铜催化磷酰基叠氮参与的三组分聚合制备聚膦酰基脒

Copper-catalyzed,Three-component Polymerization for the Synthesis of Polyphosphonylamidines

为进一步发展高效的多组分聚合方法,构建有应用前景的高分子材料,本文报道了一种基于一价铜催化的,以叠氮磷酸二苯酯(DPPA)、二炔和二胺为单体的多组分聚合方法,在N,N-二甲基甲酰胺(DMF)中室温反应4 h,制备了一系列聚膦酰基脒,产率高达90%,重均分子量高达54000 g/mol,仅生成氮气为副产物.DPPA参与聚合具有后修饰的潜在应用,克服传统磺酰基叠氮后修饰困难的缺点.以含缩硫酮的二胺为聚合单体可制备具有特殊结构、活性氧敏感的聚膦酰基脒,在活性氧刺激下实现聚合物的降解.通过核磁共振波谱,凝胶色谱及基质辅助激光解吸飞行时间质谱确定聚合物结构、分子量及重复单元,并研究了炔类单体的刚柔性和胺类单体的位阻效应对聚合反应的影响.该聚合方法为多组分聚合提供了一种新的途径,拓宽了高分子材料的应用范围,为下阶段探索聚脒材料的应用奠定基础.

Multicomponent polymerization(MCP)could efficiently synthesize multi-functional polymers with structural diversity.In order to further expand MCP and construct the polymers with potential application,in this work,we report an efficient Cu-catalyzed MCP technique that enables the synthesis polyphosphonylamidines of high molecular weight(up to 54000 g/mol)and high yield(up to 90%)from monomers of diphenyl phosphate azide(DPPA),diynes and diamines,in N,N-dimethylformamide(DMF)at room temperature for 4 h.The obtained polymers have more potential in application after post-functionalization,compared with the polymers prepared by the sulfonyl azide.Reactive oxygen species responsive polyphosphonylamidines with special construction are prepared by using thioketal diamine as polymeric monomer,and these polymers exhibit excellent degradation property by ROS-triggered.The structure,molecular weight and repeat units of all synthetic polymers are determined by nuclear magnetic resonance(NMR),gel permeation chromatography(GPC)and MALDI-TOF.The effects of rigidity and flexibility of diynes and steric hindrance of diamines on the MCP are investigated.This polymerization method provides a powerful approach for MCP to synthesize functional polymers and broadens the application fields of polymer science.