脂溶性及纳米酞菁化合物的合成表征及性质研究
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摘要
酞菁(Phthalocyanine)类化合物因具有独特的物理化学性质,一直是科学家研究的热点课题。经历了近百年的发展,其在高科技领域中的应用越来越广泛,现已被普遍应用于超导材料、化工、生物模拟、非线性材料、信息储存、智能识别、医疗等众多尖端技术领域。然而,由于酞菁的难溶、难提纯等因素的存在,在很大程度上限制了酞菁在上述领域中的深度开发。
本文在一类溶解性较好、纯度高、易于衍生化的酞菁材料——氨基酞菁的基础上合成了易溶于乙醇、氯仿、丙酮等有机溶剂中的酞菁衍生物,即由四氨基锌酞菁分别和戊醛和庚醛,经schiff碱反应,合成了四戊亚胺基酞菁及四庚亚胺基酞菁,并对它们进行了紫外可见光谱等表征。
此外,本文又尝试采用溶剂热法合成酞菁,即以邻苯二甲腈为原料,由乙二醇为溶剂在反应釜中合成了Fe、Co、Ni、Cu、Zn等金属酞菁化合物。通过对采用不同合成方法得到的两种四硝基取代的金属酞菁进行比较,发现采用溶剂热法合成的酞菁化合物具有产量高、后续处理方法简便、未经色层分离即可得到纯度较高的产品等特点。我们对它们进行了质谱、XRD、电子扫描电镜、紫外可见光谱及红外光谱表征。
表征的结果发现:(1)由Zn(1),ZnO(2), Zn(Ac)2 (3),三种不同的金属源都可以在相同的反应条件下合成锌酞菁,且产品纯度高、产率大。而其中由氧化物和锌盐为源形成的产物通过XRD可以发现晶型相同,单质的则不同。(2)由不同金属铁、钴、镍、铜、锌的盐为配体形成的酞菁化合物,经过简单的水洗,就能够得到纯度很好的不同形貌酞菁化合物。(3)在硝基取代的的金属酞菁中,通过3-NO2邻苯二腈与铜形成的(9)中,从电镜照片中可以看出,由于取代基的存在,3位取代四硝基酞菁铜为中空的纳米球。(4)通过schiff碱反应,合成了四戊亚胺基酞菁及四庚亚胺基酞菁。
展望金属酞菁的未来,我们希望把有机合成与溶剂热化学方法更有效的结合起来,通过修饰前体化合物,合成更多的具有优异功能的酞菁类化合物,相较于单一有机方法的多步分离、提纯,可以提高产率及产品的纯度。
The particular physical and chemical properties of phthalocyanines (Pcs) have been paid close attention more and more in science field by the scientist. As a kind of advanced functional materials in high-tech field, their applications are increasing steadily for a hundred year. Pcs are widely applied in some sophisticated technique such as super conducting materials, chemistry, biology simulation, nonlinear optics, information storage, intellective recognition ,medical , and so on. However, in certain extent their applications are limited due to the bad dissolution, difficulty in purification .
We sythesised a kind of Pc derivation which solved in most organic solvent such as ethanol、chloroform、acetone and so on,based on the amino-phthalocyanines M(Ⅱ) with excellent solubility, easy derivatization and high purity . Tetraamylimido-phthalocyanine Zn (Ⅱ)and tetraageimino-phthalocyanine have been prepared through schiff reaction of some amino- phthalocyanines Zn(Ⅱ) with amyl aldehyde and heptanal, respectively. They are characterized using UV-vis method.
In addition,we experimented the solvethermal method with 1,2-dicyanobenzene and glycol getting the Fe、Co、Ni、Cu、Zn’s phthalocyanine compound in reactionkettle.Compared with organic synthesis method,we find that the Pc compound which come from solvethermal method have characteristic of good yield easily tretment and highly purified. We characterized them by MS ,XRD, SEM ,UV-vis and IR.
The characterization results show that (1) three different kinds of Zn simplesubstance or compounds also can synthesis Zn-Pc fruitfully and high purity.From XRD,we can see simplesubstance Zn-Pc is differents to others.(2)Five differernt pattern metal phthalocyanine compounds have been got through simple washing.(3)Tetra-4-nitro phthalocyanine Cu which come from 4-nitro-1,2-benzenedicarbonitrile and Cu(Ac)2, formated the microballoon sphere in XRD.(4)Tetraamylimido-phthalocyanine Zn (Ⅱ) and tetraageimino-phthalocyanine have been prepared through schiff reaction.
To expect the future of metal-phthalocyanines M(Ⅱ), we will synthesis a kind of desired excellent fuction phthalocyanine compound combination organic synthesis and solvethermal. Compare with the organic synthesis way, it doesn’t need multi-steps purification and seperation. Solvethermal may improve the phthalocyanine compound’s yield and purity.
本文在一类溶解性较好、纯度高、易于衍生化的酞菁材料——氨基酞菁的基础上合成了易溶于乙醇、氯仿、丙酮等有机溶剂中的酞菁衍生物,即由四氨基锌酞菁分别和戊醛和庚醛,经schiff碱反应,合成了四戊亚胺基酞菁及四庚亚胺基酞菁,并对它们进行了紫外可见光谱等表征。
此外,本文又尝试采用溶剂热法合成酞菁,即以邻苯二甲腈为原料,由乙二醇为溶剂在反应釜中合成了Fe、Co、Ni、Cu、Zn等金属酞菁化合物。通过对采用不同合成方法得到的两种四硝基取代的金属酞菁进行比较,发现采用溶剂热法合成的酞菁化合物具有产量高、后续处理方法简便、未经色层分离即可得到纯度较高的产品等特点。我们对它们进行了质谱、XRD、电子扫描电镜、紫外可见光谱及红外光谱表征。
表征的结果发现:(1)由Zn(1),ZnO(2), Zn(Ac)2 (3),三种不同的金属源都可以在相同的反应条件下合成锌酞菁,且产品纯度高、产率大。而其中由氧化物和锌盐为源形成的产物通过XRD可以发现晶型相同,单质的则不同。(2)由不同金属铁、钴、镍、铜、锌的盐为配体形成的酞菁化合物,经过简单的水洗,就能够得到纯度很好的不同形貌酞菁化合物。(3)在硝基取代的的金属酞菁中,通过3-NO2邻苯二腈与铜形成的(9)中,从电镜照片中可以看出,由于取代基的存在,3位取代四硝基酞菁铜为中空的纳米球。(4)通过schiff碱反应,合成了四戊亚胺基酞菁及四庚亚胺基酞菁。
展望金属酞菁的未来,我们希望把有机合成与溶剂热化学方法更有效的结合起来,通过修饰前体化合物,合成更多的具有优异功能的酞菁类化合物,相较于单一有机方法的多步分离、提纯,可以提高产率及产品的纯度。
The particular physical and chemical properties of phthalocyanines (Pcs) have been paid close attention more and more in science field by the scientist. As a kind of advanced functional materials in high-tech field, their applications are increasing steadily for a hundred year. Pcs are widely applied in some sophisticated technique such as super conducting materials, chemistry, biology simulation, nonlinear optics, information storage, intellective recognition ,medical , and so on. However, in certain extent their applications are limited due to the bad dissolution, difficulty in purification .
We sythesised a kind of Pc derivation which solved in most organic solvent such as ethanol、chloroform、acetone and so on,based on the amino-phthalocyanines M(Ⅱ) with excellent solubility, easy derivatization and high purity . Tetraamylimido-phthalocyanine Zn (Ⅱ)and tetraageimino-phthalocyanine have been prepared through schiff reaction of some amino- phthalocyanines Zn(Ⅱ) with amyl aldehyde and heptanal, respectively. They are characterized using UV-vis method.
In addition,we experimented the solvethermal method with 1,2-dicyanobenzene and glycol getting the Fe、Co、Ni、Cu、Zn’s phthalocyanine compound in reactionkettle.Compared with organic synthesis method,we find that the Pc compound which come from solvethermal method have characteristic of good yield easily tretment and highly purified. We characterized them by MS ,XRD, SEM ,UV-vis and IR.
The characterization results show that (1) three different kinds of Zn simplesubstance or compounds also can synthesis Zn-Pc fruitfully and high purity.From XRD,we can see simplesubstance Zn-Pc is differents to others.(2)Five differernt pattern metal phthalocyanine compounds have been got through simple washing.(3)Tetra-4-nitro phthalocyanine Cu which come from 4-nitro-1,2-benzenedicarbonitrile and Cu(Ac)2, formated the microballoon sphere in XRD.(4)Tetraamylimido-phthalocyanine Zn (Ⅱ) and tetraageimino-phthalocyanine have been prepared through schiff reaction.
To expect the future of metal-phthalocyanines M(Ⅱ), we will synthesis a kind of desired excellent fuction phthalocyanine compound combination organic synthesis and solvethermal. Compare with the organic synthesis way, it doesn’t need multi-steps purification and seperation. Solvethermal may improve the phthalocyanine compound’s yield and purity.
引文
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[2]刘颖.三种取代酞菁的合成、结构及性质研究.东北师范大学.2005年5月
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