聚炔共轭高分子的分子设计、合成及性能研究

【作者】 余芹；

【导师】 徐洪耀；

【作者基本信息】 安徽大学 ， 高分子化学与物理， 2002， 硕士

【摘要】 本论文根据Schweig非线性光学理论，将具有较大二阶极化率的非线性生色团引入到具有较好三阶非线性的共轭聚炔主链上，合成了一类新型的聚炔衍生物，目的增加聚炔化合物的非线性性能。主要工作内容如下： 1．本论文详细探讨了各类炔烃化合物聚合催化剂的催化机理和催化条件，介绍了聚炔化合物在多个领域的应用现状和前景。 2．阐述分子设计的理论基础，设计了两个系列的共五个目标单炔，并选择了合适的合成路线。本论文共合成了13个化合物，其中六个未见报道。 3．用[Rh（nbd）Cl]₂作聚合催化剂，成功聚合五个目标单炔中的四个。详细研究了聚合条件（温度、溶剂、催化剂、共催化剂）对聚合的影响。并将C₆₀与单体共聚，发现C₆₀除作为单体的功能外，还具有一定的共催化作用。为改善聚合物溶解性，将单炔化合物与苯乙炔共聚，有效的提高了这种非线性取代聚乙炔的溶解性。 4．对五个单炔化合物和部分聚合物进行了光限幅效应研究，发现它们对超快脉冲（40ps）和长波段（1064nm）的激光有较好的限幅效应。并探讨了其限幅机理及分子结构与材料限幅性能之间的关系，为将来新型光限幅材料的设计及应用奠定了基础。更多还原

【Abstract】 Based on the Schweig’s nonlinear optical theory, some kinds of novelpolyacetylenes were synthesized by incorporating the azo-compounds with biggertwo-order non1inear coefficients to the u-conjugated polymer chain. Their opticallimiting properties were measured and the relationship between polymer molecularstructure and their properties was investigated. The main points of this dissertationconsist of the following points:l. Polymerization of acetylenic monomers, their polymerization mechanism anddevelopment of the conjugated polyacetylenes were systematically summarized.2. According to the theory of nonlinear optics, five objective monomer moleculeswere designed and their synthetic routes were selected. In the work, thirteencompounds were synthesized and six of them have never been reported.3. Five objective molecules were polymerized and their copolymers with C60 wereprepared, using [An(nbd)Cl], as polymeric catalyst. It was found that the functionof C,, in the copolymerizations was not only as monomer, bul also as cocatalyst.Influence of different polymeric conditions, such as temperatyre’ solvent. catalystand cocatalyst, on polymerizations of acetyl<Ilic monomers were investigated indetail. To improve the solubi1ity of these homopolymers, the acetylenic monomerswere copoIymerized with phenylacetylene to give soluble polymers.4. The optical limiting effects of these five monomers and some copolymers werestUdied. The exPerimental results revealed that they all possessed optical limitingproperties under suPerfast laser pulses (40 ps) at long wavelength (1064 nm). Theoptical limiting mechanism and the relationship between molecular structure andoptical limiting properties was discussed, which would establish some base for thedesign and aPplication of novel optical limiting materials in future.更多还原