Synthesis of Polyphosphazenes by a Fast Perfluoroaryl Azide-Mediated Staudinger Reaction
Synthesis of Polyphosphazenes by a Fast Perfluoroaryl Azide-Mediated Staudinger Reaction
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DOI：
10.1021/acs.macromol.8b00618
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发表时间：
2018-06-26
期刊：
影响因子：
5.5
通讯作者：
Yan, Mingdi
中科院分区：
文献类型：
--
作者：
Sundhoro, Madanodaya;Park, Jaehyeung;Yan, Mingdi
本文报道了双-PFAA(全氟芳基叠氮)与双膦试剂通过快速Staudinger反应合成聚磷腈的方法。在常温下，将N3和两种单体(20 Mm)混合在CH3CN中，在30 mm内聚合，得到相对分子质量大于59000、窄分散度(D)为1.1~1.2的聚磷腈。这比由经典的Staudinger反应得到的聚磷腈有了显著的改进，后者具有较低的相对分子质量((M)over bar(N)=10 000-25 000)和较高的D(1.7)。该反应适用于带有芳香族或脂肪族连接基的双PFAA和双膦。溶剂的极性影响聚合度，与二氯甲烷等极性较弱的溶剂相比，乙腈等极性较大的溶剂可得到较高分子量的聚合物。合成的聚磷腈具有很高的热稳定性，其中芳香族聚磷腈的分解温度高达441℃，焦产率高达53%。
We report the synthesis of polyphosphazenes by a fast Staudinger reaction between a bis-PFAA (perfluoroaryl azide) and a bis-phospine. Polymerization was completed within 30 mM after mixing N3 the two monomers (20 mM) in CH3 CN under ambient conditions to give polyphosphazene with molecular weight of up to over 59 000 and a narrow dispersity (D) of 1.1-1.2. This is a significant improvement over the polyphosphazenes obtained from the classic Staudinger reaction which had lower molecular weight ((M) over bar (n) = 10 000-25 000) and higher D (1.7). This reaction applies to bis-PFAAs and bis-phosphines with either an aromatic or an aliphatic linker. Polarity of the solvent influenced the degree of polymerization, and more polar solvents such as acetonitrile gave higher molecular weight polymer in comparison to less polar solvents such as dichloromethane. The synthesized polyphosphazenes showed high thermal stability, with the aromatic polyphosphazenes giving decomposition temperature and char yield of up to of 441 degrees C and 53%, respectively.