The Preparation Of Poly Phosphinates

As a new way of polymerization, carbene polymerization has the incomparable advantage compared to traditional addition polymerization. Until now, only a few literatures have reported the polymerization of a-carbonyl-carbenes, but the polymerization of phosphory lcarbenes has never been reported in any literature.In the paper we first prepared a series of diethyl phosphonates by Arbuzov reaction which were then through mono-hydrolysis and chlorination to afford phosphonic chlorides with different substituents, and then their reactions with diazomethane to afford a series of poly-ethyl methylenephosphinates were further studied.The mechanism of polymer formation is proved by chemical correlation to be phosphorylcarbene insertion, and carbene insertion position is a position of phosphorylcarbene. The solid-NMR data certified the mechanism. Meanwhile, the polymer with the highest yield synthesized from phosphonomethoxybenzyl carbene is characterized by GPC, TG, the results of which indicate the superior physical and chemical properties of the polymers.Because of the special structure and composition of the polymers synthesized from phosphorylcarbenes, they have outstanding thermal stability, high phosphorus content and good ability to resist organic solvents. With all the advantages they have, the polymers synthesized from phosphorylcarbenes have a very high potential value.