有机非线性分子4-硝基-4-N，N-二缩水甘油氨基偶氮苯的设计与合成研究
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摘要
本文设计了一种有机非线性分子:4-硝基-4′-N,N-二缩水甘油氨基偶氮苯。偶氮苯类发色团具有大的非线性系数,环氧基团能够改善发色团分子的掺杂性能,通过与其他分子反应生成热固性聚合物或生成交联网状结构的聚合物材料,把发色团分子的空间取向固定下来,从而提高材料的热稳定性。
用ZINDO—SOS的方法对所设计的分子4-硝基-4′-N,N-二缩水甘油氨基偶氮苯进行了计算,分析了分子的键结构、激发态和前线轨道的性能,探讨了分子光学非线性的起因。计算得到发色团分子的二阶非线性光学系数在偶极矩μ方向的投影β_μ=-27.3479×10~(-30)esu,偶极矩μ=7.832D。理论上证明了所设计分子具有较好的非线性性能。
采用两步合成实验方法:先N—烷基化,后重氮化,得到4-硝基-4′-N,N-二缩水甘油氨基偶氮苯的最终产率为56%。并用红外(FTIR)、质谱(MS)、核磁共振氢谱(~1HNMR)、凝胶渗透色谱(GPC)、元素分析和紫外可见光谱(UV/VIS)等分析测试手段对产物进行了表征,分析确认了产物的结构。
把带双环氧基团的目标分子4-硝基-4′-N,N-二缩水甘油氨基偶氮苯与苯胺聚合反应生成聚合物(1),然后在ITO导电玻璃上涂膜,用自己设计组装的电晕极化装置对得到的聚合物薄膜进行了极化,观察到明显的电致变色现象:469nm处特征吸收峰降低到原来的40%,同时红移到了478nm。研究了60℃和室温下的退极化情况。通过对薄膜各极化参数与极化效果之间的关系的研究总结出极化参数选取的原则:极化温度应在玻璃化转变温度附近;放电电流<20mA,应避免出现放电击穿烧坏薄膜及导电玻璃;尽量使极化前后能够观察到
Based on the molecule design, a new D- π -A structure nonlinear optical chromophore molecule [4-Nitro-4'-N,N-di(glycidyl) aminoazobenzene (NGDA) ] has been designed . Azobenzene has large nonlinear coefficient and epoxy makes it easy to dope in polymer. The thermal stability should be improved by reacting or crosslinking with other molecules, than the orientation of the chromophores can be fixed in polymer films.4-Nitro-4'-N,N-di(glycidyl) aminoazobenzene has been researched by ZINDO-SOS, and the facts for molecular nonlinear properties have been analyzed by quantum mechanics. Meanwhile, the results such as the equilibrium bond structure, excited states, frontier orbits, second harmonic generation (SHG) and dipole have been give out, which indicate the molecule designed has very good nonlinear optical properties.4-Nitro-4'-N,N-di(glycidyl) aminoazobenzene has been synthesized by N-alkyl and diazotized, the last yield is 56%. The structure of NGDA has been confirmed by analyzed element analysis, MS, ~1HNMR, GPC, FTIR and UV-Vis spectra.The polymer 1 has been synthesized with NGDA and aniline, then the films of polymer 1 on ITO conducted glass have been poled under electric field. The orientation stability of the chromophores in films was studied by UV-vis spectrum measurement and decreasing and moving to long wave of their absorption peaks have been observed after poled. Then some experiential principals for select the
parameters of poled have been summarized by many experiments.A network polymer was synthesized from toluene-2,4-di-iso-cyanate and polymer 1 by crosslinking reaction for better orientation thermal stability of organic non-linear optical films. However, the relaxation of the poled film was not observed after 5 days by poling and crosslinking for lh at 140°C. Another, a new organic and inorganic hybrid has been synthesized by doping NGDA into silica-sol dried and poled under electronic field. Results show that the transparence of films has improved. But there are some small cracks appeared with large doping, it wishes to be ameliorated by bonded the chromophores into inorganic network in future research.
用ZINDO—SOS的方法对所设计的分子4-硝基-4′-N,N-二缩水甘油氨基偶氮苯进行了计算,分析了分子的键结构、激发态和前线轨道的性能,探讨了分子光学非线性的起因。计算得到发色团分子的二阶非线性光学系数在偶极矩μ方向的投影β_μ=-27.3479×10~(-30)esu,偶极矩μ=7.832D。理论上证明了所设计分子具有较好的非线性性能。
采用两步合成实验方法:先N—烷基化,后重氮化,得到4-硝基-4′-N,N-二缩水甘油氨基偶氮苯的最终产率为56%。并用红外(FTIR)、质谱(MS)、核磁共振氢谱(~1HNMR)、凝胶渗透色谱(GPC)、元素分析和紫外可见光谱(UV/VIS)等分析测试手段对产物进行了表征,分析确认了产物的结构。
把带双环氧基团的目标分子4-硝基-4′-N,N-二缩水甘油氨基偶氮苯与苯胺聚合反应生成聚合物(1),然后在ITO导电玻璃上涂膜,用自己设计组装的电晕极化装置对得到的聚合物薄膜进行了极化,观察到明显的电致变色现象:469nm处特征吸收峰降低到原来的40%,同时红移到了478nm。研究了60℃和室温下的退极化情况。通过对薄膜各极化参数与极化效果之间的关系的研究总结出极化参数选取的原则:极化温度应在玻璃化转变温度附近;放电电流<20mA,应避免出现放电击穿烧坏薄膜及导电玻璃;尽量使极化前后能够观察到
Based on the molecule design, a new D- π -A structure nonlinear optical chromophore molecule [4-Nitro-4'-N,N-di(glycidyl) aminoazobenzene (NGDA) ] has been designed . Azobenzene has large nonlinear coefficient and epoxy makes it easy to dope in polymer. The thermal stability should be improved by reacting or crosslinking with other molecules, than the orientation of the chromophores can be fixed in polymer films.4-Nitro-4'-N,N-di(glycidyl) aminoazobenzene has been researched by ZINDO-SOS, and the facts for molecular nonlinear properties have been analyzed by quantum mechanics. Meanwhile, the results such as the equilibrium bond structure, excited states, frontier orbits, second harmonic generation (SHG) and dipole have been give out, which indicate the molecule designed has very good nonlinear optical properties.4-Nitro-4'-N,N-di(glycidyl) aminoazobenzene has been synthesized by N-alkyl and diazotized, the last yield is 56%. The structure of NGDA has been confirmed by analyzed element analysis, MS, ~1HNMR, GPC, FTIR and UV-Vis spectra.The polymer 1 has been synthesized with NGDA and aniline, then the films of polymer 1 on ITO conducted glass have been poled under electric field. The orientation stability of the chromophores in films was studied by UV-vis spectrum measurement and decreasing and moving to long wave of their absorption peaks have been observed after poled. Then some experiential principals for select the
parameters of poled have been summarized by many experiments.A network polymer was synthesized from toluene-2,4-di-iso-cyanate and polymer 1 by crosslinking reaction for better orientation thermal stability of organic non-linear optical films. However, the relaxation of the poled film was not observed after 5 days by poling and crosslinking for lh at 140°C. Another, a new organic and inorganic hybrid has been synthesized by doping NGDA into silica-sol dried and poled under electronic field. Results show that the transparence of films has improved. But there are some small cracks appeared with large doping, it wishes to be ameliorated by bonded the chromophores into inorganic network in future research.
引文
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