酞菁氧钛的绿色合成和绿色转型及其应用研究

发布时间：2018-05-09 14:22

本文选题：酞菁氧钛 + 绿色工艺　；参考：《天津大学》2015年硕士论文

【摘要】：酞菁氧钛是一种应用广泛的有机功能材料。在现有的酞菁氧钛合成方法中,用于合成酞菁氧钛的常规工艺一般使用喹啉、四氢萘、N-甲基吡咯烷酮、1-氯萘、邻二氯苯等高沸点有机溶剂。使用这些溶剂存在以下缺点:毒性较大,存在安全及环保等问题;合成过程中会产生含氯或氮杂环的杂质,降低TiOPc纯度,后处理困难。无定型酞菁氧钛的转型诱导溶剂多使用一氯苯、二氯苯、氯萘等含卤素的有机溶剂,容易对环境和人体健康造成危害。本文以钛酸四丁酯和1,3-二亚胺基异吲哚啉为原料,分别使用二甲基硅油、十二烷基苯和二苯基甲烷为反应溶剂,对酞菁氧钛的绿色合成进行了研究。通过对比,二苯基甲烷作为反应溶剂时,酞菁氧钛产率最高,后处理最容易。对二苯基甲烷作为反应溶剂制备酞菁氧钛进行了正交实验,得到最佳反应条件:反应温度200°C,反应时间3 h,钛酸四丁酯和1,3-二亚胺基异吲哚啉投料摩尔比为3.5:1,反应中滴加钛酸四丁酯的温度120～130°C。通过实验验证,上述条件下得到酞菁氧钛产率为76.8%。通过X射线衍射、红外光谱、串联时间飞行质谱和元素分析对产物进行了检测。对以二苯基甲烷为溶剂合成的酞菁氧钛实验进行了放大,使用5 L反应器进行反应,得到酞菁氧钛收率在70%以上。以苯、甲苯、二甲苯、均三甲苯、二苯基甲烷、乙苯、正丙苯、十二烷基苯等烷基芳烃与水的混合溶剂在不同温度和时间下对无定型酞菁氧钛进行转型,通过对转型产品的X射线衍射分析,发现取代基较少、烷基链较短时,烷基芳烃更容易使无定型酞菁氧钛转化为Y-TiOPc;苯、甲苯、二甲苯和乙苯等芳烃由于转型能力过强,在一定条件下会使转型产品出现β-TiOPc的特征衍射峰。使用甲苯/水、二甲苯/水、均三甲苯/水、乙苯/水体系转型得到的Y-TiOPc制备了光导鼓器件,所得器件残余电位60～80 V,暗衰率20～25 V/s,光敏性达到0.12～0.14μJ/cm~2。将TiOPc作为空穴传输材料应用在钙钛矿电池中,β-TiOPc制备的电池PCE为3.14%;使用α-TiOPc作为光吸收剂与CH3NH3PbI3一起用在钙钛矿电池中,使电池的JSC由9.40 mA/cm~2增加到12.65 mA/cm~2。
[Abstract]:Titanium phthalocyanine is a widely used organic functional material. In the existing synthetic methods of titanium phthalocyanine, the conventional process for the synthesis of titanium phthalocyanine is generally using quinoline, tetrahydronaphthalene N-methylpyrrolidone 1-chloronaphthalene, o-dichlorobenzene and other high boiling organic solvents. The use of these solvents has the following disadvantages: high toxicity, safety and environmental protection, impurities containing chlorine or nitrogen heterocycles will be produced in the synthesis process, the purity of TiOPc will be reduced, and the post-treatment will be difficult. The transformation inducing solvents of amorphous titanium phthalocyanine are usually used in organic solvents, such as monochlorobenzene, dichlorobenzene and chloronaphthalene, which are easily harmful to the environment and human health. In this paper, the green synthesis of titanium phthalocyanine was studied using tetrabutyl titanate and 1-diimindoline as raw materials, using dimethyl silicone oil, dodecyl benzene and diphenyl methane as the reaction solvents, respectively. By contrast, the yield of titanium phthalocyanine is the highest when diphenyl methane is used as the reaction solvent, and the post treatment is the easiest. The orthogonal experiment was carried out on the preparation of titanium phthalocyanine with diphenyl methane as the reaction solvent. The optimum reaction conditions were obtained as follows: reaction temperature 200 掳C, reaction time 3 h, molar ratio of tetrabutyl titanate and 1 diimino isoindoline 3.5: 1, and the temperature of dropping tetrabutyl titanate 120 掳C. The experimental results show that the yield of titanium phthalocyanine is 76. 8% under the above conditions. The products were detected by X-ray diffraction, infrared spectroscopy, tandem time flight mass spectrometry and elemental analysis. The experiment of synthesizing titanium phthalocyanine with diphenyl methane as solvent was carried out in a 5L reactor. The yield of titanium phthalocyanine was over 70%. A mixture of benzene, toluene, xylene, trimethylbenzene, diphenyl methane, ethylbenzene, n-propylbenzene, dodecylbenzene and water was used to transform amorphous titanium phthalocyanine at different temperatures and time. By X-ray diffraction analysis of the transition products, it is found that alkyl aromatics are more likely to convert amorphous phthalocyanine oxygen to Y-TiOPc when there are fewer substituents and shorter alkyl chains, and benzene, toluene, xylene and ethylbenzene are more easily converted to Y-TiOPc.The conversion ability of benzene, toluene, xylene and ethylbenzene is too strong. Under certain conditions, the characteristic diffraction peaks of 尾-TiOPc will appear in the transition products. A photoconductive drum device was prepared by using Y-TiOPc transformed from toluene / water, xylene / water, terylene / water and ethylbenzene / water system. The residual potential of the device was 6080 V, the dark decay rate was 2025 V / s, and the Guang Min property was 0.12 ~ 0.14 渭 J / cm ~ (-2) 路cm ~ (-2). Using TiOPc as hole transport material in perovskite cell, the PCE of 尾 -TiOPc battery is 3.14, and 伪 -TiOPc is used in perovskite battery with CH3NH3PbI3 as optical absorbent. The JSC of the cell increases from 9.40 mA/cm~2 to 12.65 Ma / cm ~ (-2).
【学位授予单位】：天津大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TB34

【相似文献】