【作者】 王建军；

【导师】 王立；

【作者基本信息】 浙江大学 ， 高分子化学与物理， 2006， 博士

【摘要】 二茂铁基聚合物是一类具有独特的光、电、磁等性能的新型功能聚合物，在改性电极、电化学传感器、非线性光学器件等方面具有很好的应用前景，关于二茂铁基聚合物的研究正越来越多地受到人们的重视。本文对各种二茂铁基聚合物的合成、性能及应用进行了综述；合成了系列新型二茂铁基聚合物并对其进行了表征；探讨了二茂铁基聚合物的电化学性能、掺杂导电和自组装机理；探索了所得二茂铁基聚合物在掺杂导电材料、自组装以及新型光刻胶等方面的应用；获得了如下主要结果：本文合成了2个系列聚二茂铁硅烷（PFS）：聚二茂铁二甲基硅烷（PFDMS）和聚二茂铁甲基苯基硅烷（PFMPS）；探讨了聚合条件（温度、时间和单体纯度等）对聚合物分子量及分子量分布的影响，发现延长聚合时间可以提高PFDMS的分子量，而延长聚合时间对PFMPS分子量的影响不明显；考察了PFS的溶解性、结晶性和成膜性，建立了调控薄膜厚度的方法；采用碘溶液扩散掺杂法制得了掺杂PFS薄膜，通过UV／Vis研究发现碘和二茂铁单元之间的电子转移可能是引起碘掺杂聚合物薄膜电子性能变化的主要原因；采用Van dePauw技术测量了聚二茂铁硅烷薄膜的电性能，考察了掺杂后薄膜的电导率、载流子浓度和载流子迁移率的变化，发现掺杂时间为5hr的PFDMS薄膜的电导率σ为2.08×10^-3／（cm·Ω），载流子浓度R_H+为2.55×10¹³／cm³，空穴迁移率μ为170cm²／（V·s），并且发现掺杂时间对σ、R_H+和μ影响很大，探讨了可能的导电机理。本文合成5种二茂铁基聚合物：聚二茂铁甲基氯硅烷（PFMCS）、聚二茂铁硼烷（PBF）、聚二茂铁甲基丁基硅烷（PFMBS）、甲氧基丁基聚二茂铁硅烷（MeO-Bu-PFS）和萘乙氧基丁基聚二茂铁硅烷（Np-Bu-PFS），其中PFMBS、MeO-Bu-PFS和Np-Bu-PFS为首次报道；对所得二茂铁基聚合物的溶液电化学进行了研究发现：溶液电位降补偿iR在一定范围内的变化不影响CV谱；CH₂Cl₂具有适中的介电常数ε，较低的粘度η，较小的电位降补偿iR，是比较理想的二茂铁基聚合物溶液电化学研究选用介质；在电化学研究时，聚合物浓度以低于3.0mM比较合适；聚二茂铁硅烷发生电化学反应时，有分步氧化还原现象，也会发生在电极表面的沉积；不同的聚合物结构（如不同的桥和不同桥头取代基）对CV行为有很大的影响；根据电化学理论，计算得到了不同分子量聚二茂铁硅烷的表观扩散系数D_app的范围为10^-7～10^-5cm²／s。本文合成了6种含丙烯酸酯基的聚二茂铁硅烷：丙烯酸酯基聚二茂铁硅烷（HEMA-PFS）、甲氧基丙烯酸酯基聚二茂铁硅烷（MeO-HEMA-PFS-a和MeO-HEMA-PFS-b）、萘乙氧基丙烯酸酯基聚二茂铁硅烷（Np-HEMA-PFS）、稳定自由基丙烯酸酯基聚二茂铁硅烷（TEMPOL-HEMA-PFS）和丁基丙烯酸酯基聚二茂铁硅烷（Bu-HEMA-PFS），其中Np-HEMA-PFS、TEMPOL-HEMA-PFS和Bu-HEMA-PFS为首次报道；对所得聚合物溶液的UV／Vis研究发现：聚合物硅原子上丙烯酸酯基的数量及基团种类对聚合物的UV／Vis吸收具有较大的影响，可以通过硅原子上取代基团的数量和种类的改变来调节PFS溶液UV／Vis吸收峰特性；对所得聚合物的溶液电化学研究发现：硅上丙烯酸酯基的数量及基团种类对聚合物的CV谱具有较大的影响，可以通过改变硅原子上丙烯酸酯基的数量及基团种类来调节PFS上相邻二茂铁之间相互作用的强弱；制得了1种基于丙烯酸酯基聚二茂铁硅烷的新型光刻胶，经紫外光照射，得到了精细的光刻图案；对HEMA-PFS、MeO-HEMA-PFS-a、MeO-HEMA-PFS-b和Np-HEMA-PFS的自组装行为进行了研究，发现聚合物浓度、混合溶剂组成、陈化时间等因素对自组装行为有重要影响；在混合溶剂中，聚合物HEMA-PFS、MeO-HEMA-PFS-a和Np-HEMA-PFS能自组装形成空心纳米粒子，MeO-HEMA-PFS-b能自组装成花状囊泡结构；向组装体溶液中加入光引发剂，经紫外照射并且陈化，可得到交联的稳定核壳复合囊泡组装体。更多还原

【Abstract】 Ferrocene-based polymers have emerged as an important category of functional polymer with unique electrical, optical and magnetic properties. Considerable attention was paid to development of these polymer systems, which were useful materials for modification of electrodes, as electrochemical sensors and as nonlinear optical materials. In this paper the synthesis, property and application of ferrocene-based polymers were reviewed. A series of novel ferrocene-based polymers were synthesized and characterized, and used as doping conducting materials, self-assembly materials and photoresist. The electrochemistry properties and the mechanisms of doping conductivity and self-assembly were discussed. The main conclusions are listed as follows.In this paper, two series of poly（ferrocenylsilanes） （PFS） including polyferocenyldimethylsilane （PFDMS） and polyferrocenylmethylphenylsilane （PFMPS） were prepared. The influences of polymerization time, polymerization temperature, and monomer purity on polymer molecular weight and polydispersity were discussed. It was found that molecular weight of PFDMS could be increased by prolonging the polymerization time, but this method had no effect on molecular weight of PFMPS. Solubility, crystallizability and filming properties of PFS were investigated, and the process to obtain controllable PFS films was built up. PFS films were doped by saturated iodine solution in hexane. By the UV/Vis investigation, it was found that the electronic structure change of PFS was attributed to electron transfer between iodine and ferrocenic units at PFS. The charge transport properties of PFS films were tested by Van de Pauw techniques, and it was found that the conductivity σ, carrier density R_H+ and mobility μ. of films were 2.08×10^-3 /（cm·Ω）, 2.55×10¹³ /cm³ and 170 cm²/（V’S） respectively after the films were doped for 5 hr. The possible conducting mechanisms were discussed.In this paper, five kinds of ferrocene-based polymers including poly（ferrocenylmethylchloro-silane） （PFMCS）, poly（boraferrocene） （PBF）, poly（ferrocenylmethylbutylsilane） （PFBMS）, methoxyl- and butyl-substituted PFS （MeO-Bu-PFS） and naphthylethoxyl- and butyl-substituted PFS （Np-Bu-PFS） were synthesized, and PFBMS, MeO-Bu-PFS and Np-Bu-PFS were reported first. By investigation into electrochemistry in polymer solution, it was found that the fluctuation of solution ohmic potential iR did not affect the compensated cyclic voltammograms （CV）, and CH₂Cl₂ was the optimal solvent during PFS electrochemistry investigation due to its moderate dielectric constants （ε）, low viscosity factors （η） and small iR. In electrochemistry the properferrocene-based polymer concentration was lower than 3.0 mM. In solution, PFS were oxidized gradually and electrodeposited on the electrode surface. The electrochemical behaviors of ferrocene-based polymer solution were affected by variable, substitution group and atom bridge. The apparent diffusion coefficients of PFS with the different molecular weight were 10^-7～10^-5 cm²/s according to calculation.In this paper, six kinds of methacrylate-based PFSs including methacrylate-substituted PFS （HEMA-PFS）, methoxyl- and methacrylate-substituted PFS （MeO-HEMA-PFS-a and MeO-HEMA-PFS-b）, naphthylethoxyl- and methacrylate-substituted PFS （Np-HEMA-PFS）, 2,2,6,6-tetramethyl-1-piperidinyloxy- （TEMPOL） and methacrylate-substituted PFS （TEMPOL-HEMA-PFS） and butyl- and methacrylate-substituted PFS （Bu-HEMA-PFS） were prepared, and Np-HEMA-PFS, TEMPOL-HEMA-PFS and Bu-HEMA-PFS were reported first. By investigation into UV/Vis spectra of methacrylate-based PFS solution, the characteristic peaks could be modulated by different quantitative methacrylate groups and different substitution groups on Si. The CV of methacrylate-based PFS were affected by different quantitative methacrylate groups and different substitution groups on Si, and it was found that the Fe-Fe interaction in PFS could be modulated by different quantitative methacrylate groups and different substitution groups on Si too. A novel photoresist based on methacrylate-substituted PFS was prepared, and polymer films were photopatterned by photolithography process. The self-assembly behaviors of methacrylate-based PFSs （HEMA-PFS, MeO-HEMA-PFS-a, MeO-HEMA-PFS-b and Np-HEMA-PFS） in mixture solvents were investigated. It was found that the self-assembly behaviors were affected by PFS concentration, composition of solvents, aging time and so on. In mixture solvents HEMA-PFS, MeO-HEMA-PFS-a and Np-HEMA-PFS could self-assembl into nanoparticles with hollow cores, and MeO-HEMA-PFS-b could self-assembl into flower-like large-compond-capsules. Photo-cross-linking of self-assembled particles from PFS with various methacryiate side group numbers afforded core-shell nanoparticles by adding photoinitiator, irradiating and aging, and these particles proved to be stable.更多还原