Preparation Of Nano-sized AS Resin And Its Application In Supercapacitor Electrode Materials

Polymeric nanomaterials exhibit great application prospects in nanoreactors,catalysts,cosmetics,biological medicine due to their unique morphologies,structures and properties.Polymerization-induced self-assembly and reorganization?PISR?is a newly developed method which can prepare polymeric nanomaterials with various morphologies simply and efficiently.Broadening polymerization systems and applications of this method is another challenge.Polymeric AS resin nanomaterials is rarely reported in the literature,though AS resin is one of the highest yield of engineering plastics.It is very important and promising to study the preparation of nano-sized AS resin to improve the potential performances and applications of engineering plastics.Therefore,this dissertation focus on the preparation and morphology control of nano-sized AS resin.What's more,the application of polyacrylonitrile nanomaterials as the Precursor of Nitrogen-doped carbon material is also studied.The primary results are listed as follows.?1?Polymerization induced self-assembly and reorganization?PISR?is conducted via RAFT dispersion polymerization of acrylonitrile and the copolymerization of acrylonitrile and styrene in ethanol using P4VP-TC as macro RAFT agent.Various morphologies of nano-sized AS resin are fabricated by adjusting the initial ratio of acrylonitrile to styrene.With the increase of styrene content in the initial feed ratio,the assemble aggregates undergo a variety of morphological changes ranging from needle-like aggregates,spheres,thick-walled vesicles,microspheres with different surface features to vesicles.The morphologies of Polyacrylonitrile can be changed from needle-like aggregations to spheres by adding a small amount of styrene.It's thought to be caused by the decrease in crystallinity of the block polymer.?2?Polymerization induced self-assembly and reorganization?PISR?is conducted via RAFT dispersion polymerization of acrylonitrile and styrene in ethanol using P4VP-TC as macro RAFT agent.At the initial molar feed ratio of 1:1?styrene to acrylonitrile?,“pin-cushion”,“Wax-berry”and asymmetric compound vesicles are successfully fabricated.The results of ¹H NMR,GPC and TEM show that these three types of microspheres respectively undergo the evolution process from solid spheres,thick-wall vesicles,vesicles which caused by different DP of the block copolymers in polymerization.At the initial molar feed ratio of 76:24?styrene to acrylonitrile?,Large vesicles are successfully fabricated.At this ratio,constant ratio copolymerization is carried out where DP_PS/DP_PAN is a constant of about 2.4 by ¹H NMR.Decomposition and reorganization of small vesicles were observed by TEM.A variety of polyacrylonitrile nanocomposites with different morphologies can be prepared by adding good solvent?DMSO,DMF?to the polymerization system.The addition of good solvent can improve the compatibility of the solvent to the polyacrylonitrile segment and promote the diffusion of monomers into the micellar nucleus.Therefore,the preparation of nanomaterials with different morphologies of polyacrylonitrile can be fabricated.?3?Three groups of Nitrogen-doped carbon materials dedriving from PAN polymeric nanomaterials were prepared after preoxidation and carbonation process.The skeleton and the large/medium pore structure of PAN nanomaterials can be retained.Nitrogen content of carbon materials can reach 10%¹5%and these nitrogen atoms which is either pyridine nitrogen or nitrogen nitrogen possess electrochemical activity.Quinone oxygen of the carbon materials can also improve the chemical properties.Electrochemical performance is tested by CV and GCD.The results show that the specific capacitance of these carbon materials can reach 200F·g^-1,and the retention rate of specific capacitance from the current density of 0.5 A·g^-1 to 10A·g^-11 can reach 58.85%.After five hundred cycles of charge and discharge,the specific capacitance only attenuated by 1.75%.