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以2-(6-氧化-6-氢-二苯基(c,e)<1,2>氧杂磷酰基)-1,4-二羟基苯(ODOPB)结构单元为中心,在两侧通过酯化反应分别引入4-乙炔基苯甲酰基和4-烷氧基苯甲酰基,并作为乙炔单体,在[Rh(nbd)Cl]2催化下,30℃聚合得到了含磷酰杂菲(DOPO)基团的聚乙炔.1H-NMR和GPC分析表明,由于DOPO存在较大π共轭结构和较强极性效应,在诱导聚乙炔主链采取高反式构型的同时,增加了分子链内相邻侧基之间的相互作用,使整个分子链趋向二维共平面结构,有利于增强分子链之间的相互作用.TGA显示,与不含磷酰杂菲侧基的模型聚乙炔相比,DOPO的引入使聚乙炔呈现良好的热稳定性,起始热分解温度(T5%)接近400℃,说明通过增强分子链内侧基间相互作用有助于提高热稳定性.
(2-oxo-6-oxo-diphenyl (c, e) <1,2> oxaphosphoyl) -1,4-dihydroxybenzene (ODOPB) In the esterification reaction, 4-ethynylbenzoyl and 4-alkoxybenzoyl groups were introduced respectively and acetylene monomer was polymerized at 30 ℃ under the catalysis of [Rh (nbd) Cl] 2 to obtain phosphoraphane (DOPO) group .1H-NMR and GPC analysis showed that due to the existence of a larger π-conjugated structure and a more polar effect, DOPO induced a high trans-configuration of the polyacetylene backbone and increased Interaction between adjacent side groups in the molecular chain, the entire molecular chain tends to two-dimensional coplanar structure, is conducive to enhancing the interaction between the molecular chains .TGA showed that the side groups with no phosphoryl phenanthrene poly Compared with acetylene, the introduction of DOPO makes the polyacetylene exhibit good thermal stability and the initial thermal decomposition temperature (T5%) is close to 400 ℃, which indicates that the thermal stability can be improved by enhancing the intermolecular interaction inside the molecular chain.