【作者】 邱凤仙；

【导师】 刘举正； 周钰明；

【作者基本信息】 东南大学 ， 材料物理与化学， 2005， 博士

【摘要】 本文以制备具有高非线性活性和热稳定性的光学聚合物材料为目的,以简便的方法合成了一系列聚酰亚胺有机-无机杂化材料,并对其各项性能进行了研究。1.本文合成了偶氮类NLO生色分子HMNB,以6FHP和6FDA或PMDA为单体,合成了含氟聚酰亚胺,采用溶胶-凝胶法得到新的不同无机组分含量的热稳定性高的有机-无机杂化材料。将制得的含氟聚酰亚胺/SiO₂杂化材料,采用FT-IR、SEM、TEM、XRD和TGA性能测试装置对材料的结构、表面形貌、无机粒子大小、晶体结构和热性能等进行了表征。电光系数γ₃₃达23pm/V。电光系数γ33只在开始阶段有一定的衰减,从200min以后衰减非常缓慢,基本保持其初始值的95%以上,该杂化材料能初步满足器件化要求。通过测定膜于极化前后的紫外-可见光谱,得到取向发色团的序参数Φ,结果表明极化效率较高,材料的结构设计合理,并由一维刚性气体模型计算了材料的宏观二阶非线性光学系数χ（2）,经60h序参数几乎不变,有好的极化取向稳定性。2.改变有机生色分子,使用了DR1,同法合成有机-无机杂化材料。采用固态²⁹Si MAS NMR谱研究了杂化材料的形成过程,结果表明杂化材料中是以T³、Q³、Q⁴结构为主,说明在杂化材料中形成了交联网状结构。杂化材料的玻璃化转变温度比聚合物高出77℃,电光系数γ33达28 pm/V。改变二酐分子,以6FDA代替PMDA,则杂化材料的玻璃化转变温度比聚合物高出76℃,电光系数γ33高达29 pm/V,该杂化材料为制备高性能的光学器件提供了基础。3.合成了苯并噻唑类衍生物的NLO生色分子NBDPA和不同无机组分含量的含氟聚酰亚胺/SiO2杂化材料。利用DSC法测定了FB^-2和PB^-2杂化材料的重要的热物理性质之—比热,实验结果用最小二乘法对273 ³64K温度范围内的Cp实测值进行拟合,得到下列符合较好的方程: FB^-2:C_p =1.1552 J K^-1 g^-1 + 4.28×10^-4 J K^-2 g^-1 T– 3.00×104 J K g^-1 T^-2 ; PB^-2:C_p =1.1032 J K^-1 g^-1 + 3.79×10^-4 J K^-2 g^-1 T– 4.50×104 J K g^-1 T^-2;杂化材料的玻璃化转变温度较聚酰亚胺高出120¹50℃,电光系数γ₃₃达27pm/V,基本达到实用化要求。4.合成了含氟的可制作光波导器件的、具有良好热稳定性的PI-19有机聚合物,测得该聚合物Tg为256℃,5%的热失重温度为380℃。材料在光通讯波段（1.3和1.55μm）,有2个较低吸收的“窗口”,表明PI-19可以用来制作低损耗的光通讯器件、光开关等。制得的聚合物材料具有较大的热光系数,其值为-4.13 -3.72×10^-4℃^-1（从650nm到1310nm）,这为研制具有低驱动功率的新型数字热光开关具有一定意义。更多还原

【Abstract】 Abstract: In order to prepare optical polymer materials with high nonlinear activity and thermal stability, a series of polyimide organic/inorganic hybrid materials were successfully synthesized and their properties were studied in this dissertation.In this paper,azo and benzothiazol NLO chromophores were synthesized The fluorine-containing polyimide was synthesized using the monomers 6FHP and 6FDA or PMDA.. The novel hybrid materials were obtained with different inorganic contents and high thermal stability by sol-gel technique. They were characterized by the methods of FT-IR, SEM, TEM, XRD and TGA measuring apparatus to get their surface structure, morphology, particle size, crystal structure and thermal performance. The electro-optical coefficients reached 23pm/V. The film’γ₃₃ still kept 95% of the initial value for 200min, which showed the hybrid materials had application for devices. The order parametersφwere measured through determination of the UV -Vis spectrum before and after polarized film, which showed high-polarized efficiency and good structural design. The second-order nonlinear optical propertiesχ^（2） of the poled films were stuided according to the one-dimensional rigid oriented gas model. Long-term stability of the dipole alignment was demonstrated for the hybrid. It washown that polymers had good orientational stability.The organic-inorganic hybrids were synthesized containing DR1 NLO chromophore. When PMDA or 6FDA were used, the Tg of the obtained hybrid materials was higher 77,76℃than the corresponding pure polyimide and the electro-optical coefficients reached 28, 29pm/V respectively. Results revealed that T³, Q³ and Q⁴ are the major microstructure forming a network structure from the solid-state ²⁹Si NMR spectra of the hybrid.Novel organic-inorganic hybrids were synthesized containing benzothiazol NLO chromophore. Theheat capacities of FB-2 and PB-2 were carried out with DSC method. The experimental heat capacities were fitted using least square method （range from 273 to 363 K）. The fitted equation: FB-2:Cp =1.1552 J K^-1 g^-1 + 4.28×10^<sup>-4 J K-2 g^-1 T– 3.00×104 J K g^-1 T^-2 ;PB-2:Cp =1.1032 J K^-1 g^-1 + 3.79×10^-4 J K-2 g^-1 T– 4.50×104 J K g^-1 T^-2. The Tg of the obtained hybrid materials was higher 120 to 150℃than the corresponding pure polyimide and the electro-optical coefficients reached 27pm/V which showed the hybrid materials had high thermal stability and practical application.The fluorine-containing organic polymer PI^-19 was synthesized with making optical waveguide device and having good thermal stability. It’s Tg was 256℃and thermal loss weight（5%） was 380℃. It had two low absorbent windows at optical communication wavelength（1.3 and 1.55μm）. It had higher thermal-optical coefficient which could reach ^-4.13 -3.72×10^-4℃^-1（from 650nm to 1310nm）.These showed that PI^-19 could be made low loss optical communication device ang optical switch . The conclusion had a little significance to develop new thpe digital optical switch with low driving power.更多还原