Controlled Living Anionic Polymerization of Propylene Oxide Initiated by Onium Salts in the Presence of Triethyl Borane
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    摘要:

    首次报道了一种由卤代季铵盐或季磷盐等鎓(PO)活性阴离子开环体系,可有效抑制聚合副反应的发生,提高聚合反应活性,并成功制备了相对分子质量及其分布可控的环氧丙烷聚合物(PPO)。通过考察不同烷基硼催化剂用量下,环氧丙烷单体核磁氢谱化学位移变化,证明了该类催化剂对单体具有显著的活化作用。同时,研究了聚合溶剂和鎓盐离子大小对聚合活性的影响,并提出了相关的聚合机理和过程。由于这种聚合体系具有“不死”聚合特征,向体系加入第二单体如环氧乙烷(EO)等,可有效制备结构可控的嵌段聚醚共聚物(PPO-b-PEO)。

    Abstract:

    In this work, a series of novel metal-free anionic polymerization systems, which are composed of onium salts (including some kinds of quaternary ammonium and phosphonium halides) as initiators in combination with alkyl borane as catalyst, were developed for the first time. These systems present excellent polymerization activity and inhibition on side reactions, especially chain transfer reactions. Polypropylene oxides (PPO) with well controlled molecular weights and distributions were successfully synthesized. The chemical shift changes of PO characterized by 1H-NMR spectra clearly confirm the activation of alkyl borane to monomer PO, which has a great relationship with the amounts of borane catalyst. Meanwhile, the effects of solvents and the sizes of onium salts on polymerization were also studied to verify the mechanism and process of polymerization. Owing to its notable living polymerization feature, block polyether (PPO-b-PEO) with definite structures can be easily fabricated through the sequential polymerization of propylene oxide (PO) and ethylene oxide (EO).

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叶李薇,彭华乔,杨 刚,张东岳,夏祖西.烷基硼-鎓盐Metal-free体系应用于环氧丙烷/乙烷活性阴离子可控聚合反应[J].高分子材料科学与工程,2018,34(1):1-5.

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  • 在线发布日期: 2018-01-20
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