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在三氟甲磺酸稀土盐(Ln(OTf)3,Ln=La,Nd,Sm,Y)的存在下,光学纯N-邻唑啉苯基甲基丙烯酰胺((S)-MeOPMAM)经自由基聚合反应得到相应的光学活性聚合物.考察了稀土盐种类、用量及溶剂性质等因素对聚合反应立体化学的影响.研究发现,以Y(OTf)3为调节剂、正丁醇为溶剂的体系能在一定程度上提高聚合反应的全同立体定向性.聚合物的手性光学性质明显依赖于立构规整度,随全同含量增大,聚合物的比旋光度和π-π*电子跃迁区域的Cotton效应强度呈下降趋势.利用1H-NMR技术研究了上述聚合物与1,1′-联-2-萘酚(BINOL)的对映选择性相互作用,结果表明,全同三元组含量较高的聚合物不仅使酚羟基质子峰向低场位移,而且导致信号分裂.
An optically pure N-ortho-oxazoline phenylmethacrylamide ((S) -MeOPMAM) is present in the presence of rare earth triflate salt (Ln (OTf) 3, Ln = La, Nd, Sm, The corresponding optically active polymers were obtained by free radical polymerization.The effects of rare earth salt, dosage and solvent on the stereochemistry of the polymerization were investigated.The results showed that n (OTf) 3 The solvent system can improve the stereospecificity of the polymerization to a certain extent.The chiral optical properties of the polymer obviously depend on the stereoregularity, with the increase of the same content, the specific rotation of the polymer and π-π * The intensity of Cotton effect in the electronic transition region showed a decreasing trend.The enantioselective interaction between the above polymer and 1,1’-bi-2-naphthol (BINOL) was studied by 1H-NMR. The results showed that all the same Polymers with higher triads not only shift the phenolic hydroxyl proton peak to a lower field, but also cause signal splitting.