New Polymerizations Based On Ynamide Or Benzyne Monomers

The exploition of new polymerization methodology plays a vital role in the development of polymer science.Alkynes have been used as polymerization monomers to construct functional polymers for decades for the high reactivity of the carbon-carbon triple bond.The research on alkyne-based polymerization focuses on developing new polymerization reactions.To enrich the family of alkyne-based polymerization,in this thesis,new polymerization reactions based on ynamide monomers and benzyne monomers were successfully established.The detailed contents are described as follows.Firstly,a new rhodium-catalyzed ynamide-azide click polymerization was successfully developed.Using[Rh?CO?₂Cl]₂ as catalyst,the polymerization of diynamide and diazide were carried out in N,N-dimethylformamide at room temperature for 5 h,and poly?5-sulfonamide triazole?with weight-average molecular weight?M_w?up to 75 300 were obtained in 95%yield.The poly?5-sulfonamide triazole?s showed excellent solubility and thermal stability.The polymers constructed with tetraphenylethene?TPE?showed aggregation-induced emission?AIE?property.Secondly,a metal-free[2+2+2]polycyclotrimerization of ynamide with nitrile was developed.Using trimethylsilyl trifluoromethanesulfonate?TMSOTf?as catalyst,the polymerization of diynamide and mononitrile proceeded in 1,2-dichloroethane at room temperature for 6 h,polypyridines with M_w up to 59 500 and regioregularity were obtained.The thermal stability of the polymers were studied.Thirdly,a new benzyne-azide[2+3]polycycloaddition was developed.Dibenzyne monomers generated from their precursors in the presence of cesium fluoride could react with diazides in a Husigen 1,3-dipolar polycycloaddition way and the N-1-substituted polybenzotriazoles with M_w up to 13 000 were produced in 75%yields.The thermal stability,refractive index and photophysical properties of the polymers were studied.Finally,an N-arylation polymerization of benzynes and secondary amines were developed.Poly?tertiary amine?s with M_w up 55 200 were prepared.The photophysical properties of the resultant polymers were studied.At the same time,based on these monomers,a stoichiometric unbalanced polymerization was established.It provided a new and efficient strategy for the preparation of poly?tertiary amine?s.