CN105646503A - Preparation method of zinc phthalocyanine hollow balls - Google Patents
Preparation method of zinc phthalocyanine hollow balls Download PDFInfo
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- CN105646503A CN105646503A CN201610024796.3A CN201610024796A CN105646503A CN 105646503 A CN105646503 A CN 105646503A CN 201610024796 A CN201610024796 A CN 201610024796A CN 105646503 A CN105646503 A CN 105646503A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
Abstract
The invention discloses a preparation method of zinc phthalocyanine hollow balls, and belongs to the technical field of metal phthalocyanine. Preparation is achieved with 4-nitrophthalonitrile and zinc salt as the raw materials and ammonium molybdate as the catalyst. The preparation method includes the following steps of firstly, mixing polyethylene glycol with distilled water, and stirring and dissolving the mixture at 60 DEG C to obtain mixed solvent; secondly, adding 4-nitrophthalonitrile, zinc salt and ammonium molybdate to mixed solvent to be stirred magnetically for 30-40 minutes to obtain a mixed solution, dripping the mixed solution to a catechol water solution to be stirred for 2-4 minutes, and transferring the mixed solution to a reaction still to be sealed; thirdly, putting the reaction still in a constant-temperature oven at 160-180 DEG C to be heated for 8-10 hours, taking out the reaction still to be cooled to a room temperature, opening the still to take out reactant at the bottom of the still, and conducting washing and drying to obtain the zinc phthalocyanine hollow balls. A solvent thermal method is adopted, operation is easy and convenient, long-term processing is not needed, and the reaction time is shortened to 8-10 hours from the existing preparation time of 14-32 hours.
Description
Technical field
The invention belongs to the technical field of metal phthalocyanine complex, relate to the ZnPc of hollow-core construction, the preparation method being specifically related to a kind of ZnPc hollow ball. Method preparation technology provided by the present invention is succinct, is that efficient operation is easy, cheap, be prone to large-scale production for one.
Background technology
Metal phthalocyanine be in a kind of ring hole can hold that diameter with it matches such as the macrocyclic complex of many transition metal such as ferrum, cobalt, nickel, phthalocyanine ring itself is the big two-dimentional conjugated system with 18 pi-electrons, as a kind of macrocyclic complex, the reaction of its metal ion also determines the coordination catalysis ability that it is excellent, and the catalytic action of metal phthalocyanine complex largely ranges coordination catalysis effect.
The synthetic route of symmetric metal phthalocyanine includes phthalonitrile route, benzene bitter wine-urea route, adjacent itrile group Benzoylamide route, 1,3-di-imidogen iso-indoles route, phthalocyanine and phthalocyanine complex transformation routes. From synthetic method, it is divided into again solid-phase synthesis, DBU liquid phase method and microwave assisting method. Can by raw material 4-nitrophthalonitrile, p-aminophenol, P-hydroxybenzoic acid, oxine, benzaldehyde, hydroxy benzaldehyde and zinc chloride etc. 1,8-diazacyclo [5,4,0] synthesized under the catalysis of hendecene-7 (DBU) containing the big six kinds of new zinc phthalocyanines of class of aryloxy group and Schiff's base group two. But the preparation of hollow ZnPc is required further study.
Summary of the invention
The present invention solves defect of the prior art, it is provided that the preparation method of a kind of ZnPc hollow ball.
The present invention the technical scheme is that for realizing its purpose
A kind of preparation method of ZnPc hollow ball, with 4-nitro phthalic nitrile and zinc salt for raw material, ammonium molybdate is that catalyst is prepared, and comprises the following steps:
(1) being mixed with distilled water by Polyethylene Glycol, at 60 DEG C, stirring is to dissolving, and obtains mixed solvent;
(2) under room temperature, 4-nitro phthalic nitrile, zinc chloride and ammonium molybdate are joined in above-mentioned mixed solvent, magnetic agitation 30-40min, obtain mixed liquor, then in mixed liquor, instill catechol aqueous solution, after stirring 2-4min, mixed liquor is transferred in reactor, seal, the 78-82% that amount is reactor volume of mixed liquor;
(3) reactor is placed in the constant temperature oven of 160-180 DEG C and heats 8-10h, take out reactor afterwards, be cooled to room temperature, drive still and take out bottom reactant, washing, dry, obtain ZnPc hollow ball.
The mol ratio of 4-nitro phthalic nitrile and zinc chloride is (3-5): 1.
The mass ratio of zinc chloride and ammonium molybdate is (5.7-6.2): 1.
The weight ratio of Polyethylene Glycol and distilled water is 1 �� 10-4: (2.8-3.2).
The concentration of described catechol aqueous solution is 0.01mol/L.
The hydrochloric acid solution adopting 1mol/L during washing cleans once, then uses ethanol purge twice again, finally cleans 2 times with distilled water again.
Drying described in step (3), is dry in the baking oven of 50-70 DEG C.
The invention has the beneficial effects as follows:
The present invention adopts solvent thermal process, easy and simple to handle, it is not necessary to long time treatment, and the response time is shortened to 8-10 hour in 14-32 hour by existing preparation time; And dicyandiamide solution changes Aqueous Solutions of Polyethylene Glycol into, the reunion of ZnPc can be reduced, additionally the addition of catechol, it is possible to achieve the slow releasing in zinc source, the volume ratio forming unique ZnPc hollow ball, catechol and distilled water is 0.1:(2.8-3.2). Solving the response time in prior art long, preparation process is loaded down with trivial details, and by-product is more not to be easily purified, and uses more toxic and volatile medicine in reagent, the defects such as product is random and not easily repeats.
By ZnPc soilless sticking phenomenon prepared by the inventive method, hollow ball has inside and outside bilayer, therefore has higher specific surface area, and existing ZnPc mostly is random graininess, and it is more serious to reunite, and greatly reduces the effective ratio area of ZnPc.
ZnPc hollow ball prepared by the present invention can be used for light catalytic purifying sewage disposal and electrode material for super capacitor aspect, the utilization rate to sunlight can be increased for the former, increase the contact area of polluter in photocatalyst and sewage simultaneously, pollutant in effective degradation of sewage, improve photocatalysis efficiency; It is applied to the latter and can realize the contact area of electrode material and electrolyte, accelerate electrolytical transmission, improve the electric property of material.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of ZnPc hollow ball of the present invention.
Fig. 2 is the magnified sweep Electronic Speculum figure of ZnPc hollow ball of the present invention.
Fig. 3 is the XRD figure of ZnPc hollow ball of the present invention
Fig. 4 is the uv absorption spectra of ZnPc hollow ball of the present invention.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further illustrated.
Embodiment 1
0.5mg Polyethylene Glycol (PEG, molecular weight 4000) join in 15ml distilled water, 60 degrees Celsius of stirrings are to dissolving, under room temperature, by the 4-nitro phthalic nitrile of 0.9mmol, the zinc chloride of 0.21mmol, the ammonium molybdate of 5.0mg once joins in above-mentioned solution, mixed solution stirs half an hour when magnetic agitation, after stirring, instills 0.5ml, 0.01mmolL-1Catechol aqueous solution stirs 2 minutes, is proceeded in polytetrafluoroethylkettle kettle core by mixed liquor afterwards. Reactor is sealed and placed in the constant temperature oven of 160 DEG C to heat, take out, be naturally cooling to room temperature after 8 hours. Driving still and take out reactor substrate, obtained bluish violet material uses 1MHCl solution, distilled water respectively, and ethanol is carried out, and is finally put in 60 DEG C of baking ovens and dries, namely obtains the ZnPc hollow ball material of uniform particle diameter, and productivity reaches 97%.
Embodiment 2
0.5mg Polyethylene Glycol (PEG, molecular weight 4000) join in 14ml distilled water, 60 DEG C of stirrings are to dissolving, under room temperature, by the 4-nitro phthalic nitrile of 0.8mmol, the zinc chloride of 0.26mmol, the ammonium molybdate of 6.17mg once joins in above-mentioned solution, mixed solution stirs half an hour when magnetic agitation, after stirring, instills 0.5ml, 0.01mmolL-1Catechol aqueous solution stirs 2 minutes, is proceeded in polytetrafluoroethylkettle kettle core by mixed liquor afterwards.Reactor is sealed and placed in the constant temperature oven of 170 DEG C to heat, take out, be naturally cooling to room temperature after 9 hours. Driving still and take out reactor substrate, obtained bluish violet material uses 1MHCl solution, distilled water respectively, and ethanol is carried out, and is finally put in 50 DEG C of baking ovens and dries, namely obtains the ZnPc hollow ball material of uniform particle diameter, and productivity reaches 96.5%.
Embodiment 3
0.5mg Polyethylene Glycol (PEG, molecular weight 4000) join in 16ml distilled water, 60 DEG C of stirrings are to dissolving, under room temperature, by the 4-nitro phthalic nitrile of 0.8mmol, the zinc chloride of 0.16mmol, the ammonium molybdate of 3.53mg once joins in above-mentioned solution, mixed solution stirs half an hour when magnetic agitation, after stirring, instills 0.5ml, 0.01mmolL-1Catechol aqueous solution stirs 2 minutes, is proceeded in polytetrafluoroethylkettle kettle core by mixed liquor afterwards. Reactor is sealed and placed in the constant temperature oven of 180 DEG C to heat, take out, be naturally cooling to room temperature after 10 hours. Driving still and take out reactor substrate, obtained bluish violet material uses 1MHCl solution, distilled water respectively, and ethanol is carried out, and is finally put in 55 DEG C of baking ovens and dries, namely obtains the ZnPc hollow ball material of uniform particle diameter, and productivity reaches 96.8%.
Embodiment 4
0.5mg Polyethylene Glycol (PEG, molecular weight 4000) join in 14.5ml distilled water, 60 DEG C of stirrings are to dissolving, under room temperature, by the 4-nitro phthalic nitrile of 0.8mmol, the zinc chloride of 0.217mmol, the ammonium molybdate of 4.94mg once joins in above-mentioned solution, mixed solution stirs half an hour when magnetic agitation, after stirring, instills 0.5ml, 0.01mmolL-1Catechol aqueous solution stirs 2 minutes, is proceeded in polytetrafluoroethylkettle kettle core by mixed liquor afterwards. Reactor is sealed and placed in the constant temperature oven of 175 DEG C to heat, take out, be naturally cooling to room temperature after 9.5 hours. Driving still and take out reactor substrate, obtained bluish violet material uses 1MHCl solution, distilled water respectively, and ethanol is carried out, and is finally put in 60 DEG C of baking ovens and dries, namely obtains the ZnPc hollow ball material of uniform particle diameter, and productivity reaches 97.2%.
Embodiment 5
0.5mg Polyethylene Glycol (PEG, molecular weight 4000) join in 15.5ml distilled water, 60 DEG C of stirrings are to dissolving, under room temperature, by the 4-nitro phthalic nitrile of 0.8mmol, the zinc chloride of 0.168mmol, the ammonium molybdate of 3.77mg once joins in above-mentioned solution, mixed solution stirs half an hour when magnetic agitation, after stirring, instills 0.5ml, 0.01mmolL-1Catechol aqueous solution stirs 2 minutes, is proceeded in polytetrafluoroethylkettle kettle core by mixed liquor afterwards. Reactor is sealed and placed in the constant temperature oven of 170 DEG C to heat, take out, be naturally cooling to room temperature after 8.5 hours. Driving still and take out reactor substrate, obtained bluish violet material uses 1MHCl solution, distilled water respectively, and ethanol is carried out, and is finally put in 65 DEG C of baking ovens and dries, namely obtains the ZnPc hollow ball material of uniform particle diameter, and productivity reaches 97.5%.
Embodiment 6
0.5mg Polyethylene Glycol (PEG, molecular weight 4000) join in 15.8ml distilled water, 60 DEG C of stirrings are to dissolving, under room temperature, by the 4-nitro phthalic nitrile of 0.8mmol, the zinc chloride of 0.19mmol, the ammonium molybdate of 4.33mg once joins in above-mentioned solution, mixed solution stirs half an hour when magnetic agitation, after stirring, instills 0.5ml, 0.01mmolL-1Catechol aqueous solution stirs 2 minutes, is proceeded in polytetrafluoroethylkettle kettle core by mixed liquor afterwards.Reactor is sealed and placed in the constant temperature oven of 170 DEG C to heat, take out, be naturally cooling to room temperature after 9 hours. Driving still and take out reactor substrate, obtained bluish violet material uses 1MHCl solution, distilled water respectively, and ethanol is carried out, and is finally put in 60 DEG C of baking ovens and dries, namely obtains the ZnPc hollow ball material of uniform particle diameter, and productivity reaches 97.9%.
Embodiment 7
0.5mg Polyethylene Glycol (PEG, molecular weight 4000) join in 14ml distilled water, 60 DEG C of stirrings are to dissolving, under room temperature, by the 4-nitro phthalic nitrile of 0.8mmol, the zinc chloride of 0.226mmol, the ammonium molybdate of 5.14mg once joins in above-mentioned solution, mixed solution stirs half an hour when magnetic agitation, after stirring, instills 0.5ml, 0.01mmolL-1Catechol aqueous solution stirs 2 minutes, is proceeded in polytetrafluoroethylkettle kettle core by mixed liquor afterwards. Reactor is sealed and placed in the constant temperature oven of 172 DEG C to heat, take out, be naturally cooling to room temperature after 9 hours. Driving still and take out reactor substrate, obtained bluish violet material uses 1MHCl solution, distilled water respectively, and ethanol is carried out, and is finally put in 58 DEG C of baking ovens and dries, namely obtains the ZnPc hollow ball material of uniform particle diameter, and productivity reaches 96.5%.
Embodiment 8
0.5mg Polyethylene Glycol (PEG, molecular weight 4000) join in 15ml distilled water, 60 DEG C of stirrings are to dissolving, under room temperature, by the 4-nitro phthalic nitrile of 0.8mmol, the zinc chloride of 0.191mmol, the ammonium molybdate of 4.41mg once joins in above-mentioned solution, mixed solution stirs half an hour when magnetic agitation, after stirring, instills 0.5ml, 0.01mmolL-1Catechol aqueous solution stirs 2 minutes, is proceeded in polytetrafluoroethylkettle kettle core by mixed liquor afterwards. Reactor is sealed and placed in the constant temperature oven of 170 DEG C to heat, take out, be naturally cooling to room temperature after 8.5 hours. Driving still and take out reactor substrate, obtained bluish violet material uses 1MHCl solution, distilled water respectively, and ethanol is carried out, and is finally put in 63 DEG C of baking ovens and dries, namely obtains the ZnPc hollow ball material of uniform particle diameter, and productivity reaches 96.8%.
Embodiment 9
0.5mg Polyethylene Glycol (PEG, molecular weight 4000) join in 15ml distilled water, 60 DEG C of stirrings are to dissolving, under room temperature, by the 4-nitro phthalic nitrile of 0.8mmol, the zinc chloride of 0.162mmol, the ammonium molybdate of 3.68mg once joins in above-mentioned solution, mixed solution stirs half an hour when magnetic agitation, after stirring, instills 0.5ml, 0.01mmolL-1Catechol aqueous solution stirs 2 minutes, is proceeded in polytetrafluoroethylkettle kettle core by mixed liquor afterwards. Reactor is sealed and placed in the constant temperature oven of 178 DEG C to heat, take out, be naturally cooling to room temperature after 9.6 hours. Driving still and take out reactor substrate, obtained bluish violet material uses 1MHCl solution, distilled water respectively, and ethanol is carried out, and is finally put in 63 DEG C of baking ovens and dries, namely obtains the ZnPc hollow ball material of uniform particle diameter, and productivity reaches 97.3%.
Embodiment 10
0.5mg Polyethylene Glycol (PEG, molecular weight 4000) join in 15ml distilled water, 60 DEG C of stirrings are to dissolving, under room temperature, by the 4-nitro phthalic nitrile of 0.8mmol, the zinc chloride of 0.196mmol, the ammonium molybdate of 4.44mg once joins in above-mentioned solution, mixed solution stirs half an hour when magnetic agitation, after stirring, instills 0.5ml, 0.01mmolL-1Catechol aqueous solution stirs 2 minutes, is proceeded in polytetrafluoroethylkettle kettle core by mixed liquor afterwards.Reactor is sealed and placed in the constant temperature oven of 175 DEG C to heat, take out, be naturally cooling to room temperature after 9 hours. Driving still and take out reactor substrate, obtained bluish violet material uses 1MHCl solution, distilled water respectively, and ethanol is carried out, and is finally put in 65 DEG C of baking ovens and dries, namely obtains the ZnPc hollow ball material of uniform particle diameter, and productivity reaches 96.8%.
The above-mentioned ZnPc hollow ball prepared by this method is scanned Electronic Speculum test, and result as shown in Figure 1-2, is as can be seen from Figure 1 spherical by the ZnPc obtained by the method, spheroid soilless sticking phenomenon, and can be seen that spheroid seems to be hollow-core construction; As can be seen from Figure 2 obtained ZnPc spheroid is hollow-core construction, and sphere size is about for 4-6 micron, and therefore this material can improve the effective rate of utilization of ZnPc surface area.
The above-mentioned ZnPc hollow ball prepared by this method is carried out X-ray diffraction test, the phase purity of sample is obtained for inspection institute, result is as shown in Figure 3, the XRD figure that Fig. 3 is obtained and standard card JCPDS21-1985 contrast, result display sample obtained by the present invention is ��-ZnPc, and not finding other dephasign diffraction maximum, this just describes products therefrom well is pure ��-ZnPc crystal formation.
The above-mentioned ZnPc hollow ball prepared by this method is carried out uv absorption experiment, result is as shown in Figure 4, as can be seen from Figure 4, there are two main absorption bands, one is positioned at 550-750nm, and another is positioned at 300-450nm, is belonging respectively to Q band characteristic absorption and the B band characteristic absorption of ZnPc, 669 and 604nm place, this should be attributed to Pc-2Ring is by the transformation of ��-�� * between HOMO to LUMO monomer, it addition, there is also a 641nm peak clearly between two characteristic peaks of Q band, this is to be caused by the electronic vibration band between single aggressiveness and polymer. This figure illustrates that ZnPc has stronger absorption at visible light wave range, and this makes metal phthalocyanine that visible ray can be utilized as light source degradable organic pollutant, and is widely used in sewage disposal. This feature also compensate for conventional semiconductors metal oxide photocatalyst only with the wavelength <ultraviolet light of 400 nanometers, and for the deficiency that the wavelength visible ray more than 400nm does not respond to, improve the photocatalyst utilization rate to sunlight.
The existing method preparing ZnPc, such as DBU Liquid preparation methods ZnPc, generally at 140 DEG C, each reactant to be heated to reflux 48 hours, afterwards with dichloromethane extraction, clean with water, remove solvent then through decompression distillation, obtain crude zinc phthalocyanine product, finally also will through column chromatography, the ZnPc productivity nonetheless obtained is only 15%, and the random pattern of product. And each reactant is directly proceeded in polytetrafluoroethylkettle kettle core by the present invention, reactor is sealed and placed in the constant temperature oven of 160 DEG C to heat, reacted through 8 hours, 1MHCl solution, distilled water, ethanol purge can be prepared by ZnPc hollow ball for several times, and productivity is up to 96-98%; Meanwhile, this method adds catechol and Polyethylene Glycol can obtain the ZnPc with special empty spherical structure in reaction system.
Claims (7)
1. a preparation method for ZnPc hollow ball, with 4-nitro phthalic nitrile and zinc salt for raw material, ammonium molybdate is that catalyst is prepared, it is characterised in that comprise the following steps:
(1) being mixed with distilled water by Polyethylene Glycol, at 60 DEG C, stirring is to dissolving, and obtains mixed solvent;
(2) under room temperature, 4-nitro phthalic nitrile, zinc chloride and ammonium molybdate are joined in above-mentioned mixed solvent, magnetic agitation 30-40min, obtain mixed liquor, in mixed liquor, then instill catechol aqueous solution, after stirring 2-4min, mixed liquor is transferred in reactor, seals;
(3) reactor is placed in the constant temperature oven of 160-180 DEG C and heats 8-10h, take out reactor afterwards, be cooled to room temperature, drive still and take out bottom reactant, washing, dry, obtain ZnPc hollow ball.
2. the preparation method of a kind of ZnPc hollow ball according to claim 1, it is characterised in that the mol ratio of 4-nitro phthalic nitrile and zinc chloride is (3-5): 1.
3. the preparation method of a kind of ZnPc hollow ball according to claim 1, it is characterised in that the mass ratio of zinc chloride and ammonium molybdate is (5.7-6.2): 1.
4. the preparation method of a kind of ZnPc hollow ball according to claim 1, it is characterised in that the weight ratio of Polyethylene Glycol and distilled water is 1 �� 10-4: (2.8-3.2).
5. the preparation method of a kind of ZnPc hollow ball according to claim 1, it is characterised in that the concentration of described catechol aqueous solution is 0.01mol/L.
6. the preparation method of a kind of ZnPc hollow ball according to claim 1, it is characterised in that adopt the hydrochloric acid solution of 1mol/L to clean once during washing, then use ethanol purge twice again, finally clean 2 times with distilled water again.
7. the preparation method of a kind of ZnPc hollow ball according to claim 1, it is characterised in that the drying described in step (3), is dry in the baking oven of 50-70 DEG C.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109251728A (en) * | 2018-11-28 | 2019-01-22 | 航天科工武汉磁电有限责任公司 | A kind of absorbing material and preparation method thereof |
| CN114335882A (en) * | 2021-12-09 | 2022-04-12 | 河北工程大学 | Modified PE-based lithium ion battery diaphragm and preparation method thereof |
| CN114335885A (en) * | 2021-12-22 | 2022-04-12 | 河北工程大学 | NiPc/PVDF modified PE diaphragm and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109251728A (en) * | 2018-11-28 | 2019-01-22 | 航天科工武汉磁电有限责任公司 | A kind of absorbing material and preparation method thereof |
| CN109251728B (en) * | 2018-11-28 | 2021-07-13 | 航天科工武汉磁电有限责任公司 | Wave-absorbing material and preparation method thereof |
| CN114335882A (en) * | 2021-12-09 | 2022-04-12 | 河北工程大学 | Modified PE-based lithium ion battery diaphragm and preparation method thereof |
| CN114335882B (en) * | 2021-12-09 | 2024-01-30 | 河北工程大学 | Modified PE-based lithium ion battery diaphragm and preparation method thereof |
| CN114335885A (en) * | 2021-12-22 | 2022-04-12 | 河北工程大学 | NiPc/PVDF modified PE diaphragm and preparation method thereof |
| CN114335885B (en) * | 2021-12-22 | 2024-01-26 | 河北工程大学 | NiPc/PVDF modified PE diaphragm and preparation method thereof |
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