CN103787302A - Preparation method of tetrafluoropropoxy-substituted metal phthalocyanine/carbon nanotube composite material - Google Patents
Preparation method of tetrafluoropropoxy-substituted metal phthalocyanine/carbon nanotube composite material Download PDFInfo
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Abstract
The invention discloses a preparation method of a tetrafluoropropoxy-substituted metal phthalocyanine/carbon nanotube composite material, relating to a preparation method of a substituted metal phthalocyanine/carbon nanotube composite material, and aiming to solve the problems of complex process, severe reaction condition, long period, low yield, high cost and poor material performance in the conventional method for preparing the metal phthalocyanine/carbon nanotube composite material. The method comprises the following steps: adding tetrafluoropropoxyphthalonitrile, absolute ethyl alcohol, metal salt, a carboxylated carbon nanotube, 1,8-diazabicyclo[5.4.0]undec-7-ene into a reaction kettle in sequence; performing a solvothermal reaction; centrifuging or filtering; washing by using acetone, hydrochloric acid and water, and drying. The preparation method has the advantages of simple preparation process, low equipment requirement, rich raw material source, low production cost, short synthesizing period, mild reaction condition, easiness in separating products, high yield, environmental friendliness and high material performance, and is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of preparation method of substituted metal phthalocyanine/carbon nano tube compound material.
Background technology
Because carbon nanotube has excellent physics, chemistry and mechanical property, such as unique quasi-one dimensional nanostructure, huge specific surface area, quite high specific conductivity and stable physico-chemical property, become gas sensor and field of biosensors in recent years and fall over each other one of focus of research.But because carbon nanotube is easily assembled bunchy or winding, surperficial relative inertness, the dispersity in common solvent is low, becomes membrane means limited, and gas sensing performance is also not ideal enough, such as, time of recovery is slow, selectivity is poor, and these have greatly restricted its widespread use.The main way addressing the above problem is at present to adopt the means such as doping, finishing by carbon nanotube and other Material cladding, wherein metal phthalocyanine is as the matrix material of organic semiconductor gas sensitive and the compound preparation of carbon nanotube, due to the synergy of the two, the sensitive properties such as its time of recovery and sensitivity significantly improve, and are expected to the sensitive material as high-performance gas sensor and biosensor.
The method report of preparing at present metal phthalocyanine/carbon nano-tube matrix material is less, mainly contains two kinds, i.e. physical mixed method and chemical bonding.Physical mixed method generally has two steps, and the first step is under inert atmosphere, to pass through template reaction (catalysis), carries out organic synthesis, and obtains the metal phthalocyanine of purifying by the separation means such as column chromatography or vacuum-sublimation; Second step is by the metal phthalocyanine of carbon nanotube and purifying long-time stirring or ultrasonic reaction in strong solvent solvent (as DMF), obtain product (Yanyan Wang etc., J.Mater.Chem.21 (2011) 3779-3787 through processes such as micro-pore-film filtrations; Racheal O.Ogbodu etc., Dalton Trans.42 (2013) 10769-10777; Edith Antunes etc., Polyhedron60 (2013) 59 – 67; Bin Wang etc., Sensors and Actuators B190 (2014) 157-164).Physical mixed method also has under protection of inert gas, high boiling solvent (oil of mirbane or trichlorobenzene or quinoline, noxious solvent! ) in the method for heat prepare without substituted metal phthalocyanine/carbon nano tube compound material (Zuo Xia etc., patent ZL200810103806.8).Chemical bonding generally can be divided into three steps, and the first step is, by organic synthesis means, carbon nano tube surface is modified into particular functional group; Second step is to synthesize metal phthalocyanine by methods such as condensations with very low productive rate under inert atmosphere, and obtains having specified substituent group metal phthalocyanine by separating technologies such as complicated column chromatographies; The 3rd step is by the specified substituent group of the particular functional group of carbon nanotube and metal phthalocyanine, there is chemical reaction under certain condition, obtain combination product (Wadzanai Chidawanyika etc., Carbon48 (2010) 2831-2838 through the process such as micro-pore-film filtration or high speed centrifugation; Elena Jubete etc., Electrochimica Acta56 (2011) 3988-3995; Tebello Nyokong etc., Electrochimica Acta68 (2012) 44-51; Tawanda Mugadza etc., Synthetic Metals160 (2010) 2089-2098).
Summing up existing methodical feature all needs multistep organic synthesis and the separating-purifying process of condition harshness, complexity, relate to anhydrous and oxygen-free operation, stirring, backflow, underpressure distillation, column chromatography, ultrasonic, micro-pore-film filtration etc., preparation cycle is long, productive rate is low, single preparation amount is few, general milligram level.The matrix material that wherein physical mixed method makes, phthalocyanine be combined with carbon nanotube undertighten, be easy to come off, poor stability, the simultaneously skewness of phthalocyanine on carbon nanotube, fraction of coverage is not high, and is easy to assemble, solvent dispersion is poor; Although chemical bonding can improve stability to a certain extent, building-up process is very complicated and difficult, and productive rate is extremely low, and performance is restive.In some methods, also relate to using and discharging of hazardous and noxious substances.Therefore the preparation method who, seeks simple and efficient metal phthalocyanine/carbon nano-tube matrix material is still major issue urgently to be resolved hurrily at present.
Summary of the invention
The present invention seeks in order to solve the existing method of preparing metal phthalocyanine/carbon nano-tube matrix material, there is complex process, severe reaction conditions, the cycle is long, productive rate is low, cost is high and material property is poor problem, and a kind of preparation method of tetrafluoro propoxy-substituted metal phthalocyanine/carbon nano tube compound material is provided.
A preparation method for tetrafluoro propoxy-substituted metal phthalocyanine/carbon nano tube compound material, realizes according to the following steps:
One, according to weight percent take 4.04%～4.05% tetrafluoro propoxy-phthalic nitrile, 2.17%～2.31% metal-salt, 0.35%～0.36% carboxylic carbon nano-tube, 7.73%～7.74% 1,8-diazabicylo [5.4.0] 11 carbon-7-alkene (DBU) and 85.56%～85.68% dehydrated alcohol;
Two, by the tetrafluoro propoxy-phthalic nitrile, dehydrated alcohol, metal-salt, the carboxylic carbon nano-tube and 1 that take in step 1,8-diazabicylo [5.4.0] 11 carbon-7-alkene joins in reactor successively, after stirring evenly at 100～160 ℃ solvent thermal reaction 1～10h, then be cooled to 10～50 ℃, after centrifugal or filtration, gained precipitation is successively with acetone is washed, mass concentration is 1%～5% salt pickling and washing, dry, complete the preparation of tetrafluoro propoxy-substituted metal phthalocyanine/carbon nano tube compound material;
Wherein the metal-salt described in step 1 is cupric chloride, iron protochloride, cobalt chloride, nickelous chloride, zinc chloride, Palladous chloride, lead chloride or Manganous chloride tetrahydrate;
Tetrafluoro propoxy-phthalic nitrile described in step 1 is 4-(2,2,3,3-tetrafluoro propoxy-) phthalic nitrile, 3-(2,2,3,3-tetrafluoro propoxy-) phthalic nitrile or 4,5-bis-(2,2,3,3-tetrafluoro propoxy-) phthalic nitrile;
Carboxylic carbon nano-tube described in step 1 is carboxylated Single Walled Carbon Nanotube or carboxylated multi-walled carbon nano-tubes.
The advantage of the present invention and prior art contrast is:
1. preparation method of the present invention mixes all raw materials, adopt simple solvent-thermal method one step to prepare tetrafluoro propoxy-substituted metal phthalocyanine/carbon nano tube compound material, complicated, harsh, long multistep organic synthesis process that the present invention has avoided, does not need the loaded down with trivial details separation means such as column chromatography and micro-pore-film filtration and equipment simultaneously yet.It is simple that preparation method of the present invention has preparation technology, and equipment requirements is low, and starting material source is abundant, low production cost, synthesis cycle is short, reaction conditions is gentle, and product separation is easy, the advantages such as productive rate is high, and environmental friendliness and material property are good, are applicable to suitability for industrialized production.
2. preparation method's environmental protection of the present invention, ethanol used is really accomplished nontoxic, and other reaction raw materials is had to strong dissolving and dispersive ability, whole preparation process does not need to pass into other protection of inert gas, emits without poisonous, obnoxious flavour yet.
3. the present invention utilizes the electronegative groups such as a large amount of carboxyls in carboxylic carbon nano-tube surface, hydroxyl, and electrostatic interaction between metal-salt positively charged ion is evenly adsorbed on metal ion original position the surface of carbon nanotube.Fluorine atom on tetrafluoro propoxy-phthalic nitrile has strong electron-withdrawing power, can be dissolved in completely in alcohol solvent, under solvent thermal reaction condition, tetrafluoro propoxy-substituted metal phthalocyanine is directly synthesized in carbon nano tube surface original position, cover equably the surface of carbon nanotube, combine closely by π-π effect, hydrogen bond and coordination and carbon nanotube.This had both increased quantity (fraction of coverage) and the firmness of metal phthalocyanine molecule in carbon nano tube surface, also effectively prevented the gathering of metal phthalocyanine molecule self and the reunion of carbon nanotube, heavily piled up, made the matrix material of gained there is high stability and good solvent dispersion.Structural advantage makes to obtain tetrafluoro propoxy-substituted metal phthalocyanine/carbon nano tube compound material ammonia is shown to good gas sensitization performance, has potential using value in toxic and harmful detection field.
4. preparation method of the present invention can be extended to the matrix material preparation of other metal phthalocyanine compound and carbon nanotube.
Accompanying drawing explanation
Fig. 1 be in embodiment 1 preparation 2,9,16, the scanning electronic microscope (SEM) of 23-tetra-tetrafluoro propoxy-copper phthalocyanine/carbon nano tube compound materials figure;
Fig. 2 be in embodiment 1 preparation 2,9,16, the Cu of 23-tetra-tetrafluoro propoxy-copper phthalocyanine/carbon nano tube compound materials
2px-ray photoelectron power spectrum (XPS) figure;
Fig. 3 be in embodiment 1 preparation 2,9,16, the F of 23-tetra-tetrafluoro propoxy-copper phthalocyanine/carbon nano tube compound materials
1sx-ray photoelectron power spectrum (XPS) figure;
Fig. 4 be in embodiment 5 preparation 2,9,16,23-tetra-tetrafluoro propoxy-cobalt phthalocyanine/carbon nano tube compound materials are scattered in 5 kinds of different solvents (concentration is 0.1mg/mL), leave standstill figure after 2 months, wherein A solvent is water; B solvent is methyl alcohol; C solvent is ethanol; D solvent is acetone; E solvent is DMF;
Fig. 5 be in embodiment 5 preparation 2,9,16, the 23-tetra-uv-visible absorption spectra figures of tetrafluoro propoxy-cobalt phthalocyanine/carbon nano tube compound material in ethanol, wherein curve a represents carboxylated multi-walled carbon nano-tubes, and curve b represents 2,9,16,23-, tetra-tetrafluoro propoxy-cobalt phthalocyanine/carbon nano tube compound materials;
Fig. 6 be in embodiment 5 preparation 2,9,16, the thermogravimetric-differential thermogravimetric (TG-DTG) of 23-tetra-tetrafluoro propoxy-cobalt phthalocyanine/carbon nano tube compound materials under nitrogen atmosphere figure;
Fig. 7 be in embodiment 5 preparation 2,9,16,23-tetra-tetrafluoro propoxy-cobalt phthalocyanine/carbon nano tube compound materials are for the gas sensitization response restorability figure of different concns ammonia.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the preparation method of a kind of tetrafluoro propoxy-of present embodiment substituted metal phthalocyanine/carbon nano tube compound material, realizes according to the following steps:
One, according to weight percent take 4.04%～4.05% tetrafluoro propoxy-phthalic nitrile, 2.17%～2.31% metal-salt, 0.35%～0.36% carboxylic carbon nano-tube, 7.73%～7.74% 1,8-diazabicylo [5.4.0] 11 carbon-7-alkene and 85.56%～85.68% dehydrated alcohol;
Two, by the tetrafluoro propoxy-phthalic nitrile, dehydrated alcohol, metal-salt, the carboxylic carbon nano-tube and 1 that take in step 1,8-diazabicylo [5.4.0] 11 carbon-7-alkene joins in reactor successively, after stirring evenly at 100～160 ℃ solvent thermal reaction 1～10h, then be cooled to 10～50 ℃, after centrifugal or filtration, gained precipitation is successively with acetone is washed, mass concentration is 1%～5% salt pickling and washing, dry, complete the preparation of tetrafluoro propoxy-substituted metal phthalocyanine/carbon nano tube compound material;
Wherein the metal-salt described in step 1 is cupric chloride, iron protochloride, cobalt chloride, nickelous chloride, zinc chloride, Palladous chloride, lead chloride or Manganous chloride tetrahydrate;
Tetrafluoro propoxy-phthalic nitrile described in step 1 is 4-(2,2,3,3-tetrafluoro propoxy-) phthalic nitrile, 3-(2,2,3,3-tetrafluoro propoxy-) phthalic nitrile or 4,5-bis-(2,2,3,3-tetrafluoro propoxy-) phthalic nitrile;
Carboxylic carbon nano-tube described in step 1 is carboxylated Single Walled Carbon Nanotube or carboxylated multi-walled carbon nano-tubes.
In present embodiment, tetrafluoro propoxy-phthalic nitrile is 4-(2,2,3,3-tetrafluoro propoxy-) phthalic nitrile, 3-(2,2,3,3-tetrafluoro propoxy-) phthalic nitrile or 4,5-bis-(2,2,3,3-tetrafluoro propoxy-) phthalic nitrile, their synthetic method reference literature Eur.J.Inorg.Chem.2010,1220 – 1230 are synthetic.
In present embodiment, other raw materials and reagent are business purchase.
Embodiment two: what present embodiment was different from embodiment one is, in step 1 according to weight percent take 4.045% tetrafluoro propoxy-phthalic nitrile, 2.2% metal-salt, 0.355% carboxylic carbon nano-tube, 7.735% 1,8-diazabicylo [5.4.0] 11 carbon-7-alkene and 85.665% dehydrated alcohol.Other step and parameter are identical with embodiment one.
Embodiment three: present embodiment is different from embodiment one or two, the reactor described in step 1 is stainless steel lined tetrafluoroethylene reactor.Other step and parameter are identical with embodiment one or two.
Embodiment four: present embodiment is different from one of embodiment one to three, after stirring evenly in step 2 at 140 ℃ solvent thermal reaction 5h, be then cooled to 30 ℃.Other step and parameter are identical with one of embodiment one to three.
Adopt following examples to verify beneficial effect of the present invention:
Embodiment 1:
A preparation method for tetrafluoro propoxy-substituted metal phthalocyanine/carbon nano tube compound material, realizes according to the following steps:
One, take 4.04% 4-(2 according to weight percent, 2,3,3-tetrafluoro propoxy-) phthalic nitrile, 2.31% cupric chloride, 0.36% carboxylated multi-walled carbon nano-tubes, 7.73% 1,8-diazabicylo [5.4.0] 11 carbon-7-alkene and 85.56% dehydrated alcohol;
Two, by the 4-taking in step 1 (2, 2, 3, 3-tetrafluoro propoxy-) phthalic nitrile, dehydrated alcohol, cupric chloride, carboxylated multi-walled carbon nano-tubes and 1, 8-diazabicylo [5.4.0] 11 carbon-7-alkene joins in reactor successively, after stirring evenly at 150 ℃ solvent thermal reaction 4h, then be cooled to 25 ℃, after centrifugal, gained precipitation is washed with acetone successively, mass concentration is 3% salt pickling and washing, dry, complete the preparation of tetrafluoro propoxy-substituted metal phthalocyanine/carbon nano tube compound material, obtain 2, 9, 16, 23-tetra-tetrafluoro propoxy-copper phthalocyanine/carbon nano tube compound materials.
Reactor described in the present embodiment step 1 is stainless steel lined tetrafluoroethylene reactor.
In the present embodiment, prepare gained 2,9,16,23-tetra-tetrafluoro propoxy-copper phthalocyanine/carbon nano tube compound materials, its scanning electronic microscope (SEM) is schemed as shown in Figure 1.Its productive rate is: 99%, dispersible in common solvent, as water, ethanol, methyl alcohol, acetone, tetrahydrofuran (THF), DMF.
In the present embodiment, prepare gained 2,9,16, the x-ray photoelectron power spectrum (XPS) of 23-tetra-tetrafluoro propoxy-copper phthalocyanine/carbon nano tube compound materials is schemed as shown in Figures 2 and 3:
Electronic absorption spectroscopy (UV-Vis) (etoh solvent): λ
max(nm) (absorbance A)=671 (0.851).
The charateristic avsorption band of infrared spectra is: 3441,1634,1391,1195cm
-1.
X-ray photoelectron power spectrum (XPS) characteristic peak data: 286.44ev (C
1s), 401.80ev (N
1s), 535.30ev (O
1s), 687.70ev (F
1s), 955.20ev (Cu
2p1/2), 934.70ev (Cu
2p3/2).
The sample of 1.0mg (preparing gained 2,9,16 in embodiment 1,23-tetra-tetrafluoro propoxy-copper phthalocyanine/carbon nano tube compound materials) is scattered in the dehydrated alcohol of 2.0mL, is mixed with the dispersion liquid of 0.5mg/mL.Draw 10 μ L dispersion liquids with microsyringe, be added drop-wise to interdigital electrode (refer to that spacing is 50 μ m, 30 pairs interdigital) upper, after seasoning, obtain surface uniform, constitutionally stable composite material film.This film has response (50ppm faster to ammonia at 25 ℃, be less than 40 seconds) recovery (50ppm, be less than 500 seconds) speed, good reversibility and stability and low detectability (100ppb), can be used as the sensitive material that toxic and harmful detects.
Embodiment 2:
A preparation method for tetrafluoro propoxy-substituted metal phthalocyanine/carbon nano tube compound material, realizes according to the following steps:
One, take 4.04% 4-(2 according to weight percent, 2,3,3-tetrafluoro propoxy-) phthalic nitrile, 2.31% cupric chloride, 0.36% carboxylated multi-walled carbon nano-tubes, 7.73% 1,8-diazabicylo [5.4.0] 11 carbon-7-alkene and 85.56% dehydrated alcohol;
Two, by the 4-taking in step 1 (2, 2, 3, 3-tetrafluoro propoxy-) phthalic nitrile, dehydrated alcohol, cupric chloride, carboxylated multi-walled carbon nano-tubes and 1, 8-diazabicylo [5.4.0] 11 carbon-7-alkene joins in reactor successively, after stirring evenly at 160 ℃ solvent thermal reaction 6h, then be cooled to 28 ℃, after centrifugal, gained precipitation is washed with acetone successively, mass concentration is 3% salt pickling and washing, dry, complete the preparation of tetrafluoro propoxy-substituted metal phthalocyanine/carbon nano tube compound material, obtain 2, 9, 16, 23-tetra-tetrafluoro propoxy-copper phthalocyanine/carbon nano tube compound materials.
Reactor described in the present embodiment step 1 is stainless steel lined tetrafluoroethylene reactor.
In the present embodiment, prepare gained 2,9,16,23-tetra-tetrafluoro propoxy-copper phthalocyanine/carbon nano tube compound materials, its productive rate is: 99%, dispersible in common solvent, as water, ethanol, methyl alcohol, acetone, tetrahydrofuran (THF), DMF.
Electronic absorption spectroscopy (UV-Vis) (solvent is ethanol): λ
max(nm) (absorbance A)=671 (0.840).
The charateristic avsorption band of infrared spectra is: 3439,1630,1380,1193cm
-1.
X-ray photoelectron power spectrum (XPS) characteristic peak data: 286.34ev (C
1s), 401.70ev (N
1s), 535.20ev (O
1s), 686.70ev (F
1s), 953.20ev (Cu
2p1/2), 936.67ev (Cu
2p3/2).
Embodiment 3:
A preparation method for tetrafluoro propoxy-substituted metal phthalocyanine/carbon nano tube compound material, realizes according to the following steps:
One, take 4.04% 3-(2 according to weight percent, 2,3,3-tetrafluoro propoxy-) phthalic nitrile, 2.17%～2.31% cupric chloride, 0.36% carboxylated multi-walled carbon nano-tubes, 7.73% 1,8-diazabicylo [5.4.0] 11 carbon-7-alkene and 85.56% dehydrated alcohol;
Two, by the 3-taking in step 1 (2, 2, 3, 3-tetrafluoro propoxy-) phthalic nitrile, dehydrated alcohol, cupric chloride, carboxylated multi-walled carbon nano-tubes and 1, 8-diazabicylo [5.4.0] 11 carbon-7-alkene joins in reactor successively, after stirring evenly at 140 ℃ solvent thermal reaction 3h, then be cooled to 28 ℃, after centrifugal, gained precipitation is washed with acetone successively, mass concentration is 3% salt pickling and washing, dry, complete the preparation of tetrafluoro propoxy-substituted metal phthalocyanine/carbon nano tube compound material, obtain 1, 8, 15, 22-tetra-tetrafluoro propoxy-copper phthalocyanine/carbon nano tube compound materials.
Reactor described in the present embodiment step 1 is stainless steel lined tetrafluoroethylene reactor.
In the present embodiment, prepare gained 1,8,15,22-tetra-tetrafluoro propoxy-copper phthalocyanine/carbon nano tube compound materials, its productive rate is: 98%, dispersible in common solvent, as water, ethanol, methyl alcohol, acetone, tetrahydrofuran (THF), DMF.
Electronic absorption spectroscopy (UV-Vis) (solvent is ethanol): λ
max(nm) (absorbance A)=669 (0.859).
The charateristic avsorption band of infrared spectra is: 3450,1630,1390,1135cm
-1.
X-ray photoelectron power spectrum (XPS) characteristic peak data: 285.44ev (C
1s), 400.80ev (N
1s), 534.30ev (O
1s), 685.70ev (F
1s), 950.20ev (Cu
2p1/2), 937.65ev (Cu
2p3/2).
Embodiment 4:
A preparation method for tetrafluoro propoxy-substituted metal phthalocyanine/carbon nano tube compound material, realizes according to the following steps:
One, take 4.05% 4-(2 according to weight percent, 2,3,3-tetrafluoro propoxy-) phthalic nitrile, 2.17% iron protochloride, 0.36% carboxylated multi-walled carbon nano-tubes, 7.74% 1,8-diazabicylo [5.4.0] 11 carbon-7-alkene and 85.68% dehydrated alcohol;
Two, by the 4-taking in step 1 (2, 2, 3, 3-tetrafluoro propoxy-) phthalic nitrile, dehydrated alcohol, iron protochloride, carboxylated multi-walled carbon nano-tubes and 1, 8-diazabicylo [5.4.0] 11 carbon-7-alkene joins in reactor successively, after stirring evenly at 140 ℃ solvent thermal reaction 4h, then be cooled to 28 ℃, after centrifugal or filtration, gained precipitation is washed with acetone successively, mass concentration is 3% salt pickling and washing, dry, complete the preparation of tetrafluoro propoxy-substituted metal phthalocyanine/carbon nano tube compound material, obtain 2, 9, 16, 23-tetra-tetrafluoro propoxy-iron-phthalocyanine/carbon nano tube compound materials.
Reactor described in the present embodiment step 1 is stainless steel lined tetrafluoroethylene reactor.
In the present embodiment, prepare gained 2,9,16,23-tetra-tetrafluoro propoxy-iron-phthalocyanine/carbon nano tube compound materials, its productive rate is: 98%, dispersible in common solvent, as water, ethanol, methyl alcohol, acetone, tetrahydrofuran (THF), DMF.
Electronic absorption spectroscopy (UV-Vis) (solvent is ethanol): λ
max(nm) (absorbance A)=642 (0.950).
The charateristic avsorption band of infrared spectra is: 3460,1627,1370,1151cm
-1.
X-ray photoelectron power spectrum (XPS) characteristic peak data: 287.44ev (C
1s), 401.60ev (N
1s), 534.30ev (O
1s), 684.30ev (F
1s), 718.20ev (Fe
2p1/2), 705.20ev (Fe
2p3/2).
Embodiment 5:
A preparation method for tetrafluoro propoxy-substituted metal phthalocyanine/carbon nano tube compound material, realizes according to the following steps:
One, take 4.05% 4-(2 according to weight percent, 2,3,3-tetrafluoro propoxy-) phthalic nitrile, 2.24% cobalt chloride, 0.36% carboxylated multi-walled carbon nano-tubes, 7.73% 1,8-diazabicylo [5.4.0] 11 carbon-7-alkene and 85.62% dehydrated alcohol;
Two, by the 4-taking in step 1 (2, 2, 3, 3-tetrafluoro propoxy-) phthalic nitrile, dehydrated alcohol, cobalt chloride, carboxylated multi-walled carbon nano-tubes and 1, 8-diazabicylo [5.4.0] 11 carbon-7-alkene joins in reactor successively, after stirring evenly at 150 ℃ solvent thermal reaction 3h, then be cooled to 20 ℃, after centrifugal, gained precipitation is washed with acetone successively, mass concentration is 3% salt pickling and washing, dry, complete the preparation of tetrafluoro propoxy-substituted metal phthalocyanine/carbon nano tube compound material, obtain 2, 9, 16, 23-tetra-tetrafluoro propoxy-cobalt phthalocyanine/carbon nano tube compound materials.
Reactor described in the present embodiment step 1 is stainless steel lined tetrafluoroethylene reactor.
In the present embodiment, prepare gained 2,9,16,23-tetra-tetrafluoro propoxy-cobalt phthalocyanine/carbon nano tube compound materials, its productive rate is: 99%, dispersible in common solvent, as water, ethanol, methyl alcohol, acetone, tetrahydrofuran (THF), DMF; Fig. 4 is shown in by the picture being wherein scattered in 5 kinds of different solvents (concentration is 0.1mg/mL): A solvent is water; B solvent is methyl alcohol; C solvent is ethanol; D solvent is acetone; E solvent is DMF.
Electronic absorption spectroscopy (UV-Vis) (solvent is ethanol): λ
max(nm) (absorbance A)=673 (0.976), 606 (0.718).
The charateristic avsorption band of infrared spectra is: 3458,1622,1383,1131cm
-1.
X-ray photoelectron power spectrum (XPS) characteristic peak data: 286.64ev (C
1s), 401.70ev (N
1s), 536.30ev (O
1s), 685.90ev (F
1s), 770.40ev (Co
2p1/2), 789.20ev (Co
2p3/2).
In the present embodiment, prepare gained 2,9,16,23-tetra-tetrafluoro propoxy-cobalt phthalocyanine/carbon nano tube compound materials, it is scattered in 5 kinds of different solvents (concentration is 0.1mg/mL), as shown in Figure 4, it all has good solvent dispersion and permanent stability (not assembling) to standing figure after 2 months in 5 kinds of common solvents as seen.As shown in Figure 5, it has had the charateristic avsorption band of 2,9,16,23-, tetra-tetrafluoro propoxy-cobalt phthalocyanines and carboxylated multi-walled carbon nano-tubes simultaneously as seen, illustrates that it is successfully prepared for its uv-visible absorption spectra figure in ethanol.Its thermogravimetric-differential thermogravimetric (TG-DTG) under nitrogen atmosphere is schemed as shown in Figure 6, and it has high thermostability as seen.It responds restorability figure as shown in Figure 7 for the gas sensitization of different concns ammonia, and it shows good gas sensitization performance to ammonia as seen.
Embodiment 6:
A preparation method for tetrafluoro propoxy-substituted metal phthalocyanine/carbon nano tube compound material, realizes according to the following steps:
One, take 4.04% 4-(2 according to weight percent, 2,3,3-tetrafluoro propoxy-) phthalic nitrile, 2.31% zinc chloride, 0.36% carboxylated multi-walled carbon nano-tubes, 7.73% 1,8-diazabicylo [5.4.0] 11 carbon-7-alkene and 85.56% dehydrated alcohol;
Two, by the 4-taking in step 1 (2, 2, 3, 3-tetrafluoro propoxy-) phthalic nitrile, dehydrated alcohol, zinc chloride, carboxylated multi-walled carbon nano-tubes and 1, 8-diazabicylo [5.4.0] 11 carbon-7-alkene joins in reactor successively, after stirring evenly at 150 ℃ solvent thermal reaction 6h, then be cooled to 28 ℃, after centrifugal or filtration, gained precipitation is washed with acetone successively, mass concentration is 3% salt pickling and washing, dry, complete the preparation of tetrafluoro propoxy-substituted metal phthalocyanine/carbon nano tube compound material, obtain 2, 9, 16, 23-tetra-tetrafluoro propoxy-ZnPc/carbon nano tube compound materials.
Reactor described in the present embodiment step 1 is stainless steel lined tetrafluoroethylene reactor.
In the present embodiment, prepare gained 2,9,16,23-tetra-tetrafluoro propoxy-ZnPc/carbon nano tube compound materials, its productive rate is: 97%, dispersible in common solvent, as water, ethanol, methyl alcohol, acetone, tetrahydrofuran (THF), DMF.
Electronic absorption spectroscopy (UV-Vis) (solvent is ethanol): λ
max(nm) (absorbance A)=661 (0.830).
The charateristic avsorption band of infrared spectra is: 3454,1634,1389,1193cm
-1.
X-ray photoelectron power spectrum (XPS) characteristic peak data: 286.54ev (C
1s), 400.80ev (N
1s), 534.30ev (O
1s), 685.50ev (F
1s), 1040.50ev (Zn
2p1/2), 1019.40ev (Zn
2p3/2).
Embodiment 7:
A preparation method for tetrafluoro propoxy-substituted metal phthalocyanine/carbon nano tube compound material, realizes according to the following steps:
One, take 4.05% 4-(2 according to weight percent, 2,3,3-tetrafluoro propoxy-) phthalic nitrile, 2.17% Manganous chloride tetrahydrate, 0.36% carboxylated multi-walled carbon nano-tubes, 7.74% 1,8-diazabicylo [5.4.0] 11 carbon-7-alkene and 85.68% dehydrated alcohol;
Two, by the 4-taking in step 1 (2, 2, 3, 3-tetrafluoro propoxy-) phthalic nitrile, dehydrated alcohol, Manganous chloride tetrahydrate, carboxylated multi-walled carbon nano-tubes and 1, 8-diazabicylo [5.4.0] 11 carbon-7-alkene joins in reactor successively, after stirring evenly at 140 ℃ solvent thermal reaction 4h, then be cooled to 28 ℃, after centrifugal or filtration, gained precipitation is washed with acetone successively, mass concentration is 6% salt pickling and washing, dry, complete the preparation of tetrafluoro propoxy-substituted metal phthalocyanine/carbon nano tube compound material, obtain 2, 9, 16, 23-tetra-tetrafluoro propoxy-manganese phthalocyanine/carbon nano tube compound materials.
Reactor described in the present embodiment step 1 is stainless steel lined tetrafluoroethylene reactor.
In the present embodiment, prepare gained 2,9,16,23-tetra-tetrafluoro propoxy-manganese phthalocyanine/carbon nano tube compound materials, its productive rate is: 98%, dispersible in common solvent, as water, ethanol, methyl alcohol, acetone, tetrahydrofuran (THF), DMF.
Electronic absorption spectroscopy (UV-Vis) (solvent is ethanol): λ
max(nm) (absorbance A)=714 (0.891).
The charateristic avsorption band of infrared spectra is: 3469,1623,1371,1185,1099cm
-1.
X-ray photoelectron power spectrum (XPS) characteristic peak data: 286.34ev (C
1s), 401.70ev (N
1s), 534.30ev (O
1s), 686.60ev (F
1s), 648.12ev (Mn
2p1/2), 636.60ev (Mn
2p3/2).
Embodiment 8:
A preparation method for tetrafluoro propoxy-substituted metal phthalocyanine/carbon nano tube compound material, realizes according to the following steps:
One, take 4.04% 4-(2 according to weight percent, 2,3,3-tetrafluoro propoxy-) phthalic nitrile, 2.31% cupric chloride, 0.36% carboxylated Single Walled Carbon Nanotube, 7.73% 1,8-diazabicylo [5.4.0] 11 carbon-7-alkene and 85.56% dehydrated alcohol;
Two, by the 4-taking in step 1 (2, 2, 3, 3-tetrafluoro propoxy-) phthalic nitrile, dehydrated alcohol, cupric chloride, carboxylated Single Walled Carbon Nanotube and 1, 8-diazabicylo [5.4.0] 11 carbon-7-alkene joins in reactor successively, after stirring evenly at 150 ℃ solvent thermal reaction 4h, then be cooled to 25 ℃, after centrifugal or filtration, gained precipitation is washed with acetone successively, mass concentration is 3% salt pickling and washing, dry, complete the preparation of tetrafluoro propoxy-substituted metal phthalocyanine/carbon nano tube compound material, obtain 2, 9, 16, 23-tetra-tetrafluoro propoxy-copper phthalocyanine/carbon nano tube compound materials.
Reactor described in the present embodiment step 1 is stainless steel lined tetrafluoroethylene reactor.
In the present embodiment, prepare gained 2,9,16,23-tetra-tetrafluoro propoxy-copper phthalocyanine/carbon nano tube compound materials, its productive rate is: 99%, dispersible in common solvent, as water, ethanol, methyl alcohol, acetone, tetrahydrofuran (THF), DMF.
Electronic absorption spectroscopy (UV-Vis) (etoh solvent): λ
max(nm) (absorbance A)=670 (0.852).
The charateristic avsorption band of infrared spectra is: 3440,1728,1570,1485,1383,735cm
-1.
X-ray photoelectron power spectrum (XPS) characteristic peak data: 286.54ev (C
1s), 401.70ev (N
1s), 535.50ev (O
1s), 686.70ev (F
1s), 956.20ev (Cu
2p1/2), 935.70ev (Cu
2p3/2).
Claims (4)
1. a preparation method for tetrafluoro propoxy-substituted metal phthalocyanine/carbon nano tube compound material, is characterized in that it realizes according to the following steps:
One, according to weight percent take 4.04%～4.05% tetrafluoro propoxy-phthalic nitrile, 2.17%～2.31% metal-salt, 0.35%～0.36% carboxylic carbon nano-tube, 7.73%～7.74% 1,8-diazabicylo [5.4.0] 11 carbon-7-alkene and 85.56%～85.68% dehydrated alcohol;
Two, by the tetrafluoro propoxy-phthalic nitrile, dehydrated alcohol, metal-salt, the carboxylic carbon nano-tube and 1 that take in step 1,8-diazabicylo [5.4.0] 11 carbon-7-alkene joins in reactor successively, after stirring evenly at 100～160 ℃ solvent thermal reaction 1～10h, then be cooled to 10～50 ℃, after centrifugal or filtration, gained precipitation is successively with acetone is washed, mass concentration is 1%～5% salt pickling and washing, dry, complete the preparation of tetrafluoro propoxy-substituted metal phthalocyanine/carbon nano tube compound material;
Wherein the metal-salt described in step 1 is cupric chloride, iron protochloride, cobalt chloride, nickelous chloride, zinc chloride, Palladous chloride, lead chloride or Manganous chloride tetrahydrate;
Tetrafluoro propoxy-phthalic nitrile described in step 1 is 4-(2,2,3,3-tetrafluoro propoxy-) phthalic nitrile, 3-(2,2,3,3-tetrafluoro propoxy-) phthalic nitrile or 4,5-bis-(2,2,3,3-tetrafluoro propoxy-) phthalic nitrile;
Carboxylic carbon nano-tube described in step 1 is carboxylated Single Walled Carbon Nanotube or carboxylated multi-walled carbon nano-tubes.
2. the preparation method of a kind of tetrafluoro propoxy-substituted metal phthalocyanine/carbon nano tube compound material according to claim 1, it is characterized in that in step 1 according to weight percent take 4.045% tetrafluoro propoxy-phthalic nitrile, 2.2% metal-salt, 0.355% carboxylic carbon nano-tube, 7.735% 1,8-diazabicylo [5.4.0] 11 carbon-7-alkene and 85.665% dehydrated alcohol.
3. the preparation method of a kind of tetrafluoro propoxy-substituted metal phthalocyanine/carbon nano tube compound material according to claim 1 and 2, is characterized in that the reactor described in step 1 is stainless steel lined tetrafluoroethylene reactor.
4. the preparation method of a kind of tetrafluoro propoxy-substituted metal phthalocyanine/carbon nano tube compound material according to claim 3, after it is characterized in that stirring evenly in step 2 at 140 ℃ solvent thermal reaction 5h, be then cooled to 30 ℃.
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| CN104959166A (en) * | 2015-07-06 | 2015-10-07 | 常州大学 | In-situ preparation method of zinc phthalocyanine/carbon nanotube composite catalyst based on solvothermal method |
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