-
摘要: 为有效对抗高、超光谱成像侦察威胁，实现迷彩绿色涂料与植物的"同谱同色"，本文基于酞菁与叶绿素卟啉结构的相似性，开展酞菁化合物合成及植物光谱特征拟合研究。构建吸电子取代基团和二价过渡族中心离子的平面酞菁结构，采用DBU催化法和自制合成装置合成酞菁化合物，探究最佳合成条件和提纯方法，采用分光光度计测试产物的吸收光谱和反射光谱，研究中心离子与聚集方式对酞菁化合物光谱性能的影响。实验结果表明，在催化剂作用下，四硝基金属酞菁在240~250℃时反应时间最短；钴酞菁比铁、锌、铜等作为中心取代离子形成的酞菁产物具有更尖锐的吸收峰，与绿色植物光谱曲线更相似；酞菁化合物的光谱反射曲线随温度、纯度及分散状态对产物聚集状态影响而产生移动。在220~240℃下合成20~30 min的四-硝基钴酞菁吸收光谱符合酞菁化合物Q带吸收特征，且其峰值波长与植物光谱相拟合，为酞菁类颜料在军事、纺织、染料、仿生等领域的应用提供了新方法和新途径。Abstract: In order to effectively resist the threat of hyperspectral imaging and reconnaissance and achieve "the same spectrum and color" of camouflage paint and plants, based on the similarity between phthalocyanine and chlorophyll porphyrin structure, the synthesis of phthalocyanine compounds and the fitting of plant spectral features are carried out. The planar phthalocyanine structure of the electron-withdrawing substituent and the divalent transition center ion is constructed. The phthalocyanine compounds are synthesized by DBU catalysis and self-made synthesis equipment. The optimal synthesis conditions and purification methods are investigated. The absorption and reflectance spectra of the products are tested by spectrophotometer to study the influence of central ion and aggregation on the spectral properties of phthalocyanine compounds. The experimental results show that the reaction time of tetranitrometal phthalocyanine is the shortest at 240~250℃ under the action of catalyst; cobalt phthalocyanine has a sharper absorption peak than the phthalocyanine product formed by iron, zinc, copper and other centrally substituted ions, which is more similar to the green plant spectral curve; the spectral reflection curve of the phthalocyanine compound shifts with the influence of temperature, purity and dispersion state on the product aggregation state. The absorption spectrum of tetra-nitro cobalt phthalocyanine synthesized at 220~240℃ for 20~30 min are in agreement with the Q band absorption characteristics of phthalocyanine compounds, and its peak wavelengths are matched with the plant spectrum. It provides new methods and new approaches for the application of phthalocyanine pigments in the fields of military, textile, dye and bionic etc.
-
Key words:
- phthalocyanine synthesis /
- spectral characteristics /
- chlorophyll /
- hyperspectral image
-
图 1 金属酞菁DBU催化合成原理示意图
Figure 1. A schematic diagram of DBU catalytic synthesis of metal phthalocyanine
图 2 自主设计合成装置及合成工艺示意图
(1.聚四氟乙烯磁子, 2.高温温度计, 3.冷凝管, 4.集热式磁力搅拌器, 5.甲基硅油油浴锅, 6.反应液)
Figure 2. Schematic diagram of self-designed synthesis device and synthetic process
(1.Teflon polyethylene magneton; 2.High temperature thermometer; 3.Condensing tube; 4.Heat magnetic mixer; 5.Methyl silicone oil bath wok; 6.Reaction liquid)
图 4 不同中心金属的反应时间与反应温度
Figure 4. Reaction time and reaction temperature of different central metals
图 6 酞菁吸收峰曲线(上)与光谱反射曲线(下)
Figure 6. Phthalocyanine absorption peak curve(top) and spectral reflection curve(below)
图 7 不同纯度四硝基酞菁铁的光谱反射曲线
Figure 7. Spectral reflectance curves of different purity tetral phthalocyanine iron metals
图 8 不同纯度四硝基酞菁钴的光谱反射曲线
Figure 8. Spectral reflectance curves of different purity tetra-nitrophthalocyanine cobalt metals
图 10 不同浓度、湿度的样品反射光谱曲线
Figure 10. Sample reflectance spectra of different concentrations and humidity
图 11 不同温度分散的样品反射光谱曲线
Figure 11. Sample reflectance spectra of different temperature dispersion
表 1 原料剂表
Table 1. Ingredient list
名称 规格 试剂厂家 N, N-二甲基乙酰胺 AR 科龙化工 二氯甲烷 AR Tansoole DBU 99% 阿拉丁 乙醇 AR 南京化学试剂厂 甲醇 AR 西陇化工 各种金属氯化物 AR 西陇化工 4-硝基邻苯二甲腈 98% 阿拉丁 石英砂 60~80目AR 南京化学试剂厂 硅胶 200目AR 南京化学试剂厂 
下载: 导出CSV
表 2 金属酞菁最佳合成条件
Table 2. Optimum synthesis conditions of metal phthalocyanine
产物 反应温度/℃ 反应时间/min 表观颜色 四硝基酞菁铁(TNFePC) 270±5 50±3 墨绿色 四硝基酞菁铬(TNCrPC) 230±5 30±3 深靛色 四硝基酞菁钴(TNCoPC) 230±5 30±3 深绿色 四硝基酞菁镍(TNNiPC) 220±5 20±3 深青色 四硝基酞菁铜(TNCuPC) 240±5 30±3 深蓝色 四硝基酞菁锌(TNZnPC) 220±5 20±3 青绿色
下载: 导出CSV
-
[1] 张良培.高光谱目标探测的进展与前沿问题[J].武汉大学学报信息科学版, 2014, 39(12):1387-1394. http://d.old.wanfangdata.com.cn/Periodical/whchkjdxxb201412001ZHANG L P. Advance and future challenges in hyperspectral target detection[J]. Geomatics and Information Science of Wuhan University, 2014, 39(12):1387-1394.(in Chinese) http://d.old.wanfangdata.com.cn/Periodical/whchkjdxxb201412001 [2] 蒋晓军, 吕绪良, 潘家亮, 等.基于光学和红外特征模拟的植物仿生材料设计制备[J].光谱学与光谱分析, 2015, 35(7):1835-1839. doi: 10.3964/j.issn.1000-0593(2015)07-1835-05JIANG X J, LÜ X L, PAN J L, et al.. Design and preparation of plant bionic materials based on optical and inf rared features simulation[J]. Spectroscopy and Spectral Analysis, 2015, 35(7):1835-1839.(in Chinese) doi: 10.3964/j.issn.1000-0593(2015)07-1835-05 [3] 张薇, 于媛媛, 张宇, 等.新型水溶性金属酞菁化合物的合成与表征[J].分子科学学报(中、英文), 2015, 31(4):270-275. http://d.old.wanfangdata.com.cn/Periodical/fzkxxb201504002ZHANG W, YU A A, ZHANG Y, et al.. Synthesis and characterization of novel water-soluble metallophthalocyanines[J]. Journal of Molecular Science, 2015, 31(4):270-275.(in Chinese) http://d.old.wanfangdata.com.cn/Periodical/fzkxxb201504002 [4] BENSON G ONGARORA, XIAO K H, HAI R L, et al. Syntheses and properties of trimethylaminophenoxy-substituted Zn(Ⅱ)-phthalocyanines[J]. MedChemComm, 2012, 3(2):179-194. doi: 10.1039/C1MD00232E [5] 周茂清, 李尧, 姚博, 等.基于并五苯/酞菁铅异质结的近红外光敏有机场效应管[J].发光学报, 2014, 35(3):342-348. http://cdmd.cnki.com.cn/Article/CDMD-10730-1014297970.htmZHOU M Q, LI Y, YAO B, et al.. Near infrared photoresponsive organic field-effect transistors by utilizing pentacene/lead phthalocyanine heterojunction[J]. Chinese Journal of Luminescence, 2014, 35(3):342-348.(in Chinese) http://cdmd.cnki.com.cn/Article/CDMD-10730-1014297970.htm [6] 王殿巍, 左青卉, 陆永波, 等.菲并咪唑衍生物蓝光材料的合成、光物理性质及理论计算[J].发光学报, 2016, 37(11):1346-1352. http://d.old.wanfangdata.com.cn/Periodical/fgxb201611007WANG D W, ZUO Q H, LU Y B, et, al.. Synthesis, photophysical properties and theoretical study of blue luminescence materials based on phenanthro[9, 10-d] imidazole[J]. Chinese Journal of Luminescence, 2016, 37(11):1346-1352.(in Chinese) http://d.old.wanfangdata.com.cn/Periodical/fgxb201611007 [7] 赵地顺, 刘猛帅, 葛京京, 等.双核离子液体的合成及其对酯化反应的催化活性[J].有机化学, 2012, 32(12):002382-2389. http://d.old.wanfangdata.com.cn/Periodical/yjhx201212027ZHAO D S, LIU M S, GE J J, et al.. Synthesis of binuclear ionic liquids and their catalytic activity for esterification[J]. Chinese Journal of Organic Chemistry, 2012, 32(12):2382.(in Chinese) http://d.old.wanfangdata.com.cn/Periodical/yjhx201212027 [8] 王颖, 任奇志, 郭琳童, 等.四磺酸酞菁及其金属配合物的合成、表征及对1, 5-萘二酚的光敏催化氧化性能[J].高等学校化学学报, 2013, 34(7):1576-1584. http://d.old.wanfangdata.com.cn/Periodical/gdxxhxxb201307003WANG Y, RENG Q ZH, GUO L T, et al.. Synthesis, characterization and photocatalytic oxidation for 1, 5-dihydroxynaphthalene of tetrasulfophthalocyanine and its metallophthalocyanine complex[J]. Chemical Journal of Chinese Universities, 2013, 34(7):1576-1584.(in Chinese) http://d.old.wanfangdata.com.cn/Periodical/gdxxhxxb201307003 [9] 王东兴, 刘晓廉, 焦兵兵, 等.Al/CuPC/Cu肖特基气敏二极管制备与特性[J].哈尔滨理工大学学报, 2012, 17(2):127-130. doi: 10.3969/j.issn.1007-2683.2012.02.029WANG D X, LIU X L, JIAO B B, et al.. Gas-sensitive characteristics research of Al/CuPC/Cu schottky diode[J]. Journal of Harbin University of Science and Technology, 2012, 17(2):127-130.(in Chinese) doi: 10.3969/j.issn.1007-2683.2012.02.029 [10] 杜文强, 苏斌, 田沛东, 等.酞菁类金属化合物在有机太阳能电池中的应用[J].吉林师范大学学(自然科学版), 2015, 36(1):42-49. http://d.old.wanfangdata.com.cn/Periodical/slxk-zrkx201501008DU W Q, SU B, TIAN P D, et al.. Research of the application of phthalocyanine metal compound in organic solar cells[J]. Jilin Normal University Journal:Natural Science Edition, 2015, 36(1):42-49.(in Chinese) http://d.old.wanfangdata.com.cn/Periodical/slxk-zrkx201501008 [11] 李占国, 张玉婷, 谢强, 等.基于p-6P异质诱导生长酞菁铜薄膜的NO2传感器[J].物理化学学报, 2016, 32(4):1005-1011. http://d.old.wanfangdata.com.cn/Periodical/wlhxxb201604036LI Z G, ZHANG Y T, XIE Q, et al.. NO2 sensors based on p-6P heterogametic induction growth of copper phthalocyanine thin films[J]. Acta Physico-Chimica Sinica, 2016, 32(4):1005-1011.(in Chinese) http://d.old.wanfangdata.com.cn/Periodical/wlhxxb201604036 [12] 郑亚开, 韦一, 孙磊, 等.衬底温度对TiOPC光敏有机场效应管的影响[J].发光学报, 2016, 37(6):725-730. http://d.old.wanfangdata.com.cn/Periodical/fgxb201606015ZHENG Y K, WEI Y, SUN L, et al.. Substrate temperature dependent performance of photoresponsive organic field effect transistors based on itanyl-phthalocyanine[J]. Chinese Journal of Luminescence, 2016, 37(6):725-730.(in Chinese) http://d.old.wanfangdata.com.cn/Periodical/fgxb201606015 [13] 黄金陵, 彭亦如, 陈耐生.金属酞菁配合物结构研究的一些谱学方法[J].光谱学与光谱分析, 2001, 21(1):1-6. doi: 10.3321/j.issn:1000-0593.2001.01.001HUANG J L, PENG Y R, CHEN N S. Some spectrum methods on the structures of metal phthalocyanine[J]. Spectroscopy and Spectral Analysis, 2001, 21(1):1-6.(in Chinese) doi: 10.3321/j.issn:1000-0593.2001.01.001 [14] MA C Y, YE K Q, YU S K, et al.. Synthesis and hypochromic effect of phthalocyanines and metal phthalocyanines[J]. Dyes & Pigments, 2007, 74(1):141-147. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=JJ027436576 [15] 夏道成, 李万程, 李洁筠, 等.1, 11, 15, 25-四羟基-4, 8, 18, 22-二(桥联二丙羧基)酞菁铜的合成及性质研究[J].光谱学与光谱分析, 2015(8):2292-2296. doi: 10.3964/j.issn.1000-0593(2015)08-2292-05XIA D C, LI W C, LI J J, et al.. Synthesis and properties of 1, 11, 15, 25-tetrahydroxy-4, 8, 18, 22-di(bridged dipropionate carboxyl) phthalocyanine copper[J]. Spectroscopy and Spectral Analysis, 2015(8):2292-2296.(in Chinese) doi: 10.3964/j.issn.1000-0593(2015)08-2292-05 [16] JIN L, CHEN D J. Enhancement in photovoltaic performance of phthalocyanine-sensitized solar cells by attapulgite nanoparticles[J]. Electrochimica Acta, 2012, 72(7):40-45.(in Chinese) https://www.sciencedirect.com/science/article/pii/S0013468612005609 [17] 夏道成, 李杰筠, 李万程, 等.新型可溶性酞菁的合成及谱学性质研究[J].光谱学与光谱分析, 2017, 37(12):3793-3796. http://d.old.wanfangdata.com.cn/Periodical/gpxygpfx201712026XIA D C, LI J J, LI W C, et al.. Synthesis and characterization of 4, 8, 15, 22-tetra[3, 3-bis(P-hydroxyphenyl) phthalide] phthalocyanines[J]. Spectroscopy and Spectral Analysis, 2017, 37(12):3793-3796.(in Chinese) http://d.old.wanfangdata.com.cn/Periodical/gpxygpfx201712026 [18] 李凯, 韩蛟, 张厚玉, 等.分子聚集体的光谱模拟[J].高等学校化学学报, 2011, 32(12):2872-2876. http://d.old.wanfangdata.com.cn/Periodical/gdxxhxxb201112031LI K, HAN J, ZHANG H Y, et al.. Simulations of spectra of molecular aggregates[J]. Chemical Journal of Chinese Universities, 2011, 32(12):2872-2876.(in Chinese) http://d.old.wanfangdata.com.cn/Periodical/gdxxhxxb201112031 [19] 卢礼萍, 李明, 刘桂玲, 等.叶黄素聚集体吸收光谱的实验分析与理论模拟[J].光谱学与光谱分析, 2016, 36(10):3287-3291. http://d.old.wanfangdata.com.cn/Periodical/gpxygpfx201610045LU L P, LI M, LIU G L, et al.. Study on absorption spectra of lutein aggregate with experimental analysis and theoretical calculation[J]. Spectroscopy and Spectral Analysis, 2016, 36(10):3287-3291.(in Chinese) http://d.old.wanfangdata.com.cn/Periodical/gpxygpfx201610045 -
下载:
点击查看大图
图(11) / 表(2)
计量
- 文章访问数: 2155
- HTML全文浏览量: 530
- PDF下载量: 296
- 被引次数: 0
