Construction Of Functional Polymers By Butynoate-based Polymerizations

Construction of functional polymers by alkyne-based polymerizations has attracted considerable attention.The alkyne-azide click polymerization has become an efficient polymerization reaction.However,the alkyne monomers used in the polymerization are terminal alkynes.The polymerization of internal alkynes and azides is rarely employed for the preparation of functional polymers.In addition,the internal alkyne-alcohol polymerization towards functional polymers has been rarely reported.In this work,metal-free butynoate-azide and butynoate-alcohol polymerizations were developed,and a series of functional polymers were prepared.The effect of temperature,solvent and solvent-free on the yields and molecular weights of the polymers were investigated,and the optimal synthesis conditions were obtained.The solvent-and catalyst-free butynoate-azide polycycloaddition were developed and seven poly(methyltriazolylcarboxylate)s(PMCTs)with high molecular weights were prepared.The PMCTs possess good solubility in common organic solvents and high thermal stability.The tetraphenylethene(TPE)-containing PMCTs are non-emissive in solution,but become highly luminescent in aggregated state,showing aggregation-induced emission(AIE)characteristics.The polymers can function as explosive sensors with high sensitivity,and generate two-dimensional fluorescent photopatterns with high resolution.Furthermore,their triazolium salts show good water dispersibility,and can be utilized for cell-imaging applications.The polymerization was then carried out in DMF,affording four soluble hb-PMCTs with high molecular weights.The TPE-containing hb-PMCTs show AIE characteristics.The polymers can function as explosive sensors with high sensitivity,and generate two-dimensional fluorescent photopatterns with high resolution.Furthermore,their triazolium salts show good water dispersibility,and can be used for cell-imaging applications.The effect of temperature,time and monomer concentration on the polymerization of butynoate and benzyl alcohol was studied,and the optimal polymerization conditions were determined.The metal-free butynoate-alcohol polymerization was developed and four soluble poly(vinyl ether)with high molecular weights were prepared.Thanks to their contained TPE units,the polymers exhibit AIE properties,and can serve as chemosensors to detect explosive.