【作者】 张海昌；

【导师】 杨文君；

【作者基本信息】 青岛科技大学 ， 材料加工工程， 2010， 硕士

【摘要】 共轭有机高分子材料在分子传感,非线性光学,有机场效应晶体管,光致发光和电致发光材料中具有广泛的应用,本论文中,我们合成了一些新颖的含蒽或三聚芴的共轭高分子,并研究了它们的双光子吸收、电致发光及热学性质。这些工作包括:1具有热和光稳定性的空穴与电子传输平衡性的新型蓝光聚合物具有重要的研究和实际意义,聚芴是典型的蓝光发射材料,我们的目标是在聚芴的主链或侧链引入不同的功能单元,研究这种多功能基团集成在同一分子链上是否可以提高该聚合物的综合光电性质。我们以三聚芴与苯并呋喃交替共聚物为主链,苯基噁二唑为侧链合成了一种新的蓝光聚合物(PBF-OXD),结果表明,PBF-OXD具有良好的热稳定性,光学稳定性和较高玻璃化转变温度及荧光量子产率。以PBF-OXD为发光层的结构为ITO/PEDOT:PSS/PBF-OXD/Ba/Al器件发出稳定的蓝光(λmax = 434 nm),发光亮度为1400 cd?m-2,最大发光效率为0.95 cd?A-1。这些结果表明,我们设计合成了一个可溶的多功能集成的性能优良的电致蓝光发射材料。2设计并合成具有大的双光子吸收截面的共轭聚合物具有重要的研究和实际意义。聚2,6-蒽基乙烯和含2,6-蒽基乙烯的聚合物的合成是比较困难的,所以对这方面的文献报道较少。我们利用了9,10-二(3,4-二(2-乙基己氧基)苯基)-2,6-二磷脂基蒽和N-辛基-3,6/2,7-二醛基咔唑通过Wittig–Homer反应,成功的合成了两种含有电子给体的聚合物P1和P2。结果表明P1与P2具有较高的荧光量子效率(Φf = 0.85,0.78),每个重复单元的双光子吸收截面分别为840 GM和490 GM,它们的双光子吸收截面明显的高于PAV(210GM),这表明了将供电子基团引入聚合物骨架中,形成D–π–D重复单元,比增加主链的共轭长度对双光子吸收截面的影响更大。3蒽是一种大的芳香环,可以通过空间位阻提高聚合物的刚性以及玻璃化转变温度,蒽同时也是一种功能基团,可以通过聚合以及氧化形成交联聚合物。我们用9,10-二(4-羟基苯基)蒽,双酚A和4,4’-二氯对苯砜进行缩聚,合成了新型的含蒽单元的聚芳醚砜。研究结果显示当双酚A完全被9,10-二(4-羟基苯基)蒽取代时,该聚合物具有较大的玻璃化转变温度(265℃)。该系列聚合物是可溶的,并且可以旋转涂膜。当该聚合物经紫外灯照射并在空气中加热后,可以得到交联聚合物,该聚合物热稳定性得到了提高。更多还原

【Abstract】 Conjugated organic polymeric molecules have potential applications in molecular sensors, non-linear optical materials, organic field effect transistors, photoluminescence, and electroluminescence. In this thesis, some novel anthracene- containing and terfluorene-containing polymers have been synthesized and their Two-photon absorption(TPA)、electroluminescent and thermal properties have been investigated. These include:1. The synthesis of new blue-emitting polymers with thermal- and photo- stability and with an improved imbalance of the hole and electron transport are needed. Poly-fluorene is an important blue-light emitting material, here our goal is to investigate whether the integration of different segments, each having respective functions, endow a copolymer with improved optoelectronic properties. Thus a novel blue-emitting alternating benzofuran/ter-?uorene copolymer with pendent oxadiazole groups (PBF-OXD) has been synthesized. The results showed that PBF-OXD shows good thermal and optical stability, a high glass transition temperature, and high ?uorescence quantum yield. A simple EL device with the configuration of ITO/PEDOT:PSS/PBF-OXD/Ba/Al displays a stable blue emission (λmax = 434 nm),, a maximum brightness of 1400 cd?m-2, and a maximum luminance efficiency of 0.95 cd?A-1. These results show that this solution processable alternating benzofuran/ ter?uorene copolymer is a good candidate for a stable blue-emitting material.2. The design and synthesis the conjugated polymers with large Two-photon absorption cross section are very important. To the best of our knowledge, poly(2,6-anthracenevinylene)s (PAV) and 2,6-anthracenevinylene- containing polymers are very scarce at present because of their synthetic inaccessibility before. Here we design and synthesize two novel donor-containing poly(2,6-anthracene- vinylene)-based derivatives (P1 and P2) by Wittig–Homer reaction between 9,10-bis(3,4-bis(2-ethylhexyloxy)phenyl)-2,6-bis (diethylphosphory lmethyl) anthrax- cene and N-octyl-3,6/2,7-diformylcarbazole. The results showed that P1 and P2 have high-fluorescence quantum yields (Φf = 0.85–0.78). The maximalδof P1 and P2 are 840 GM and 490 GM per repeating unit, respectively. Theseδvalues are obviously higher than that (210 GM) of their reference polymer, PAV, indicating that the incorporation of strong electron-donating moieties into the polymer backbone to form D–π–D repeating unit is more effective in enhancingδthan the extension of conjugation length.3. Anthracene is a large and planner aromatic ring, which improves the rigidity and glass transition temperature of the resulting polymers through its steric hindrance. Anthracene is also a functionalized moiety, which may perform dimerization or endo-peroxidation to form a crosslinking polymer. Here we incorporate a new bisphenol monomer containing anthracene, 9,10-bis(4-hydroxyphenyl)anthracene to the polycondensation of bisphenol A and 4,4’-dichlorodiphenyl sulfone, to synthesize novel anthracene-containing poly(arylene ether sulfone)s.These polymers showed increased glass transition temperature with the content of the 9,10-diphenylanthracene and reached up to 265℃when the bisphenol A was substituted by bis(4- hydroxyphenol)anthracene. These polymers are soluble and can be film-formed through spin-coating. Moreover, upon irradiating with UV-vis light and then heating in air, the resulting film was a cosslinked polymer, which offers the possibility of enhanced thermal.更多还原