巯基-烯点击反应制备含不同功能端基的环三磷腈衍生物  

Preparation of cyclotriphosphazene derivative with different functional terminal groups via thiol-ene click

作　　者：王海侨[1] 刘卫卫[1] 叶俊 乔志 李琦 李效玉[1] Wang Haiqiao;Liu Weiwei;Ye Jun;Qiao Zhi;Li Qi;Li Xiaoyu(Beijing Engineering Research Center for the Synthesis and Applications ofWaterborne Polymers,College of Materials Science and Engineering,Beijing University ofChemical Technology,Beijing 100029)

机构地区：[1]水性聚合物合成与应用北京市工程研究中心北京化工大学材料科学与工程学院,北京100029

出　　处：《化工新型材料》2019年第3期108-112,共5页New Chemical Materials

摘　　要：环三磷腈衍生物在阻燃添加剂、生物医药材料、电解液和液压油等领域有着广泛的应用前景,因此,近年来环三磷腈衍生物的功能化改性研究受到越来越多的关注。利用巯基化合物与丁香酚氧基环三磷腈在紫外光下的巯基-烯点击反应,制备了末端分别含有烷基、羟基和羧基等不同功能基团的系列环三磷腈衍生物,研究了反应时间、投料比和巯基反应物所带的端基官能团对反应的影响规律。发现此方法具有反应条件温和,反应时间短(≤30min),反应产率高(≥95%),可批量制备的优点;同时还可以将具有不同结构的功能基团定量的引入到目标产物中。对产物的热性能表征结果表明,C—S键的引入降低了环三磷腈衍生物的热稳定性,但产物的起始分解温度依然保持在300℃以上;末端基团的种类对产物的热稳定性和受热分解后的残炭量有一定影响。Cyclotriphosphazene derivatives have drawn increasing attention because they have significant potential applications in flame-retardant additives,biomedical material,electrolyte and hydraulic fluid,etc.A series of cyclotriphosphazene derivatives with different functional terminal groups,such as alkyl,hydroxyl or carboxyl,were synthesized through thiol-ene click reaction between thiol compounds with different functional terminal groups and cyclotriphosphazene with eugenol oxygen groups under the UV light.The effect of reaction times,feed ratios and terminal groups of thiol reactants were studied.The results revealed that this strategy for preparing cyclotriphosphazene derivatives possessed many advantages,such as mild reaction conditions,fast reaction times(≤30 min),high reaction yields(≥95%)and easy to mass-producton.Moreover,the functional terminal groups can be introduced quantitatively.The measurement on the thermal properties demonstrated that the introduced C-S bond reduced the thermal stability of targeted produces,but the onset decomposition temperature still keeps on above 300℃.Moreover,the kinds of terminal groups affected the thermal stability and the char forming of products.

关 键 词：巯基-烯点击反应 环三磷腈衍生物 末端功能化 热分解 

分 类 号：O626[理学—有机化学]