【作者】 王薇；

【导师】 王静媛；

【作者基本信息】 吉林大学 ， 高分子化学与物理， 2005， 硕士

【摘要】 ATRP 技术作为一种新颖的聚合反应方法,它能实现“活性”/可控聚合,产物的分子量分布较窄。许多烯烃单体已成功地用ATRP 方法合成出结构规整的均聚物、无规共聚物、交替共聚物、梯度共聚物、嵌段,接枝共聚物和新颖的聚合物刷;星型、树枝状大分子、超支化高分子及有机/无机杂化材料等。本文中利用自组装方法首先对SiO₂纳米粒子进行了化学修饰,得到了以SiO₂纳米粒子为支撑物的ATRP 表面引发剂。应用这种SiO2纳米粒子表面引发剂对MMA,AAM,HEMA 三种单体进行ATRP,得到单一匀聚物修饰和二嵌段聚合物修饰SiO2纳米粒子的无机有机纳米杂化材料并用IR,XPS 和TEM 进行检测。由于单体性质的不同,我们得到了具有亲水性和疏水性的接枝聚合物。这些聚合物可以控制SiO2纳米粒子表面的化学物理性质,从而使SiO2纳米粒子在某些分离,提纯及分析中能够起到更好的作用。其次以这种杂化材料为基体合成了聚合物金属络合物无机有机杂化材料。通过IR 和XPS 证明我们制得了杂化材料。ESR 和CV 对金属络合物的磁性能和电性能进行测试,结果表明金属络合物具有稳定的电化学活性和磁性质。这种以SiO2纳米粒子为支撑物的聚（AAM 或HEMA）合物金属(Cu²⁺)络合物是一种具有聚合物和金属离子多重性能的高功能性新型无机有机杂化材料,极具潜在应用价值。最后我们对金属离子进行还原,得到聚合物基金属纳米复合材料,既在SiO2纳米粒子表面上再修饰一层金属纳米粒子,通过XRD 和TEM 检测出金属纳米粒子的大小。我们相信这种新型的纳米复合材料由于其自身特殊的性质,能使其在磁性材料、电子材料、催化剂以及传感器等方面有广阔的应用前景。并且本工作为本实验室首次完成,国内外未见报道。更多还原

【Abstract】 At present, the products of radical polymerization are in the majority (about 60%)of the polymers, which indicate the essentiality of radical polymerization. This isbecause the most kinds of vinyl monomer can be polymerized by radicalpolymerization under mild conditions. Furthermore it can react in water without theoxygen. On the other hand, more monomer can copolymerized which induced moreradical polymer. There are some shortcomings in the field of traditional radicalpolymerization, such as the polymerization possess the behavior of out controllingwhich arose the results of lose of molecular weights, molecular distribution,molecular structure, molecular composing and end functions. Thus, the properties ofpolymer from radical polymerization were impaired. Some scientists pay moreattention to synthesize the polymer with well-definded structure from livingpolymerization. Jinshan Wang and K.Matyjaszewski etc introduced a living radicalpolymerization, which include initiator (halogenations alkyl), catalyzer (CuCl),ligands (bpy) and monomer (MMA). At the primary phase of initiated stage, thereducing agent of catalyzer undergoes a one-electron oxidation with concomitantabstraction of a halogen atom (X) from a dormant species R-X. Thus the livingspecies and dormant species were formed. Living species may react with monomer orform dormant species for capturing halogen atom, which induced a lowerconcentration of living species. Because the fast reversible dynamic balances wereestablished we could synthesize the target polymers or oligomers, which possesswell-defined structure, preconcerted molecular weights and low moleculardistributions. Now, the applicable studies systems of ATRP are few and far between.Thus, scientists pay more attention to synthesize the functional materials using ATRP.Comparing with other methods of “living”/ controlled polymerization the ATRP isgood at design. With the rapid development of technology, more and more materialswith function are required. Some kinds of functional materials such as nanocomposite,electrochemical materials and inorganic/organic hybrid materials attract moreattention of scientists. The applied fields include iatric materials (instrument,apparatus and slow liberative agents) electric materials, flaring materials, liquidcrystal polymer, polymer catalyzer, intelligent polymers, polymer segregator. UsingATRP method we also synthesize many kinds of polymers such as block, star, graft,hyper branched (multifunctional) copolymers, inorganic / organic hybrid materialsand nonmaterial etc. Polymer metal complex is a novel functional polymer material,which possess some new properties. The foreground of applying is quite wide. Thusthe studies of polymer metal complex from ATRP is the hardcore in this thesis.In this article introduce SiO2 nanoparticles modified with the initiator of ATRPwere synthesized. Using this initiator, several kinds of homopolymers and blockhydrophilic polymer brushes were prepared by means of “graft from”method. Thepolymer brushes were confirmed by FT-IR spectra, XPS and TEM. That these hybridparticles from the functional monomer (AAM or HEMA) via ATRP can control theproperties of surface, so SiO2 nanoparticles modified with polymer brush can widelyused in many fields. The hybrid from ATRP with the functional monomer (AAM orHEMA) can form the polymer metal complex on the surface of SiO2 nanoparticles byintroducing metal ions. Attachment of Ag+ or Cu2+ to the polymer brush wasconfirmed using IR and XPS. Magnetic properties and electrical properties of hybridparticles were characterized by ESR and CV. The results indicate that the inorganic/更多还原