Study On The Synthesis, Self-assembly And Properties Of Linear And Branched Ferrocene-based Polymers

As a new class of functional polymer, ferrocene-based polymer with special properties has extensive application prospects in optical, electronic, magnetic fields and important values in academic research. However, the time of studies on the polymers containing organoferrocenyl units in the main chain is short and there are a lot of problems need to be solved. Thus, solving these problems will benefit to enrich theory of polymer chemistry and physics, which could provide basic research datum for the application of ferrocene-based polymer.In this paper, one series of polymers including four kinds of poly(ferrocenyl -dimethylsilane)-b-poly(dimethylsiloxane) (PFS-b-PDMS) were prepared and characterized through NMR and GPC. We have studied the self-assembled behavior of PFS-b-PDMS in selective solvent and found new rules affected by the kind of copolymers, composition and solvent, temperature, aging time and additive for obtaining the various self-assembled morphologies, including sphere, rod, vesicles and nanotube etc. We may obtain nantube when the block ratio is above six and also obtain spheric self-assembled morphologies commonly when block ratio is less than six. "Sea hedgehog" self-assembled morphology could be obtained in high concentration, and secondary congregation may occur in high temperature. When we aged the self-assembly system, we could obtain "pearl like" and bamboo-shaped nanotube for the fusion of the self-assembly morphologies. The cyclic voltammetry (CV) was adopted to investigate the electrochemical behavior of PFS-b-PDMS films. It was found that the electrochemical redox processes of PFS-b-PDMS films in aqueous and organic solutions all were diffusion controlled ones, there were only small parts of ferrocene units reacted in the electrode reaction process, the PFS-b-PDMS film on electrode surface would be oxidized into cationic polyferrocenium during oxidation process and the electrolyte anions would penetrate into the film for charge neutrality. The experimental results indicated that PFS-b-PDMS films were poor-solvent-swollen in aqueous electrolyte solution and good-solvent-swollen in some organic electrolyte solutions, and the PFS-b-PDMS with different structures possessed dissimilar electrochemical behavior.In this paper, we introduced dendritic molecule to ferrocene-based polymers to obtain three series of polymers including seven kinds of novel linear-dendritic ferrocened-based polymers (PFS-b-G_n, PFS-b-PDMS-b-G_n, PFS-g-G_n). Their composition and structures were characterized through NMR and GPC. The self-assembled behaviors of linear-dendritic ferrocened-basedpolymers in selective solvent were studied. We have found some new rules for obtaining the various self-assembled morphologies, including sphere, rod and vesicles etc. through changing the kind of polymers, composition and solvent, temperature, aging time, additive. For the PFS-b-Gn self-assembly systems, change of solvent made the size different, change of concentration brought the change between sphere micelles and vesicles, hoisting temperature benefited the formation of vesicles, blending dendritic molecules into this system resulted the rodlike micelles. For the PFS-b-PDMS-b-Gn self-assembly systems, increasing of concentration made the reversion to opposite position of chain to produce new self-assembled morphologies, hoisting temperature benefited the formation of vesicles. For the PFS-g-Gn self-assembly systems, changing the factors only made the size different. The CV was adopted to study the electrochemical behavior of linear-dendritic ferrocened-based polymers films. It was found that the controllable factors of electrode process were steric hindrance of dendritic molecules and solvent-swollen of films.In this paper, we synthesized two kinds of new ferrocene-based polymers (Fc-PS-b-PTMSPMA and PTMSPMA-b-PS-Fc-PS-b-PTMSPMA). Their composition and structures were characterized through NMR and GPC. We also studied the self-assembled behavior of them in selective solvent and found new rules for obtaining the various self-assembled morphologies, including sphere, rod and vesicles. We obtained organic/inorganic hybrid nanomaterials through hydrolyzation and crosslinking reaction. One new CV method was constructed to investigate the crosslinking degree.In this paper, we synthesized three kinds of ferrocene-based polymers including TPFS, PFDBS and HPFS. PFDBS and HPFS's compositions and structures were characterized through NMR and GPC. TPFS and PFDBS were adopted to be as precursors to prepare ceramic materials. The compositions of products were analyzed and morphologies were observed. We found that the result products were magnetic and their magnetization intensity could arrive to 30 emu/g when the external field reaches 5 kOe. We developed to adopt HPFS as precursor to prepare carbon nanosphere, carbon nanorod and carbon nanotube through changing the pyrolysis condition. We also adopted HPFS film as precursor to prepare carbon nanofibers and carbon nanoropes in high temperature.