CN102181179A - Method for preparing soluble substituted phthalocyanine-carbon nano tube composite photosensitive material by click chemical method - Google Patents
Method for preparing soluble substituted phthalocyanine-carbon nano tube composite photosensitive material by click chemical method Download PDFInfo
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Abstract
The invention belongs to the technical field of organic/inorganic nano composite materials, and particularly relates to a method for preparing a soluble substituted phthalocyanine-carbon nano tube composite photosensitive material by a click chemical method. Compared with the common esterification method, amide method and the like, the method disclosed by the invention has the characteristics of mild conditions, fast reaction, high composite efficiency and the like; the dispersion uniformity and storage stability of the obtained substituted phthalocyanine-carbon nano tube composite material are obviously improved; and the soluble substituted phthalocyanine-carbon nano tube composite material prepared by the click chemical method has relatively high photosensitivity, compatibility and thermal stability as well as good solubility and photoelectric properties. The product prepared by the method is a new-generation green high-performance chemical product which is applicable to the fields of conductive materials, solar cell materials, photoconductive materials, photoelectric conversion materials and the like.
Description
Technical field
The invention belongs to the Organic technical field, be specifically related to the method that a kind of click chemistry legal system is equipped with the compound photochromics of solubility substituted phthalocyanine-carbon nanotube.
Background technology
Exhaustion day by day along with fossil energies such as coal, oil, Sweet natural gases, the energy shortage problem in the whole world is more and more outstanding, energy problem has become the significant problem that countries in the world economy, social development run into, badly influenced human existence and development, people press for the alternative energy of seeking other.Advantages such as it is inexhaustible, safe and reliable, pollution-free that sun power has more and more are subjected to people's attention.But as industrial energy, sun power has the low shortcoming of energy density, and in order to make full use of this cheapness, environmental protection, reproducible new forms of energy, produce photovoltaic solar cell cheap, efficient, the energy large-area preparation is the target that people pursued always.At present, silica-based and main flow that other inorganic metal compound photovoltaic solar cells are solar cells, photoelectric transformation efficiency can reach more than 25%.Although yet production cost declines to a great extent in recent years, the cost problem remains its major obstacle that significantly replaces traditional energy.Because inorganic solar cell production process complexity, it is very difficult further significantly to reduce cost, and the problems such as the limit of cost height and effciency of energy transfer are restricted its large-scale promotion.The most cheap and non-organic semiconductor material of attractive solar cell material does not belong to: organic materials is easy to synthesize and cost is lower, snappiness and film-forming properties are all better; Organic solar batteries processing is simple, and device cost is lower; But big area manufacturing; Environmental friendliness, easy to carry etc., so organic solar battery material has become new focus of area of solar cell.
The research of organic solar batteries starts from nineteen fifty-nine, and its structure is that the monocrystalline anthracene is clipped between 2 electrodes, but owing to the too low turnover ratio that makes of dissociation efficiency of exciton is extremely low, this individual layer Schottky device is an organic solar batteries device architecture the earliest.Early stage polymer thin-film solar cell structure is based on this Schottky-barrier, material has mainly concentrated on the organic dye such as phthalocyanine, perylene, but because being positioned at the metal electrode of battery sandwich, incident light reflected away major part, so photoelectric transformation efficiency is not high always.Along with the development of organic solar batteries, the structure of organic solar batteries is begun by individual layer Schottky device, has developed double-deck heterojunction, body heterojunction, molecule D-A knot in succession and based on the cascade device of above modular construction etc.To be material dissociate and the transmission of electric charge to absorption, the exciton of sunlight the factor of decision photoelectric transformation efficiency in the organic solar batteries, and therefore selecting suitable material is the key that obtains high performance solar cell.
As the organic materials of electron donor(ED) and hole transport body, phthalocyanine (Pc), polyvinyl carbazole (PVK), poly-to vinylbenzene (PPV), polyaniline (PANI), polypyrrole (PPy), aromatic amine and condensed ring aromatic compound etc. are arranged.Phthalocyanine is p type organic semiconductor material normally, can modify or change the performance of phthalocyanine by the type that changes substituting group on the phthalocyanine ring and central metal, obtains the different functional materials of performance; When the substituting group of phthalocyanine periphery connects when haling electron substituent group such as F, C N etc., even can be converted into the n N-type semiconductorN.And for traditional phthalocyanine, substituted phthalocyanine has than remarkable advantages and unique photoelectric properties, in common organic solvent, has good solubility, has very strong absorption at visible light and near-infrared region, maximum peak position coupling with solar spectrum, the p-N-type semiconductorN characteristic that it showed, abundant redox characteristic and thermostability relatively are suitable as the donor material of solar cell material.
As electron acceptor material, CdSe, TiO are arranged
2, C
60With carbon nanotube etc., C
60Can accept six electronics at most, higher electron affinity and ionizing potential be arranged with respect to conjugated polymers, and electron transport ability preferably, so it is higher as electron acceptor(EA) and the compound efficient of organic photovoltaic cell that can make of conjugated polymers.But C
60Solvent borne is poor in organic solvent, and easily crystallization is difficult to realize high doping content in the film process, has limited the raising of its processing characteristics and photoelectric transformation efficiency.So people have expected it is carried out graft modification, find 1-(3-methoxyl group carboxyl)-propyl group-1-phenyl-(6,6) C
61(PCBM) have solvability preferably, the doping content in polymkeric substance improves greatly and helps the formation that inierpeneirating network structure is a bulk heterojunction, has improved photoelectric transformation efficiency.
In recent years, someone's compound photosensitive material system of carbon nanotube/organic materials that begins one's study is with C
60Compare, carbon nanotube (CNTs) has good electron-transporting equally, and its special one dimension length can reduce the loss that electronics jumps and caused between carbon nanotube, thereby increases the mobility of electronics.(Synthesis such as Ballesteros in 2007, characterization and photophysical properties of a SCNT-phthalocyanine hybrid. Chem Commun, 2007,2950-2952.) introduce amido by cycloaddition reaction on the Single Walled Carbon Nanotube surface, utilize the carboxyl and the carbon nanotube that have on the phthalocyanine ring to react acquisition phthalocyanine-carbon nanotube complex light sensitive film material again, its optical property in different wavelength range has been discussed.(a kind of unsymmetrical phthalocyanine/carbon nanotube composite materials and preparation method thereof such as Yang Zhenglong, Chinese invention patent, CN 200710041170.4) utilize esterification to introduce the phthalocyanine precursor in carbon nano tube surface, carry out reaction in carbon nano tube surface again and prepare asymmetric substituted phthalocyanine, proposed the compound photochromics novel method of a kind of preparation unsymmetrical phthalocyanine-carbon nanotube.At present, also few for utilizing the click chemistry legal system to be equipped with the report of the compound photochromics of solubility substituted phthalocyanine-carbon nanotube.
Summary of the invention
The objective of the invention is to overcome the deficiency that prior art exists, invent the method that a kind of click chemistry legal system is equipped with the compound photochromics of solubility substituted phthalocyanine-carbon nanotube.
The present invention is equipped with the method for the compound photochromics of solubility substituted phthalocyanine-carbon nanotube for a kind of click chemistry legal system.This method is at first carried out chemically modified and alkynyl modification to carbon nanotube, makes its surface be with a certain amount of alkynyl; Be raw material with 4-bromo-phthalic nitrile again, 4-bromo-phthalic nitrile is carried out azide make it have a certain amount of azido group, then the phthalic nitrile of azide and the carbon nanotube that has an alkynyl are carried out the click chemistry reaction and obtain a kind of carbon nano-tube material that contains phthalic nitrile; Again a kind of substituted phthalic mitrile monomer and the above-mentioned carbon nano-tube material that contains phthalic nitrile are carried out in-situ chemical reaction and obtain the compound photochromics of a kind of solubility substituted phthalocyanine-carbon nanotube.This method with respect to common esterification process, acid amides method etc. have mild condition, speed of response is fast and characteristics such as composite efficiency height, advantages such as preparation method of the present invention has that simple process is convenient, quality product is high, input-output ratio is high, with low cost and application prospect is extensive, the product that utilizes the present invention to prepare has higher light sensitivity, consistency and thermostability, and have good solubility property and photoelectric properties, can be used for fields such as electro-conductive material, solar cell material, photoconductive material and photoelectric conversion material.
A kind of click chemistry legal system that the present invention proposes is equipped with the method for the compound photochromics of solubility substituted phthalocyanine-carbon nanotube, and concrete steps are as follows:
(1) 100 ~ 1000mg multi-walled carbon nano-tubes is added in the mixed strong acids solution of 50 ~ 300ml vitriol oil and concentrated nitric acid composition, sonic oscillation was handled 3 ~ 12 hours, poured in the deionized water, and left standstill more than 12 hours, filtered and be washed to neutrality, vacuum-drying.Obtain the carbon nanotube of band carboxyl;
(2) under nitrogen protection, place excessive thionyl chloride to reflux 12 ~ 72 hours the carbon nanotube of the above-mentioned band carboxylic acid of 80 ~ 800mg, reaction finishes, and excessive thionyl chloride is removed in underpressure distillation, and vacuum-drying obtains the carbon nanotube of chloride;
(3) carbon nanotube with the above-mentioned chloride of 15 ~ 100mg is dispersed in the N-Methyl pyrrolidone of 10 ~ 50ml, ultrasonic 10 ~ 30 minutes, the 4-(3-methyl-monosilane ethynyl that adds 0.9 ~ 6.3g again) Isopentyl nitrite of aniline and 0.6 ~ 4.5ml, under 50 ~ 90 ℃ of nitrogen protection conditions, successive reaction 24 ~ 48 hours, be cooled to precipitate in 25 ℃ of ethanol of pouring 50 ~ 200ml later on into, centrifuging, and use tetrahydrofuran (THF), methylene dichloride repeatedly washs (being generally 3-5 time), vacuum-drying, again the carbon nanotube that obtains is dispersed in the N-Methyl pyrrolidone of 10 ~ 50ml, the tetrahydrofuran solution of the tetrabutyl ammonium fluoride of 2 mol/L of adding 1 ~ 5ml, continued stirring at normal temperature 1 ~ 4 hour, again solution is poured in the ethanol of 50 ~ 200ml and precipitated, centrifugal, use tetrahydrofuran (THF), methylene dichloride repeatedly washs (being generally 3-5 time), and 30 ~ 80 ℃ of vacuum-dryings obtain the alkynyl modified carbon nanotube after 6 ~ 36 hours;
(4) take by weighing the 4-bromo-phthalic nitrile of 0.2 ~ 2.3g and the sodiumazide of 0.15 ~ 1.5g, be dissolved in the flask of the tetrahydrofuran (THF) that contains 10 ~ 100ml and 1 ~ 10ml water, 50 ~ 70 ℃ of stirrings 2 ~ 8 hours that reflux down, reaction finishes postcooling to 25 ℃, use the dichloromethane extraction reaction solution, and dewater, filter with anhydrous magnesium sulfate drying, vacuum-drying obtains flaxen 4-nitrine-phthalic nitrile;
(5) carbon nanotube with the above-mentioned alkynylization of 5 ~ 50mg adds in the flask of the N-Methyl pyrrolidone that contains 10 ~ 100ml, 4-nitrine-the phthalic nitrile that takes by weighing 2 ~ 20mg again joins in the flask, add 1 of the cuprous iodide of 2 ~ 20mg and 40 ~ 400mg again, 8-diazabicylo [5.4.0] 11 carbon-7-alkene (DBU), stirring reaction is 24 ~ 72 hours under 70 ℃ of nitrogen protections, after being cooled to 25 ℃, pour in 50 ~ 500ml ethanol and precipitate, centrifugation, and repeatedly wash (being generally 3-5 time) with tetrahydrofuran (THF) and methylene dichloride, vacuum-drying obtains the carbon nano-tube material that the surface contains the 4-phthalic nitrile;
(6) carbon nanotube that the above-mentioned surface of 5 ~ 50mg is contained the 4-phthalic nitrile is dispersed in the Pentyl alcohol of 10 ~ 100ml, the substituted phthalic mitrile of the 10 ~ 100mg that adds, 1 of the Zinc Chloride Anhydrous of 1 ~ 10mg and 20 ~ 200mg, 8-diazabicylo [5.4.0] 11 carbon-7-alkene (DBU), vigorous stirring is 24 ~ 72 hours under 90 ~ 150 ℃ and nitrogen protection condition, after being cooled to 25 ℃, pour in 50 ~ 500ml ethanol and precipitate, centrifugation, repeatedly wash (being generally 3-5 time) with tetrahydrofuran (THF) and phosgene, 20 ~ 80 ℃ of vacuum-dryings obtain a kind of solubility substituted phthalocyanine-carbon nano tube compound material after 6 ~ 36 hours;
(7) the above-mentioned solubility substituted phthalocyanine-carbon nano tube compound material of 5 ~ 50mg is dispersed in the tetrahydrofuran (THF), the concentration of this matrix material is 1 ~ 10 mg/ml, under ultrasound condition 25 ℃ ultrasonic 1 ~ 12 hour, obtain a kind of solubility substituted phthalocyanine-carbon nano tube compound material solution;
(8) adopt spin coating method that above-mentioned solubility substituted phthalocyanine-carbon nano tube compound material solution is coated on the conductive matrices, its spin speed is 1000 ~ 3000rpm/s, bake out temperature is 35-120 ℃, drying time is 0.5-6 hour, and the thickness of the compound photosensitive coating of dried solubility substituted phthalocyanine-carbon nanotube is 10 ~ 50 μ m.
Among the present invention, 4-bromo-phthalic nitrile described in the step (4) can be 4-bromo-5-nitro phthalic nitrile, 4-bromo-5-to benzyloxy-phthalic nitrile between tertiary butyl phenoxy group-phthalic nitrile, 4-bromo-5-, the adjacent benzyloxy-phthalic nitrile of 4-bromo-5-, 4-bromo-5-in benzyloxy-phthalic nitrile or the 4-bromo-5-nitro-p-isopropyl phenoxy group-phthalic nitrile etc. any.
Among the present invention, described conductive matrices can be conduction tinsel, ito glass, above scribble the poly-of conducting medium
Among the present invention, the volume ratio of the vitriol oil and concentrated nitric acid is 3:1 in the step (1).
Among the present invention, the vacuum-drying temperature is 30 ~ 80 ℃ described in step (1) and the step (2), and the time is 2-12 hour.
Among the present invention, the vacuum-drying temperature is 30 ~ 80 ℃ described in the step (3), and the time is 6 ~ 24 hours.
Among the present invention, the vacuum-drying temperature is 20 ~ 60 ℃ described in the step (4), and the time is 10 ~ 24 hours.
Among the present invention, the vacuum-drying temperature is 30 ~ 80 ℃ described in the step (5), and the time is 6-36 hour.
Among the present invention, the vacuum-drying temperature is 20 ~ 80 ℃ described in the step (6), and the time is 6 ~ 36 hours.
Advantage of the present invention is: 1. the present invention prepares the method for the compound photochromics of solvable substituted phthalocyanine-carbon nanotube for a kind of click chemistry method, this matrix material is made up of substituted phthalocyanine and carbon nanotube, absorption in visible region red shift along with the adding of carbon nanotube, compare with pure phthalocyanine, its absorption spectrum is taken into account the near infrared light zone more, can improve the composite efficiency of substituted phthalocyanine and carbon nanotube greatly by present method, it and ground solar spectrum mate more, thereby have improved it to solar energy utilization rate; 2. the product that utilizes the present invention to prepare has higher light sensitivity, consistency and thermostability, and having good solubility property and photoelectric properties, the dispersing uniformity of the compound photochromics of this solubility substituted phthalocyanine-carbon nanotube and package stability all will be much better than traditional physical blending method, esterification process and acid amides method etc.; Advantage such as preparation method 3. of the present invention has that technology is easy, quality product is high, input-output ratio is high, with low cost and application prospect is extensive, the product that utilizes the present invention to prepare is new generation of green environment-friendly and high-performance Chemicals, can be used for fields such as electro-conductive material, solar cell material, photoconductive material and photoelectric conversion material.
Description of drawings
Fig. 1 is the photo of the tetrahydrofuran solution of the compound photochromics of solubility substituted phthalocyanine-carbon nanotube, from left to right is followed successively by carbon nanotube, substituted phthalocyanine, the compound photochromics of solubility substituted phthalocyanine-carbon nanotube.
Fig. 2 is the uv-visible absorption spectrum figure of the compound photochromics of solubility substituted phthalocyanine-carbon nanotube, and A is a substituted phthalocyanine, and B is the compound photochromics of solubility substituted phthalocyanine-carbon nanotube.
Fig. 3 is the transmission electron microscope photo of the compound photochromics of solubility substituted phthalocyanine-carbon nanotube, and (a) figure is the simple physical blend of substituted phthalocyanine/carbon nanotube, and (b) figure is the compound photochromics of solubility substituted phthalocyanine-carbon nanotube of click chemistry method preparation.
Embodiment
Embodiment 1
The 500mg multi-walled carbon nano-tubes is added in the mixed strong acids solution that the 150mL vitriol oil and concentrated nitric acid form for 3:1 by volume, and sonic oscillation processing 4 hours is poured in the deionized water, and left standstill 12 hours, filter and be washed to neutrality, dry again, obtain the carbon nanotube of chemical etching; Under nitrogen protection, place the thionyl chloride of 100ml to reflux 36 hours the carbon nanotube of the above-mentioned band carboxylic acid of 400mg, reaction finishes, and excessive thionyl chloride is removed in underpressure distillation, and vacuum-drying obtains the carbon nanotube of chloride; Two (triphenyl phosphorus) palladium chlorides of 4-Iodoaniline, 400mg, 217mg cuprous iodide, 1.73ml trimethyl silane ethyl-acetylene and the new triethylamine that steams of 20ml that in the 50ml flask, add 2.5g, the normal temperature nitrogen protection was reacted 12 hours down, filter and repeatedly wash filter residue with ether, again organic phase is merged, ammonium chloride solution, sodium chloride solution with 2mol/L repeatedly washs then, add anhydrous magnesium sulfate drying at last, obtain 4-(3-methyl-monosilane ethynyl) aniline; Carbon nanotube with the above-mentioned chloride of 40mg is dispersed in the N-Methyl pyrrolidone of 25ml again; ultrasonic 30 minutes; the 4-(3-methyl-monosilane ethynyl that adds 1g) Isopentyl nitrite of aniline and 0.67ml; successive reaction is 24 hours under 70 ℃ of nitrogen protection conditions; being cooled to 25 ℃ pours into later in the 100ml ethanol and precipitates; centrifugation; and use tetrahydrofuran (THF); methylene dichloride repeatedly washs; 30 ℃ of vacuum-dryings are after 12 hours; again the carbon pipe is dispersed in the N-Methyl pyrrolidone of 25ml; the tetrahydrofuran solution that adds the 2mol/L tetra-n-butyl Neutral ammonium fluoride of 3ml 25 ℃ of stirring reactions 2 hours, is poured in the 100ml ethanol and is precipitated; centrifugation; repeatedly wash with tetrahydrofuran (THF) and methylene dichloride, 30 ℃ of vacuum-drying 12 hours promptly obtains the carbon nanotube of alkynylization.
The carbon nanotube of 10mg alkynylization is dissolved in the flask of the N-Methyl pyrrolidone that contains 10ml; 4-nitrine-phthalic nitrile with 6mg joins in the flask again; add 1 of the cuprous iodide of 6.8mg and 54mg again; 8-diazabicylo [5.4.0] 11 carbon-7-alkene (DBU); under 70 ℃ of nitrogen protections, carry out click-reaction; 48 hours postcooling to 25 of stirring reaction ℃; pour in the 100ml ethanol and precipitate; centrifugation; and repeatedly wash with tetrahydrofuran (THF) and methylene dichloride, 50 ℃ of vacuum-dryings make the carbon nanotube that the 4-phthalic nitrile is modified after 12 hours.
The carbon nanotube of getting the above-mentioned 4-phthalic nitrile modification for preparing of 8mg is dispersed in the Pentyl alcohol of 10ml; 4-benzyloxy-5-nitro-the phthalic nitrile that adds 12mg again; 1 of the Zinc Chloride Anhydrous of 1mg and 20mg; 8-diazabicylo [5.4.0] 11 carbon-7-alkene (DBU); vigorous stirring is 48 hours under 100 ℃ and nitrogen protection condition; after being cooled to 25 ℃; pour in the 100ml ethanol and precipitate; centrifugation; repeatedly wash with tetrahydrofuran (THF) and phosgene, 50 ℃ of vacuum-dryings obtain the compound photochromics of a kind of solubility substituted phthalocyanine-carbon nanotube after 12 hours.
Solubility substituted phthalocyanine-the carbon nanotube of the above-mentioned preparation of 5mg is dispersed in the tetrahydrofuran (THF), concentration is 5mg/ml, in ultrasonic pond 25 ℃ ultrasonic 2 hours, adopt spin coating method that above-mentioned phthalocyanine-carbon nanotube complex light sensitive film material solution is coated on the ITO conductive matrices again, speed of rotation is 1000 rpm/s, bake out temperature is 50 ℃, and drying time is 2 hours, and the compound photosensitive coat-thickness of dried solubility substituted phthalocyanine-carbon nanotube is 25 μ m.
The digital photograph of the tetrahydrofuran solution of the compound photochromics of this solubility substituted phthalocyanine-carbon nanotube as shown in Figure 1, Fig. 2 and Fig. 3 are respectively its uv-visible absorption spectrum figure and transmission electron microscope photo.
Embodiment 2
Identical with embodiment 1, but the reaction times of click-reaction became 24 hours by original 48 hours.
Embodiment 3
Identical with embodiment 1, but the reaction times of click-reaction became 72 hours by original 48 hours.
Embodiment 4
Identical with embodiment 1, but 4-bromo-phthalic nitrile becomes 4-bromo-5-nitro-phthalic nitrile.
Embodiment 5
Identical with embodiment 1, but 4-bromo-phthalic nitrile becomes 4-bromo-5-to tertiary butyl phenoxy group-phthalic nitrile.
Embodiment 6
Identical with embodiment 1, but the temperature of reaction in the preparation of the 3rd step solubility substituted phthalocyanine-carbon nanotube compound photochromics is become 120 ℃ by original 100 ℃.
Embodiment 7
Identical with embodiment 1, but the consumption of 4-benzyloxy-5-nitro-phthalic nitrile in the preparation of the compound photochromics of the 3rd step solubility substituted phthalocyanine-carbon nanotube is become 24mg by 12mg.
Embodiment 8
Identical with embodiment 1, but the reaction times in the penultimate stride was become 96 hours by 48 hours.
Embodiment 9
Identical with embodiment 1, but the Pentyl alcohol in the penultimate stride is become propyl carbinol.
Embodiment 10
Identical with embodiment 1, but to be become by 1000 rpm/s be 2000 rpm/s to spin speed, and bake out temperature becomes 100 ℃ by 50 ℃.
Embodiment 11
Identical with embodiment 1, but coating method changes dip coating into by spin-coating method, and conductive matrices changes metallic aluminium into by the ito glass sheet.
The compound photochromics of solubility substituted phthalocyanine-carbon nanotube that the click chemistry legal system that obtains among the embodiment 2-11 is equipped with compound photochromics of solubility substituted phthalocyanine-carbon nanotube and embodiment 1 has similar performance.
Claims (9)
1. a click chemistry legal system is equipped with the method for the compound photochromics of solubility substituted phthalocyanine-carbon nanotube, it is characterized in that concrete steps are as follows:
(1) 100 ~ 1000mg multi-walled carbon nano-tubes is added in the mixed strong acids solution of 50 ~ 300ml vitriol oil and concentrated nitric acid composition, sonic oscillation was handled 3 ~ 12 hours, poured in the deionized water, and left standstill more than 12 hours, filtered and be washed to neutrality, vacuum-drying; Obtain the carbon nanotube of band carboxyl;
(2) under nitrogen protection, place excessive thionyl chloride to reflux 12 ~ 72 hours the carbon nanotube of the above-mentioned band carboxylic acid of 80 ~ 800mg, reaction finishes, and excessive thionyl chloride is removed in underpressure distillation, and vacuum-drying obtains the carbon nanotube of chloride;
(3) carbon nanotube with the above-mentioned chloride of 15 ~ 100mg is dispersed in the N-Methyl pyrrolidone of 10 ~ 50ml, ultrasonic 10 ~ 30 minutes, the 4-(3-methyl-monosilane ethynyl that adds 0.9 ~ 6.3g again) Isopentyl nitrite of aniline and 0.6 ~ 4.5ml, under 50 ~ 90 ℃ of nitrogen protection conditions, successive reaction 24 ~ 48 hours, be cooled to precipitate in 25 ℃ of ethanol of pouring 50 ~ 200ml later on into, centrifuging, and use tetrahydrofuran (THF), washed with dichloromethane, vacuum-drying, again the carbon nanotube that obtains is dispersed in the N-Methyl pyrrolidone of 10 ~ 50ml, the tetrahydrofuran solution of the tetrabutyl ammonium fluoride of 2 mol/L of adding 1 ~ 5ml, continued stirring at normal temperature 1 ~ 4 hour, again solution is poured in the ethanol of 50 ~ 200ml and precipitated, centrifugal, use tetrahydrofuran (THF), washed with dichloromethane, 30 ~ 80 ℃ of vacuum-dryings obtain the alkynyl modified carbon nanotube after 6 ~ 36 hours;
(4) take by weighing the 4-bromo-phthalic nitrile of 0.2 ~ 2.3g and the sodiumazide of 0.15 ~ 1.5g, be dissolved in the flask of the tetrahydrofuran (THF) that contains 10 ~ 100ml and 1 ~ 10ml water, 50 ~ 70 ℃ of stirrings 2 ~ 8 hours that reflux down, reaction finishes postcooling to 25 ℃, use the dichloromethane extraction reaction solution, and dewater, filter with anhydrous magnesium sulfate drying, vacuum-drying obtains flaxen 4-nitrine-phthalic nitrile;
(5) carbon nanotube with the above-mentioned alkynylization of 5 ~ 50mg adds in the flask of the N-Methyl pyrrolidone that contains 10 ~ 100ml, 4-nitrine-the phthalic nitrile that takes by weighing 2 ~ 20mg again joins in the flask, add 1 of the cuprous iodide of 2 ~ 20mg and 40 ~ 400mg again, 8-diazabicylo [5.4.0] 11 carbon-7-alkene, stirring reaction is 24 ~ 72 hours under 70 ℃ of nitrogen protections, after being cooled to 25 ℃, pour in 50 ~ 500ml ethanol and precipitate, centrifugation, and repeatedly wash (being generally 3-5 time) with tetrahydrofuran (THF) and methylene dichloride, vacuum-drying obtains the carbon nano-tube material that the surface contains the 4-phthalic nitrile;
(6) carbon nanotube that the above-mentioned surface of 5 ~ 50mg is contained the 4-phthalic nitrile is dispersed in the Pentyl alcohol of 10 ~ 100ml, the substituted phthalic mitrile of the 10 ~ 100mg that adds, 1 of the Zinc Chloride Anhydrous of 1 ~ 10mg and 20 ~ 200mg, 8-diazabicylo [5.4.0] 11 carbon-7-alkene, vigorous stirring is 24 ~ 72 hours under 90 ~ 150 ℃ and nitrogen protection condition, after being cooled to 25 ℃, pour in 50 ~ 500ml ethanol and precipitate, centrifugation, repeatedly wash (being generally 3-5 time) with tetrahydrofuran (THF) and phosgene, 20 ~ 80 ℃ of vacuum-dryings obtain a kind of solubility substituted phthalocyanine-carbon nano tube compound material after 6 ~ 36 hours;
(7) the above-mentioned solubility substituted phthalocyanine-carbon nano tube compound material of 5 ~ 50mg is dispersed in the tetrahydrofuran (THF), the concentration of this matrix material is 1 ~ 10 mg/ml, under ultrasound condition 25 ℃ ultrasonic 1 ~ 12 hour, obtain a kind of solubility substituted phthalocyanine-carbon nano tube compound material solution;
(8) adopt spin coating method that above-mentioned solubility substituted phthalocyanine-carbon nano tube compound material solution is coated on the conductive matrices, its spin speed is 1000 ~ 3000rpm/s, bake out temperature is 35-120 ℃, drying time is 0.5-6 hour, and the thickness of the compound photosensitive coating of dried solubility substituted phthalocyanine-carbon nanotube is 10 ~ 50 μ m.
2. preparation method according to claim 1, it is characterized in that 4-bromo-phthalic nitrile described in the step (4) be 4-bromo-5-nitro phthalic nitrile, 4-bromo-5-to benzyloxy-phthalic nitrile between tertiary butyl phenoxy group-phthalic nitrile, 4-bromo-5-, the adjacent benzyloxy-phthalic nitrile of 4-bromo-5-, 4-bromo-5-in benzyloxy-phthalic nitrile or the 4-bromo-5-nitro-p-isopropyl phenoxy group-phthalic nitrile any.
3. preparation method according to claim 1, it is characterized in that described conductive matrices be conduction tinsel, ito glass, above scribble in polyester chips, drum type and the zonal conducting metal or the electrical conductivity alloy of conducting medium any.
4. preparation method according to claim 1 is characterized in that the volume ratio of the middle vitriol oil of step (1) and concentrated nitric acid is 3:1.
5. preparation method according to claim 1 is characterized in that the vacuum-drying temperature is 30 ~ 80 ℃ described in step (1) and the step (2), and the time is 2-12 hour.
6. preparation method according to claim 1 is characterized in that the vacuum-drying temperature is 30 ~ 80 ℃ described in the step (3), and the time is 6 ~ 24 hours.
7. preparation method according to claim 1 is characterized in that the vacuum-drying temperature is 20 ~ 60 ℃ described in the step (4), and the time is 10 ~ 24 hours.
8. preparation method according to claim 1 is characterized in that the vacuum-drying temperature is 30 ~ 80 ℃ described in the step (5), and the time is 6-36 hour.
9. preparation method according to claim 1 is characterized in that the vacuum-drying temperature is 20 ~ 80 ℃ described in the step (6), and the time is 6 ~ 36 hours.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103787302A (en) * | 2014-01-23 | 2014-05-14 | 黑龙江大学 | Preparation method of tetrafluoropropoxy-substituted metal phthalocyanine/carbon nanotube composite material |
| CN105728053A (en) * | 2016-01-28 | 2016-07-06 | 燕山大学 | Metal phthalocyanine/carbon-based photocatalyst and preparation method thereof |
| CN110479373A (en) * | 2019-06-12 | 2019-11-22 | 常州大学 | The preparation method of one kind 3 α-(to tert-butyl benzene oxygroup)-α-(nitro)-Phthalocyanine Zinc/multi-walled carbon nanotube catalyst |
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101100563A (en) * | 2007-05-24 | 2008-01-09 | 同济大学 | Nano composite material of asymmetric phthalocyanine and carbon nano-tube and preparation method thereof |
| CN101254916A (en) * | 2008-04-11 | 2008-09-03 | 北京工业大学 | Method for in-situ synthesis of metal phthalocyanine/carbon nano-tube compound |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101100563A (en) * | 2007-05-24 | 2008-01-09 | 同济大学 | Nano composite material of asymmetric phthalocyanine and carbon nano-tube and preparation method thereof |
| CN101254916A (en) * | 2008-04-11 | 2008-09-03 | 北京工业大学 | Method for in-situ synthesis of metal phthalocyanine/carbon nano-tube compound |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103787302A (en) * | 2014-01-23 | 2014-05-14 | 黑龙江大学 | Preparation method of tetrafluoropropoxy-substituted metal phthalocyanine/carbon nanotube composite material |
| CN103787302B (en) * | 2014-01-23 | 2015-06-10 | 黑龙江大学 | Preparation method of tetrafluoropropoxy-substituted metal phthalocyanine/carbon nanotube composite material |
| CN105728053A (en) * | 2016-01-28 | 2016-07-06 | 燕山大学 | Metal phthalocyanine/carbon-based photocatalyst and preparation method thereof |
| CN110479373A (en) * | 2019-06-12 | 2019-11-22 | 常州大学 | The preparation method of one kind 3 α-(to tert-butyl benzene oxygroup)-α-(nitro)-Phthalocyanine Zinc/multi-walled carbon nanotube catalyst |
| 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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