CN100523096C - Nano composite material of asymmetric phthalocyanine and carbon nano-tube and preparation method thereof - Google Patents
Nano composite material of asymmetric phthalocyanine and carbon nano-tube and preparation method thereof Download PDFInfo
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- CN100523096C CN100523096C CNB2007100411704A CN200710041170A CN100523096C CN 100523096 C CN100523096 C CN 100523096C CN B2007100411704 A CNB2007100411704 A CN B2007100411704A CN 200710041170 A CN200710041170 A CN 200710041170A CN 100523096 C CN100523096 C CN 100523096C
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Abstract
A nanometer composite material of asymmetric phthalocyanine and carbon nanometer tube and its production are disclosed. The process is carried out by reacting organic small-molecular chemically modified carbon nanometer tube with nitro-substituted phthalic nitrile monomer to obtain carbon nanometer tube with phthalic nitrile group, in situ reacting it with phthalic nitrile monomer to obtain final product. It's tight and homogeneous, it has excellent dissolving, filming and photoelectric performances. It can be used in conductive, luminescent, solar battery and transistor industries.
Description
Technical field
The invention belongs to the Organic technical field, be specifically related to a kind of unsymmetrical phthalocyanine and carbon nanotube composite materials and preparation method thereof.
Background technology
Research based on the Organic of phthalocyanine/carbon nanotube has become one of focus of present investigation of materials.Up to now, the preparation method of the phthalocyanine/carbon nanotube composite materials of bibliographical information generally is divided into two classes.The first kind is the method that adopts physics to fill and coat, it is compound that carbon nanotube and phthalocyanine material are carried out physics, though improved functional performances such as the solvability of carbon nano-tube material and photoelectricity, but though this method easy and simple to handle have the phthalocyanine molecule in carbon nano tube surface in conjunction with closely and easily not coming off, and uncontrollable phthalocyanine material is in the shortcomings such as uniform distribution of carbon nano tube surface.Another kind of is to obtain phthalocyanine/carbon nano tube compound material with chemical modification method or by chemical reaction, though can significantly improve dispersing uniformity and the processability of carbon nanotube in solvent, and the size of nano composite material can further reduce, and is difficult to control thermally-stabilised than problem such as property is relatively poor with nano composite material but this method also exists nano combined degree.In addition, up to now, also seldom relevant unsymmetrical phthalocyanine/carbon nanotube composite materials preparation method's report.
The present invention utilizes multistep synthesis method and in-situ reaction to prepare a kind of being evenly distributed and chemically stable unsymmetrical phthalocyanine/carbon nanotube composite materials, it overcome traditional phthalocyanine macromole carbon nano tube surface in conjunction with closely and easily do not come off and the phthalocyanine material in the difficult problems such as skewness of carbon nano tube surface, and the present invention can significantly improve the photoconductive property of phthalocyanine/carbon nano tube compound material, and obtains preferable luminous sensitivity.This unsymmetrical phthalocyanine/carbon nanotube composite materials has not only kept carbon nanotube special mechanical properties and electric property, the good solubility property, film forming properties and the photoelectric properties that have unsymmetrical phthalocyanine again, have boundless application prospect, can be applicable to photoelectric device fields such as conduction, luminous, solar cell, transistor.
Summary of the invention
The objective of the invention is to propose a kind of thermostability and chemical stability height, the unsymmetrical phthalocyanine that film forming properties, solubility property and photoelectric properties are good and carbon nanotube composite materials and preparation method thereof.
Unsymmetrical phthalocyanine and carbon nanotube composite materials that the present invention proposes, be to replace the phthalonitrile monomer reaction by carbon nanotube and nitro through the organic molecule chemical modification, make the carbon nanotube that the surface has adjacent benzene dicyan group, this carbon nanotube makes with other adjacent benzene dicyan class monomer reaction in again.Here organic molecule can be dibasic alcohol, diamine or amino-contained silane coupling agent, for example hexylene glycol, quadrol and aminopropyl triethoxysilane (KH-550) etc.
The unsymmetrical phthalocyanine that the present invention proposes and the preparation method of carbon nanotube composite materials are as follows:
(1) 100～1000mg multi-walled carbon nano-tubes is added in the mixed strong acids solution that the 50ml vitriol oil and concentrated nitric acid are 2:1～4:1 composition by volume, sonic oscillation was handled 3～12 hours, pour in the deionized water then, and leave standstill more than 12 hours, filter, be washed to neutrality, dry again, obtain the carbon nanotube of chemical etching;
(2) the above-mentioned carbon nanotube of 50～500mg is dispersed in 10～100ml anhydrous dimethyl benzene solvent, under 60～80 ℃ of conditions, drip a kind of or two or more of 10～100ml dibasic alcohol, diamine and amino-contained silane coupling agent etc., after dropwising, be warmed up to the solvent boiling point temperature, continued back flow reaction 12～48 hours, filter out carbon nanotube, use methyl alcohol and washing with acetone clean successively, vacuum-drying obtained the carbon nanotube that the surface has amido or hydroxyl more than 12 hours again;
(3) under nitrogen protection, the carbon nanotube that the above-mentioned surface of 50～100mg is had amido or hydroxyl is dispersed in the new dimethyl sulfoxide (DMSO) of steaming of 10～100ml, add 2～5g nitro again and replace phthalonitrile monomer, after the stirring and dissolving, add 2～4g Anhydrous potassium carbonate powder more in batches, reacted under the room temperature 6～12 hours, slowly be warming up to 100～120 ℃ of reactions 24～72 hours again, filter out carbon nanotube, use methyl alcohol and washing with acetone clean successively, vacuum-drying obtained the carbon nanotube that the surface has adjacent benzene dicyan group more than 12 hours again;
(4) under nitrogen protection, above-mentioned 50～100mg surface is had the alkyl of the carbon nanotube of adjacent benzene dicyan group and other kind of 0.1～0.5g or alkoxyl group to be replaced adjacent benzene dicyan and mixes, add 0.1～0.3g urea, 0.01～0.05g anhydrous metal salt, 0.01～0.05g ammonium chloride and a small amount of ammonium molybdate again, under 180～220 ℃, be solvent with 50～150ml trichlorobenzene or oil of mirbane or quinoline, stirring reaction 6～20 hours; Organic solvents such as a large amount of trichloromethanes of cooling back adding dissolve not the phthalocyanine material and the unreacted raw material of keyed jointing, filter out carbon nanotube, use washes clean such as trichloromethane organic solvent and vacuum-drying complete again, promptly obtain a kind of unsymmetrical phthalocyanine and carbon nanotube composite materials.
Among the present invention, used dibasic alcohol, be ethylene glycol, Diethylene Glycol, triethylene glycol, propylene glycol, methyl propanediol, dipropylene glycol, 3-chloro-1,2-propylene glycol, 2-butyl-2-ethyl-1, ammediol, butyleneglycol, 1,3 butylene glycol, 1,4-butyleneglycol, 1,2-pentanediol, 1,5-pentanediol, 2,2,4-trimethylammonium-1,3-pentanediol, isoamyl glycol, 2-methyl-2,4-pentanediol, neopentyl glycol, 1,6-hexylene glycol, 1,7-heptanediol, 1,8-ethohexadiol, 1,9-nonanediol or different Buddhist glycol etc.Used diamine, be quadrol, Tetramethyl Ethylene Diamine, N-ethyl-quadrol, diphenyl ethylene diamine, N, N-dibenzyl-ethylenediamin, 1,2-propylene diamine, 1,3-propylene diamine, 1,2-butanediamine, 1,3-butanediamine, 1,4-butanediamine, positive pentamethylene diamine, secondary pentamethylene diamine, isoamyl diamines, methyl ring pentamethylene diamine, diamines, nonamethylene diamine, decamethylene diamine, 1,2-diaminopropanes, N, N-diethyl-1,3-diaminopropanes, N, N-two-tertiary butyl-quadrol, TCD-diamines or isophorone diamine etc.Used amino-contained silane coupling agent is γ-amido triethoxyl silane (KH-550), N-(β-aminoethyl)-γ-An Bingjisanjiayangjiguiwan (KH-792), γ-hexamethylene aminopropyl silane coupling agent, diethyl amino Union carbide A-162, anilinomethyl triethoxysilane or N-β (aminoethyl)-γ-An Bingjisanjiayangjiguiwan etc.
Among the present invention, used nitro replaces phthalonitrile monomer, is that the 3-nitro replaces adjacent benzene dicyan, the 4-nitro replaces phthalonitrile monomer or 3, and the 4-dinitrobenzene replaces adjacent benzene dicyan.
Among the present invention, used organic solvent, can be benzene, toluene, o-Xylol, m-xylene, p-Xylol, chlorobenzene, orthodichlorobenzene, Meta Dichlorobenzene, santochlor, trichlorobenzene, ethylene dichloride, tetrachloroethane, dimethyl sulfoxide (DMSO), N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, 1,4-dioxane, methylene dichloride, trichloromethane, oil of mirbane or quinoline etc.
Advantage of the present invention is: 1. mainly be connected in the chemical bond mode between carbon nanotube and the unsymmetrical phthalocyanine molecule, so the thermostability of this unsymmetrical phthalocyanine/carbon nanotube composite materials and chemical stability are very high, it overcome traditional phthalocyanine macromole carbon nano tube surface in conjunction with closely and easily do not come off and the phthalocyanine material in the difficult problems such as skewness of carbon nano tube surface; 2. in unsymmetrical phthalocyanine/carbon nanotube composite materials, the carbon nanotube caliber still keeps nanometer scale and partial order shape, carbon nanotube special mechanical properties and electric property have not only been kept, good solubility property, film forming properties and the photoelectric properties etc. that have unsymmetrical phthalocyanine again, the present invention can significantly improve the photoconductive property of phthalocyanine/carbon nano tube compound material, and obtains preferable luminous sensitivity; 3. the compound degree of unsymmetrical phthalocyanine/carbon nanotube composite materials and size can be controlled by kind and the reaction conditionss such as quantity, temperature of reaction and catalyzer of regulating organic molecule.The present invention has important use to field of photovoltaic materials such as conduction, luminous, solar cell, transistors and is worth.
Description of drawings
Fig. 1 is the electron microscope picture of unsymmetrical phthalocyanine/carbon nanotube composite materials.
Table 1 is the photoconductive property of unsymmetrical phthalocyanine/carbon nanotube composite materials.
Embodiment
The present invention will be described in detail below in conjunction with embodiment.Do not violating under the purport of the present invention, the present invention should be not limited to the content that following examples are specifically expressed.
Embodiment 1
The 100mg multi-walled carbon nano-tubes is added in the mixed strong acids solution of the 100ml vitriol oil and concentrated nitric acid (volume ratio is 3:1) composition, sonic oscillation was handled after 6 hours, slowly poured 500ml deionized water (band stirs) into, after the standing over night, filter and wash neutral with deionized water, put into oven for drying.Repeat 3 times, obtain the carbon nano-tube material behind the chemical etching.Adopt the carbon nanotube after 100mg activates to place the 150mL single necked round bottom flask, add 12mL silane resin acceptor kh-550 and 50mL toluene, at 130 ℃ of following backflow 10h.Filter out carbon nanotube, use 150 ℃ of following vacuum-dryings behind methyl alcohol and the washing with acetone successively, obtain surface-treated carbon nanotube.The above-mentioned surface-treated carbon nanotube of weighing 100mg is dispersed in the new N that steams of 30mL, in N '-dimethyl formamide, at ambient temperature, adds adjacent benzene dicyan of 1.73g (10mmol) 3-nitro and 3.0g Anhydrous potassium carbonate in batches.Stirring at room reaction 72h under condition of nitrogen gas.Filter out carbon nanotube, use toluene, tetrahydrofuran (THF) and distilled water wash successively, 60 ℃ of following vacuum-dryings obtain the carbon nanotube of surface with adjacent benzene dicyan group fully.Get the carbon nanotube of the above-mentioned dry surface of crossing of 50mg with adjacent benzene dicyan group, replacing adjacent benzene dicyan, 1.5g urea, 0.105g cuprous chloride, 0.112g ammonium chloride and a small amount of ammonium molybdate with 0.72g (3.6mmol) dodecyloxy mixes, at 180 ℃ of following oil of mirbane is solvent, stirring reaction 6h.The cooling back adds the unreacted reactants of dissolving such as trichloromethane and ethanol, filter out carbon nanotube, with tetrahydrofuran (THF) flush away most symmetrical CuPc, again through solvent wash and purifying repeatedly, after the vacuum-drying, obtain a kind of unsymmetrical phthalocyanine/carbon nanotube composite materials at last.Its microtexture such as Fig. 1, photoconductive property is as shown in table 1.
Embodiment 2
Identical with embodiment 1, but silane resin acceptor kh-550 changes hexylene glycol into
Embodiment 3
Identical with embodiment 1, but silane resin acceptor kh-550 changes diamines into.
Embodiment 4
Identical with embodiment 1, but the consumption of silane resin acceptor kh-550 changes 15ml into by 12mL.
Embodiment 5
Identical with embodiment 1, but the consumption of silane resin acceptor kh-550 changes 8ml into by 12mL.
Embodiment 6
Identical with embodiment 1, but the concentration of the adjacent benzene dicyan of 3-nitro changes 3.46g (20mmol) into by 1.73g (10mmol).
Embodiment 7
Identical with embodiment 1, but the concentration of the adjacent benzene dicyan of 3-nitro changes 0.865g (5mmol) into by 1.73g (10mmol).
Embodiment 8
Identical with embodiment 1, but temperature of reaction changes 200 ℃ into for 180 ℃, oil of mirbane changes quinoline into, and the reaction times, 6h changed 12h into.
The material of unsymmetrical phthalocyanine/carbon nanotube composite materials that obtains among the embodiment 2-8 and embodiment 1 has similar microstructure and performance.
Table 1
| Illumination (lx) | V C(V) | DRRC (V/s) | T 1/2(s) | V R(V) | E 1/2(lux·s) | S (lux·s) -1 |
| 30 | 780 | 44 | 0.04 | 96 | 1.2 | 0.833 |
Claims (6)
1, a kind of unsymmetrical phthalocyanine and carbon nanotube composite materials, it is characterized in that it being by replacing the phthalonitrile monomer reaction through the carbon nanotube of organic molecule chemical modification and nitro, make the carbon nanotube that the surface has adjacent benzene dicyan group, this carbon nanotube makes with other adjacent benzene dicyan class monomer reaction in again, and organic molecule is dibasic alcohol, diamine or amino-contained silane coupling agent here.
2, the preparation method of a kind of unsymmetrical phthalocyanine as claimed in claim 1 and carbon nanotube composite materials is characterized in that concrete steps are:
(1) 100～1000mg multi-walled carbon nano-tubes is added in the mixed strong acids solution that the 50ml vitriol oil and concentrated nitric acid are 2:1～4:1 composition by volume, sonic oscillation was handled 3～12 hours, pour in the deionized water then, and leave standstill more than 12 hours, filter, be washed to neutrality, dry again, obtain the carbon nanotube of chemical etching;
(2) the above-mentioned carbon nanotube of 50～500mg is dispersed in 10～100ml anhydrous dimethyl benzene solvent, under 60～80 ℃ of conditions, drip a kind of or two or more of 10～100ml dibasic alcohol, diamine and amino-contained silane coupling agent, after dropwising, be warmed up to the solvent boiling point temperature, continued back flow reaction 12～48 hours, filter out carbon nanotube, use the clean final vacuum of methyl alcohol and washing with acetone dry more than 12 hours successively, obtain the carbon nanotube that the surface has amido or hydroxyl;
(3) under nitrogen protection, the carbon nanotube that the above-mentioned surface of 50～100mg is had amido or hydroxyl is dispersed in the new distillatory dimethyl sulfoxide (DMSO) of 10～100ml, add 2～5g nitro again and replace phthalonitrile monomer, after the stirring and dissolving, add 2～4g Anhydrous potassium carbonate powder more in batches, reacted under the room temperature 6～12 hours, slowly be warming up to 100～120 ℃ of reactions 24～72 hours again, filter out carbon nanotube, use methyl alcohol and washing with acetone clean successively, vacuum-drying obtained the carbon nanotube that the surface has adjacent benzene dicyan group more than 12 hours again;
(4) under nitrogen protection, above-mentioned 50～100mg surface is had the carbon nanotube of adjacent benzene dicyan group and 0.1～0.5g alkyl or alkoxyl group to be replaced adjacent benzene dicyan and mixes, add 0.1～0.3g urea, 0.01～0.05g anhydrous metal salt, 0.01～0.05g ammonium chloride and a small amount of ammonium molybdate again, under 180～220 ℃, be solvent with 50～150ml trichlorobenzene or oil of mirbane or quinoline, stirring reaction 6～20 hours; Cooling back adds a large amount of organic solvents and dissolves not the phthalocyanine material and the unreacted raw material of keyed jointing, filters out carbon nanotube, and is clean and vacuum-drying is complete with organic solvent washing again, promptly obtains a kind of unsymmetrical phthalocyanine and carbon nanotube composite materials.
3, preparation method according to claim 2 is characterized in that used dibasic alcohol is ethylene glycol, propylene glycol, butyleneglycol, isoamyl glycol, 1,6-hexylene glycol, 1,7-heptanediol, 1,8-ethohexadiol, 1,9-nonanediol or different Buddhist glycol.
4, preparation method according to claim 2 is characterized in that used diamine is quadrol, propylene diamine, butanediamine, pentamethylene diamine, hexanediamine, nonamethylene diamine or decamethylene diamine.
5, preparation method according to claim 2 is characterized in that said amino-contained silane coupling agent is γ-amido triethoxyl silane, N-(β-aminoethyl)-γ-An Bingjisanjiayangjiguiwan, γ-hexamethylene aminopropyl silane coupling agent, diethyl amino Union carbide A-162, anilinomethyl triethoxysilane or N-β (aminoethyl)-γ-An Bingjisanjiayangjiguiwan.
6, preparation method according to claim 2 is characterized in that it is that the 3-nitro replaces adjacent benzene dicyan, the 4-nitro replaces phthalonitrile monomer or 3 that said nitro replaces phthalonitrile monomer, and the 4-dinitrobenzene replaces adjacent benzene dicyan.
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| CN101254916B (en) * | 2008-04-11 | 2010-04-07 | 北京工业大学 | Method for in-situ synthesis of metal phthalocyanine/carbon nano-tube compound |
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| CN102766324A (en) * | 2012-07-03 | 2012-11-07 | 吉林大学 | Polyaryletherketone based amino replaced metal phthalocyanine-nanographite composite and preparation method thereof |
| CN103289258B (en) * | 2013-06-18 | 2016-03-30 | 上海第二工业大学 | A kind of high-dielectric composite material, Preparation Method And The Use |
| CN103920535B (en) * | 2014-05-07 | 2016-04-13 | 常州大学 | Chemical graft process prepares amino cobalt phthalocyanine/carbon nano tube composite catalyst |
| CN110931716B (en) * | 2019-11-21 | 2022-05-06 | 广州市讯天电子科技有限公司 | Storage battery with low-voltage recharging performance and green plate lead paste |
| CN112047326A (en) * | 2020-09-14 | 2020-12-08 | 中国科学院长春光学精密机械与物理研究所 | Carbon nanotube phthalocyanine nanocomposite and preparation method and application thereof |
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