In-Chain Poly(phosphonate)s via Acyclic Diene Metathesis Polycondensation
In-Chain Poly(phosphonate)s via Acyclic Diene Metathesis Polycondensation
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DOI：
10.1021/acs.macromol.6b00366
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发表时间：
2016-05-24
期刊：
影响因子：
5.5
通讯作者：
Wurm, Frederik R.
中科院分区：
文献类型：
--
作者：
Bauer, Kristin N.;Tee, Hisaschi T.;Wurm, Frederik R.
通过三种不同单体的无环二烯复合聚合制备了链内聚膦酸盐。研制了具有不对称结构的新型不饱和膦酸盐单体。这些单体可以通过三步合成获得，并且很容易按比例放大。本文首次报道了稳定的碳磷键位于聚合物主链上的烯烃复分解聚膦酸盐。与其他聚磷酸酯相比，这改变了降解产物的性质。聚合物的分子量高达31000克摩尔（-1）可以实现，并已详细表征核磁共振波谱，尺寸排除色谱法，热重法，差示扫描量热法。他们也比较了结构类似物聚磷酸盐的结晶（SAXS， WAXS）和他们的流变行为。此外，还分析了溶液生长晶体，使本文报道的一些聚膦酸盐具有有趣的缺陷聚（乙烯）样结构。
In-chain poly(phosphonate)s have been prepared via acyclic diene metathesis polymerization of three different monomers. Novel unsaturated phosphonate monomers with asymmetric structure have been developed. The monomers are accessible via a three-step synthesis that can be easily scaled up. This is the first report on poly(phosphonate)s by olefin metathesis where the stable carbon phosphorus linkage is localized in the polymer backbone. This changes the nature of the degradation products compared to other poly(phosphoester)s. Polymers with molecular weights up to 31 000 g mol(-1) can be achieved and have been characterized in detail NMR spectroscopy, size exclusion chromatography, thermogravimetry, and differential scanning calorimetry. They have been also compared to structural analogues polyphosphates with respect to crystallization (SAXS, WAXS) and their rheological behavior. Also, solution grown crystals were analyzed rendering some of the herein reported poly(phosphonate)s as interesting defect poly(ethylene)-like structures.