Preparation Of Micro-nanostructured Conducting Polymers Based On Amphiphilic Block Copolymer And Their Applications

The application of conductive polymers is influenced by the size and morphology.Therefore,the preparation of conductive nano-scale polymer materials with good properties has become a hot research topic.Amphiphilic block copolymers has a structure of easy to design and their micelles can be used as"nanoreactor"to construct conductive polymer micro/nanostructures because of their various self-assembly morphologies and ordered nanostructures.The introduction of conductive polymer blocks on amphiphilic block copolymers provides more possibilities to regulate its morphology and size and improve its functionality.At the first part of this study,amphiphilic block copolymers with stimulus response blocks were designed and synthesized.The morphology of these block copolymer micelles was controlled by changing temperature and p H value,then these micelles were used to prepare conductive polymers with controllable size and uniform morphology.The electrochemical properties of conductive polymers mentioned above were preliminarily investigated.Secondly,amphiphilic block copolymer containing polyaniline bolck was synthesized and its electrochemical properties were tested.The specific research contents are as follows:（1）A series of stimulus-responsive amphiphilic block copolymers were synthesized by RAFT polymerization,including p H response block copolymers PS_x-b-P2VP₇₀（x=38、64、101）、PS_x-b-PAA₇₀（x=38、64、101）、Pn BA₂₈-b-PS₇₅-b-P2VP₁₀₄;temperature-responsive block copolymers PS₁₁₁-b-PNIPAM_y（y=30、60、84、114）.Stimulus-responsive amphiphilic block copolymers with controllable molecular weight and narrow distribution（Mw/Mn<1.39）were obtained.（2）Polyaniline（PANI）was prepared by using amphiphilic block copolymers PS_x-b-PAA₇₀（x=38、64、101）as templates.The influence of different hydrophobic block length to the morphology and electrochemical properties of polyaniline were investigated.When the PS segment length is 101,the cylindrical fibrous micelles can adsorb relatively more aniline monomers,and has the more amount of active substances after polymerization.The morphology of PANI material is network structure,which is beneficial to electron transport,so it has the best discharge specific capacity.（3）PANI and polybenzidine（PBZ）were prepared by oxidative polymerization using p H-responsive amphiphilic block copolymer PS₁₀₁-b-P2VP₇₀,Pn BA₂₈-b-PS₇₅-b-P2VP₁₀₄with long hydrophobic segments and temperature-responsive amphiphilic block copolymer PS₁₁₁-b-PNIPAM₁₁₄as template.The morphology of the conductive polymers was adjusted only by changing the p H and temperature.Their electrochemical performances were tested by cyclic voltammetry,chronopotential,and alternating current impedance.The results showed that,PANI and PBZ with good electrochemical activity and fast charge-discharge performance were obtained.（4）Polyaniline-containing amphiphilic block copolymer PAA-b-PANI was prepared successfully.By self-assembly in solution,PAA-b-PANI was constructed into micro/nano structures.The results of electrochemical testing showed that,the resistance of PAA-b-PANI is small and its specific discharge capacity can reach 1051.51 F·g^-1at the current density of 3 A·g^-1.