【作者】 赵辉；

【导师】 唐本忠； 孙景志；

【作者基本信息】 浙江大学 ， 高分子材料科学与工程， 2010， 硕士

【摘要】 功能化是聚炔研究领域发展的主流,具有发光、荧光图案化、光导、光学限制、液晶性、细胞相容性、手性传递与放大、气体分离等功能的聚炔被设计合成出来。本课题组在用聚苯乙炔增溶碳纳米管（CNTs）方面开展了系统的研究工作,在国内外产生了一定影响。考虑到CNTs独特的纳米结构和新颖的光电与机械性能,而功能化聚炔在增溶CNTs的同时使CNTs表面功能化,这是一个可持续发展的重要研究方向。本文的基本研究思路是:设计合成一系列新型聚苯乙炔衍生物,制备这些聚苯乙炔衍生物与CNTs的复合材料,考察这些聚苯乙炔衍生物增溶CNTs的能力,进一步阐明增溶机理,并探索这些复合材料的潜在应用。选择适当的间隔基团,把多种功能基元连接到聚苯乙炔侧链,获得了一系列功能化聚炔,这些功能基元包括:三苯胺（P1）、醛基取代的三苯胺（P2）、乙烯桥联的三苯胺（P3）、咔唑（P4）、芴（P5）、D-葡萄糖（P6）、D-甘露糖（P7）、D-半乳糖（P8）。利用GPC、FTIR、¹H NMR ¹³C NMR、紫外-可见吸收光谱、荧光光谱等手段对其结构进行了明确的表征。在此基础上,采用溶液共混（P1～P5）和原位聚合方法（P6～P8）制备了聚苯乙炔衍生物与CNTs复合物,定量地测试了这些复合物中CNTs的含量,通过光谱学技术（NMR、紫外-可见吸收光谱、荧光光谱、拉曼光谱、圆二色性谱）和形态表征技术相结合的方法研究了复合物的结构以及聚炔与CNTs之间的相互作用。在若干聚苯乙炔衍生物中,发现P3表现出对CNTs异常大的增溶能力。在综合考察电子结构、溶致变色性能的基础上,提出了三苯胺基团—CNTs之间的给—受体（D—A）相互作用是导致这种现象的原因的论断。通过聚炔的结构设计（P4、P5）,排除了功能基元拓扑结构差别的影响因素,进一步实验证实D—A相互作用在增溶CNTs中发挥的关键效应。这是继π-π相互作用、亲疏水相互作用、静电排斥作用之后被发现的一种新的CNTs增溶机制。P6～P8具有良好的水溶性和细胞相容性,在CNTs存在下原位聚合可得到P6～P8/CNTs复合物,这些复合物保持了P6～P8良好的水溶性和细胞相容性。将这些复合物与壳聚糖（CS）溶液共混后制备成的CS棒材力学性能有明显提高。力学测试表明:与纯CS棒材相比,添加了P6～P8/CNTs复合物的CS棒材的弯曲强度提高18.5～30%,弯曲模量提高39～46%。更多还原

【Abstract】 Functionalization is the mainstream in the tidal current of the study of polyacetylenes.Polyacetylene derivatives with functions such as fluorescence emission,photoconductivity,photo-pattern,optical limiting,liquid crystal,chiral transfer and amplification,cyto-compatibility,and gas permeability have been designed and synthesized.In our group,a systematic research on the polyphenylacetylene（PPA） derivatives has demonstrated that they have great solvating power to carbon nanotubes（CNTs）,and these works have got good peer citation record.CNTs possess unique nano-structure and advanced electronic and mechanical properties,and the PPA derivatives functionalize the CNTs’ surface when they dissolve CNTs in organic solvents.Therefore,this is a promising research topic with great scientific value and potential technological applications.In the present thesis,a series of novel PPAs have been designed,synthesized and characterized;the composites of these PPAs and CNTs have been fabricated;and the solvating power of these PPAs to CNTs have been examined;and finally,their potential applications have been explored.Through proper spacers,a series of functional PPAs have been obtained by linking functionalities to polyacetylene backbones.The functionalities include triphenylamine （TPA）（P1）,aldehyde-TPA（P2）,stilbeniod-TPA（P3）,carbazole（P4）,fluorene（P5）. D-glucose（P6）,D-mannose（P7）,and D-galactose（P8）.Their structures have been characterized with various techniques such as GPC,FTIR,¹H NMR,¹³C NMR, UV-visible and fluorescence spectroscopy.The composites of these polymers and CNTs have been prepared through the routes of solution blending（P1～P5） and in-situ polymerization（P6～P8）,and the content of CNTs component in the composites has been quantitatively measured.Spectroscopic methods such as NMR,UV- visible, fluorescence,Raman,and circle dichromism,in combination with morphological observation techniques such as SEM and TEM have been used to investigate the structure and the interactions between PPAs and CNTs.Among the obtained PPAs（P1～P8）,P3 showed remarkable solvating power to CNTs.After carefully studying the electronic and photophysical properties of P3,we concluded that the donor-acceptor（D-A） interaction was the reason behind the phenomena.To check the D-A interaction on the effect of salvation CNTs,we synthesized carbazole- and fluorene-containing PPAs.Solubility data and TEM clearly manifested that D-A effect played an important role in the polymer-aided MWNT dispersion in organic solvents.Thus,in addition to the p-p stacking,van der Waals and electrostatic interactions,the D-A interaction offers a new strategy for the design and fabrication of macroscopically processable hybrids of CNTs and polymers.P6～P8 showed water soluble and cyto-philicity.Their hybrids with CNTs can be obtained via in-situ polymerization of corresponding monomers in the presence of CNTs,and they also showed desirable water soluble and cyto-philicity.After solution blending the hybrids with chitosan（CS）,CS rods can be fabricated and the mechanical strength of the rods can be effectively improved.According to the experiment data,in comparison with pristine CS rods,the bending strength and modulus of composite CS rods were increased by 18.5～30%and 39～46% respectively.更多还原