【作者】 杜春苹；

【导师】 张以群； 黄炜；

【作者基本信息】 华东师范大学 ， 高分子化学与物理， 2011， 硕士

【摘要】 螺旋聚合物不仅具有独特的光、电、磁性能,还在手性分离、手性合成、分子识别、不对称催化和光学材料领域具有潜在的应用前景,吸引了众多研究者的目光。取代聚乙炔作为一种重要的螺旋聚合物,由于具有半导体、非线性光学等特殊性质,近几年更成为研究的热点。在各种有机发光材料中,芴类材料是一类很有发展前景的新型发光材料。芴及其衍生物由于含有刚性的平面联苯单元,其热稳定性和化学稳定性都比较高,还可通过共聚、共混等方法进行改性使之发出不同波长的光,因此在平板显示、化学传感、非线性光学及太阳能电池等领域有潜在的应用前景。可以预见的是侧链含芴发光基团的螺旋聚乙炔将整合以上的这些特性开发出一种新型功能材料。本文合成了一类新型的单取代聚乙炔衍生物单体,以双降冰片烯二氯化二铑为催化剂催化聚合得到新型的单取代螺旋聚乙炔的均聚物：聚4-(2-芴基)-3-氧代丁酸酰胺[P1],聚4-(2-芴基)-3-氧代丁酸丙炔酯[P2],聚N-丙炔基-L-丙氨酸-4-(2-芴基)-3-氧代丁酰胺[P3],聚4-(2-芴基)-3-氧代丁酸-L-丙氨酸-丙炔酯[P4],此外,还将不同摩尔配比的单体M2和M3进行共聚得到聚乙炔的共聚物：聚{4-(2-芴基)-3-氧代丁酸丙炔酯)-(N-丙炔基-L-丙氨酸-4-(2-芴基)-3-氧代丁酰胺,M2：M3=3：7,摩尔比}[P5]和聚{4-(2-芴基)-3-氧代丁酸丙炔酯)-(N-丙炔基-L-丙氨酸-4-(2-芴基)-3-氧代丁酰胺,M2：M3=7：3,摩尔比}[P6],通过红外和核磁对聚合物的结构进行了表征,并利用紫外、荧光、圆二色谱、差热和热重分析等手段对聚合物性能进行了分析研究,结果表明这些聚合物都具有较好的发光性能和热稳定性,而且具有稳定的螺旋结构,是一类新型的具有螺旋结构的光学活性聚合物材料,在很多领域都将有它的潜在应用价值。我们对本论文合成的单取代聚乙炔衍生物进行了紫外和荧光光谱表征,发现尽管聚合物的结构不同,但在较稀溶液(1×10-5mol/L)中具有相似的吸收和发光波长,且最大发射峰均发出蓝光；我们还考察了溶液浓度对聚合物荧光光谱的影响,发现随着浓度的逐渐增大,发光波长发生红移,发光颜色和荧光强度也发生变化。圆二色光谱实验表明本论文合成的聚乙炔衍生物都具有螺旋结构,我们研究了溶剂极性和温度对聚乙炔衍生物螺旋构象的影响,发现完全不同于文献所报道的聚厶炔衍生物的螺旋构象随溶剂极性增大和温度升高而消失的现象,本论文合成的聚乙炔衍生物具有极其稳定的螺旋结构,在极性溶剂(CH3OH)含量达90%及较高的温度(60℃)条件下其螺旋构象仍然存在。对水论文的工作进行了简单总结,并对本论文合成的单取代螺旋聚乙炔衍生物的应用前景及今后的研究工作进行了展望。更多还原

【Abstract】 Helical polymers not only show unique electronic, magnetic and optical properties but also possess significant potential applications in many field due to the molecular recognition ability, catalytic ability for asymmetric synthesis, and optical resolution ability. Substitute polyacetylenes as a kind of important helical polymer have attract many interests in recent years due to their special properties, such as semiconductor, nonlinear optical, etc.Fluorene is a new type of promising luminescence materials in the area of organic light-emitting. Fluorene and its derivatives have high thermal stability and chemical stability due to the rigid planar biphenyl unit in their molecular structure, and they can emit different wavelengths of light by copolymerization, blending or other methods. Therefore, they have potential applications in the field of flat panel displays, chemical sensors, nonlinear optics and solar cells, et al. It is foreseeable that polyacetylene which contain fluorene illuminophore in the side chain will integrate these features and develop a new kind of functional materials.We synthesized a new type of mono-substituted polyacetylene monomers which polymerized under the chloronorbornadiene rhodium (Ⅱ) dimmer [(nbd)RhCl]2 catalyst, and obtained a new type of mono-substituted helical polyacetylene homopolymers, poly 4-(2-fluorene-based)-3-oxo acid amide [P1], poly 4-(2-fluorene-based)-3-oxo acid propargyl ester [P2], poly N-propinyl-L-alanine-4-(2-fluorene-based)-3-oxo butylamide [P3] and poly 4-(2-fluorene-based)-3-oxo acid-L-alanine-propargyl ester [P4], and also obtained polyacetylene copolymers with different molar ratio of monomers M2 and M3, poly {4-(2-fluorene-based)-3-oxo acid propargyl ester)-(N-propinyl-L-alanine based-4-(2-fluorene-based)-3-oxo butylamide, M2:M3=3:7, molar ratio} [P5] and poly{4-(2-fluorene-based)-3-oxo acid propargyl ester)-(N-propinyl-L-alanine based-4-(2-fluorene-based)-3-oxo butylamide, M2:M3=7:3, molar ratio} [P6], and their properties were also investigated. The structures and properties of these polyacetylenes were investigated by 1HNMR, FT-IR, UV-vis, CD, TGA, DSC, FL and other methods. The results showed that those polymers have good luminescent properties and thermal stability, and also have stable helical structure, is a new type of optical activity polyacetylene, and will have its potential applications in many areas.The substituted polyacetylenes synthesized in this thesis were characterized by UV-vis and fluorescence spectroscopy, in spite of the differences in their molecular structures, the dilute solutions (1×10-5mol/L) of these substituted polyacetylenes exhibit the same absorptions and the same blue emissions; then we investigated the effects of concentration on FL spectra of polymers, and found that the light-emitting wavelength undergo red shift, emitting color and fluorescence intensity changed as the concentration increased.CD test indicated that polyacetylenes synthesized in this thesis have helical structure, solvents-mixed and temperature-changed CD test indicated that polyacetylenes synthesized in this thesis have stable helical structure, because they still have helical structure even under the conditions of polar solvents (CH3OH) content of 90% and higher temperature (60℃), which are quite different from the helical conformation of polyacetylenes disappeared with the increase of solvent polarity and temperature that reported in previous articles.In the end we summarize the work simply, and make an outlook about the application of the mono-substituted helical polyacetylenes we prepared and the research work we will do in the future.更多还原