Study On Preparation And Properties Of Self-assembled Micro-nano Materials Of Poly(Aryl Ether Nitrile Sulfone)

Polysulfone(PSF),as a special polymer with benzene ring and ether bond in the main chain and sulfone group as the characteristic functional group,is widely used in biomedical,environmental governance and food packaging and other fields due to its corrosion resistance and biocompatibility.Poly(arylene ether nitrile)(PEN)is a special engineering plastic containing benzene rings and ether bonds in the main chain and nitrile groups in the side groups,which has the advantages of high strength,high temperature resistance,chemical corrosion resistance and easy processing,so it can be used in the fields of military industry,medical equipment and environmental protection.The research on the structure and properties of the two and the effective combination of the two have guiding significance for promoting their practical application.In this thesis,a series of studies on the structure and properties of PSF,PEN and polyarylethernitrile sulfone(PENS)were carried out,and PSF and PEN homopolymers and amphiphilic PENS block copolymers were synthesized,then amidoximation of PENS(AO-PENS)was obtained by the reaction of PENS cyano group.Then the obtained polymers were used as raw materials to prepare polymer microspheres.Finally,fluorescent functionalized cross-linked poly(aryl ether nitrile sulfone)fluorescent microspheres were obtained by combining rare earth ions with PENS and AO-PENS.The specific research contents are as follows:(1)Bisphenol A-type PSF and phenolphthaloline-type PEN homopolymers were prepared by nucleophilic substitution polycondensation,respectively,amphiphilic PENS block copolymers were obtained by copolycondensation of hydrophilic and hydrophobic segment oligomers,and AO-PENS was obtained by amidoximation of the side chain cyano moiety of PENS.The successful synthesis of polymers of various structures were verified by infrared spectroscopy and hydrogen NMR spectroscopy.The thermal properties of the obtained polymers were then characterized,indicating that the glass transition temperature of all samples was higher than 190 ^oC,and the temperature of 5%thermal weight loss was higher than 430 ^oC.(2)The solution self-assembly behavior of the synthesized PSF,PEN homopolymer,PENS and AO-PENS block copolymer was studied by changing the emulsion conditions of the emulsion solvent evaporation method.PSF,PEN,PENS and AO-PENS microspheres were prepared.It was found that PSF microspheres could be prepared when cetyltrimethylammonium bromide(CTAB)was used as surfactant.PEN microspheres with nanometer size of 200-800 nm could be obtained,when sodium dodecyl sulfonate(SDS)was used as surfactant,but can not be prepared under CTAB.Microspheres with more regular morphology and more uniform particle size can be obtained by PENS and AO-PENS,and the reduction of polymer concentration is beneficial to obtain small-sized microspheres when CTAB is used as surfactant,at the same time,the increase of volatilization temperature will cause the agglomeration of microspheres,etc.(3)Furthermore,in order to enrich the properties of PENS microspheres,the method of introducing rare earth metal ions(Tb³⁺,Eu³⁺)to coordinate with PENS and AO-PENS during the self-assembly process of copolymer emulsions was used to impart fluorescence properties,and micro-nano materials with different emission properties were obtained.The results show that Tb³⁺/Eu³⁺can successfully coordinate with the copolymer to obtain fluorescent microspheres.And the fluorescence emission intensity of the microspheres decreased with the decrease of Tb³⁺/Eu³⁺concentration,the increase of polymer concentration and the increase of volatilization temperature.At the same time,the fluorescence and morphology of the microspheres can be regulated by the concentration of rare earth ions,the amount of polymer and the volatilization temperature,which has potential application value in biological imaging,fluorescence detection and other fields.