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以Michaelis-Arbuzov反应制备的烯丙基膦酸二乙酯(Ⅰ)为原料,经过两步反应制备了一个非对称的链状端基二烯含磷化合物Ⅲ,化合物Ⅲ进行闭环复分解反应,制备了一种七元含磷、含氧杂环烯烃化合物Ⅳ。初步尝试了化合物Ⅲ的非环二烯复分解聚合(ADMET)和化合物Ⅳ的开环易位聚合(ROMP)反应,得到具有相同化合物结构的含磷聚合物P(Ⅲ)和P(Ⅳ)。通过1HNMR、~1H-~1H COSY、FTIR和GPC对目标化合物的结构进行了表征,结果表明,化合物Ⅲ、Ⅳ及P(Ⅲ)的FTIR中均存在1 633 cm-1处CC的伸缩振动吸收峰,定性分析可知,峰强度与各化合物的CC官能团数成正比;在1HNMR中,化合物Ⅲ在δ2.39处出现的四重峰即为与烯丙基相邻的碳上质子的特征峰,而化合物Ⅳ在δ5.88和δ5.70处的特征峰积分面积相等,说明化合物Ⅳ中的不饱和双键为环内双键,均聚物P(Ⅲ)在δ5.05~5.35的特征峰则归属于聚合物主链中不饱和双键上质子的特征峰;由聚合物P(Ⅲ)的GPC数据可知,其重均相对分子质量约为7 600 g/mol,PDI>1.6。
An asymmetric, chain-terminated diene phosphorus-containing compound III was prepared via a two-step reaction of diethyl allylphosphonate (I) prepared by the Michaelis-Arbuzov reaction. The compound Ⅲ was subjected to ring-closing metathesis reaction to prepare A seven - membered phosphorus, oxygen containing heterocyclic alkene compound Ⅳ. The ring-opening metathesis polymerization (ROMP) reaction of non-cyclic diene metathesis polymerization (ADMET) of compound III and P (Ⅳ) was attempted initially to obtain phosphorus-containing polymers P (Ⅲ) and P (Ⅳ) with the same compound structure. The structures of the target compounds were characterized by 1HNMR, ~ 1H- ~ 1H COZY, FTIR and GPC. The results showed that all the FTIRs of compounds Ⅲ, Ⅳ and P (Ⅲ) had CC stretching at 1 633 cm -1 Vibrational absorption peak, qualitative analysis shows that the peak intensity and the number of CC functional groups of each compound is proportional to; in 1HNMR, Compound Ⅲ quadripartite peak at δ2.39 that is adjacent to the allyl carbon on the proton , While the integral peak of the characteristic peaks at δ5.88 and δ5.70 of compound Ⅳ are equal, indicating that the unsaturated double bond in compound IV is an intracord double bond, the homopolymer P (Ⅲ) The characteristic peak of 5.35 belongs to the characteristic peak of the proton on the unsaturated double bond in the main chain of the polymer. From the GPC data of the polymer P (III), the weight average molecular weight is about 7 600 g / mol, PDI> 1.6.