CN105646503B - A kind of preparation method of ZnPc hollow ball - Google Patents
A kind of preparation method of ZnPc hollow ball Download PDFInfo
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- CN105646503B CN105646503B CN201610024796.3A CN201610024796A CN105646503B CN 105646503 B CN105646503 B CN 105646503B CN 201610024796 A CN201610024796 A CN 201610024796A CN 105646503 B CN105646503 B CN 105646503B
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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
A kind of preparation method of ZnPc hollow ball, belong to the technical field of metal phthalocyanine, using 4 nitro phthalic nitriles and zinc salt as raw material, ammonium molybdate is prepared by catalyst, is comprised the following steps：(1) polyethylene glycol is mixed with distilled water, stirring extremely dissolving, obtains mixed solvent at 60 DEG C；(2) at room temperature, 4 nitro phthalic nitriles, zinc chloride and ammonium molybdate are added to above-mentioned in the mixed solvent, the 40min of magnetic agitation 30, mixed liquor is obtained, the catechol aqueous solution is then instilled into mixed liquor, after stirring 2 4min, mixed liquor is transferred in reactor, sealed；(3) reactor is placed in 160 180 DEG C of constant temperature oven and heats 8 10h, take out reactor afterwards, be cooled to room temperature, driven kettle and take out bottom reactant, wash, drying, obtain ZnPc hollow ball.The present invention uses solvent thermal process, and easy to operate, without long time treatment, the reaction time is shorten to 8 10 hours for 14 32 hours by existing preparation time.
Description
Technical field
The invention belongs to the technical field of metal phthalocyanine complex, it is related to the ZnPc of hollow-core construction, and in particular to one
The preparation method of kind ZnPc hollow ball.Method preparation technology provided by the present invention is succinct, is a kind of efficient operation simplicity, valency
Lattice are cheap, are easy to large-scale production.
Background technology
Metal phthalocyanine is many transition gold of such as iron, cobalt, nickel that hole can accommodate that diameter therewith matches in a kind of ring
The macrocyclic complex of category, phthalocyanine ring are the big two-dimentional conjugated system with 18 pi-electrons in itself, as a kind of macrocyclic complex,
The reaction of its metal ion also determines its excellent coordination catalysis ability, and the catalytic action of metal phthalocyanine complex is largely
On range coordination catalysis effect.
The synthetic route of symmetric metal phthalocyanine includes phthalonitrile route, benzene bitter wine-urea route, adjacent itrile group benzamide
Route, 1,3- di-imidogen iso-indoles route, phthalocyanine and phthalocyanine complex transformation routes.From synthetic method, it is divided into again solid
Phase synthesi, DBU liquid phase methods and microwave assisting method.Can be by raw material 4- nitrophthalonitriles, p-aminophenol, para hydroxybenzene first
Acid, 8-hydroxyquinoline, benzaldehyde, parahydroxyben-zaldehyde and zinc chloride etc. are in 1,8- diazacyclos [5,4,0] hendecene -7 (DBU)
Catalysis under synthesized and contain aryloxy group and schiff bases group two major classes, six kinds of new ZnPcs.But to the preparation of hollow ZnPc
Require further study.
The content of the invention
A kind of the defects of present invention is solves in the prior art, there is provided preparation method of ZnPc hollow ball.
The present invention is to realize that the technical scheme that its purpose uses is：
A kind of preparation method of ZnPc hollow ball, using 4- nitros phthalic nitrile and zinc salt as raw material, ammonium molybdate is catalysis
Prepared by agent, comprise the following steps：
(1) polyethylene glycol is mixed with distilled water, stirring extremely dissolving, obtains mixed solvent at 60 DEG C；
(2) at room temperature, 4- nitros phthalic nitrile, zinc chloride and ammonium molybdate are added to above-mentioned in the mixed solvent, magnetic force
30-40min is stirred, obtains mixed liquor, the catechol aqueous solution is then instilled into mixed liquor, after stirring 2-4min, will be mixed
Liquid is transferred in reactor, sealing, and the amount of mixed liquor is the 78-82% of reactor volume；
(3) reactor is placed in 160-180 DEG C of constant temperature oven and heats 8-10h, take out reactor afterwards, be cooled to room
Temperature, drive kettle and take out bottom reactant, wash, drying, obtain ZnPc hollow ball.
The mol ratio of 4- nitros 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 of polyethylene glycol and distilled water ratio is 1 × 10-4：(2.8-3.2).
The concentration of the described catechol aqueous solution is 0.01mol/L.
Cleaned once using 1mol/L hydrochloric acid solution during washing, then cleaned twice with ethanol again, finally again with distillation
Water cleans 2 times.
Drying described in step (3), dried in 50-70 DEG C of baking oven.
The beneficial effects of the invention are as follows：
The present invention uses solvent thermal process, and easy to operate, without long time treatment, the reaction time is by existing preparation time
14-32 hours shorten to 8-10 hours；And dicyandiamide solution is changed to Aqueous Solutions of Polyethylene Glycol, it is possible to reduce the reunion of ZnPc, separately
The addition of outer catechol, it is possible to achieve the slow release in zinc source, form the ZnPc hollow ball of uniqueness, catechol and distillation
The volume ratio of water is 0.1:(2.8-3.2).Solve in the prior art that the reaction time is long, preparation process is cumbersome, accessory substance compared with
It is not easily purified more, uses more toxic and volatile medicine in reagent, product is random and the defects of being not easy to repeat.
The ZnPc soilless sticking phenomenon being prepared by the method for the present invention, hollow ball have inside and outside bilayer, therefore with higher
Specific surface area, and existing ZnPc is mostly random graininess, and it is more serious to reunite, and greatly reduces the effective of ZnPc
Specific surface area.
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 sunshine can be increased for the former, while increase the contact surface of pollution sources in photochemical catalyst and sewage
Pollutant in product, effectively degraded sewage, improves photocatalysis efficiency；Connecing for electrode material and electrolyte can be realized applied to the latter
Contacting surface is accumulated, and is accelerated the transmission of electrolyte, is improved the electric property of material.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of ZnPc hollow ball of the present invention.
Fig. 2 is the magnified sweep electron microscope of ZnPc hollow ball of the present invention.
Fig. 3 is the XRD of ZnPc hollow ball of the present invention
Fig. 4 is the uv absorption spectra of ZnPc hollow ball of the present invention.
Embodiment
With reference to specific embodiment, the present invention is further illustrated.
Embodiment 1
0.5mg polyethylene glycol (PEG, molecular weight 4000) is added in 15ml distilled water, 60 degrees Celsius of stirrings to dissolving, room
Under temperature, by 0.9mmol 4- nitro phthalic nitriles, 0.21mmol zinc chloride, 5.0mg ammonium molybdate is once added to above-mentioned molten
In liquid, mixed solution stirs half an hour under the conditions of magnetic agitation, after stirring, instills 0.5ml, 0.01mmolL-1Adjacent benzene two
The phenol aqueous solution is stirred 2 minutes, and mixed liquor is transferred in polytetrafluoroethylkettle kettle core afterwards.Reactor is sealed and placed in 160 DEG C of perseverance
Heated in warm baking oven, taken out after 8 hours, be naturally cooling to room temperature.Drive kettle and take out reaction bottoms, resulting royal purple color substance
1M HCl solutions, distilled water are used respectively, and ethanol is cleaned, is finally put in 60 DEG C of baking ovens and dries, that is, obtain uniform particle diameter
ZnPc hollow ball material, yield is up to 97%.
Embodiment 2
0.5mg polyethylene glycol (PEG, molecular weight 4000) is added in 14ml distilled water, 60 DEG C of stirrings to dissolving, room temperature
Under, by 0.8mmol 4- nitro phthalic nitriles, 0.26mmol zinc chloride, 6.17mg ammonium molybdate is once added to above-mentioned molten
In liquid, mixed solution stirs half an hour under the conditions of magnetic agitation, after stirring, instills 0.5ml, 0.01mmolL-1Adjacent benzene two
The phenol aqueous solution is stirred 2 minutes, and mixed liquor is transferred in polytetrafluoroethylkettle kettle core afterwards.Reactor is sealed and placed in 170 DEG C of perseverance
Heated in warm baking oven, taken out after 9 hours, be naturally cooling to room temperature.Drive kettle and take out reaction bottoms, resulting royal purple color substance
1M HCl solutions, distilled water are used respectively, and ethanol is cleaned, is finally put in 50 DEG C of baking ovens and dries, that is, obtain uniform particle diameter
ZnPc hollow ball material, yield is up to 96.5%.
Embodiment 3
0.5mg polyethylene glycol (PEG, molecular weight 4000) is added in 16ml distilled water, 60 DEG C of stirrings to dissolving, room temperature
Under, by 0.8mmol 4- nitro phthalic nitriles, 0.16mmol zinc chloride, 3.53mg ammonium molybdate is once added to above-mentioned molten
In liquid, mixed solution stirs half an hour under the conditions of magnetic agitation, after stirring, instills 0.5ml, 0.01mmolL-1Adjacent benzene two
The phenol aqueous solution is stirred 2 minutes, and mixed liquor is transferred in polytetrafluoroethylkettle kettle core afterwards.Reactor is sealed and placed in 180 DEG C of perseverance
Heated in warm baking oven, taken out after 10 hours, be naturally cooling to room temperature.Drive kettle and take out reaction bottoms, resulting bluish violet thing
Matter uses 1M HCl solutions, distilled water respectively, and ethanol is cleaned, is finally put in 55 DEG C of baking ovens and dries, that is, obtain uniform particle diameter
ZnPc hollow ball material, yield is up to 96.8%.
Embodiment 4
0.5mg polyethylene glycol (PEG, molecular weight 4000) is added in 14.5ml distilled water, 60 DEG C of stirrings to dissolving, room temperature
Under, by 0.8mmol 4- nitro phthalic nitriles, 0.217mmol zinc chloride, 4.94mg ammonium molybdate is once added to above-mentioned molten
In liquid, mixed solution stirs half an hour under the conditions of magnetic agitation, after stirring, instills 0.5ml, 0.01mmolL-1Adjacent benzene two
The phenol aqueous solution is stirred 2 minutes, and mixed liquor is transferred in polytetrafluoroethylkettle kettle core afterwards.Reactor is sealed and placed in 175 DEG C of perseverance
Heated in warm baking oven, taken out after 9.5 hours, be naturally cooling to room temperature.Drive kettle and take out reaction bottoms, resulting bluish violet thing
Matter uses 1M HCl solutions, distilled water respectively, and ethanol is cleaned, is finally put in 60 DEG C of baking ovens and dries, that is, obtain uniform particle diameter
ZnPc hollow ball material, yield is up to 97.2%.
Embodiment 5
0.5mg polyethylene glycol (PEG, molecular weight 4000) is added in 15.5ml distilled water, 60 DEG C of stirrings to dissolving, room temperature
Under, by 0.8mmol 4- nitro phthalic nitriles, 0.168mmol zinc chloride, 3.77mg ammonium molybdate is once added to above-mentioned molten
In liquid, mixed solution stirs half an hour under the conditions of magnetic agitation, after stirring, instills 0.5ml, 0.01mmolL-1Adjacent benzene two
The phenol aqueous solution is stirred 2 minutes, and mixed liquor is transferred in polytetrafluoroethylkettle kettle core afterwards.Reactor is sealed and placed in 170 DEG C of perseverance
Heated in warm baking oven, taken out after 8.5 hours, be naturally cooling to room temperature.Drive kettle and take out reaction bottoms, resulting bluish violet thing
Matter uses 1M HCl solutions, distilled water respectively, and ethanol is cleaned, is finally put in 65 DEG C of baking ovens and dries, that is, obtain uniform particle diameter
ZnPc hollow ball material, yield is up to 97.5%.
Embodiment 6
0.5mg polyethylene glycol (PEG, molecular weight 4000) is added in 15.8ml distilled water, 60 DEG C of stirrings to dissolving, room temperature
Under, by 0.8mmol 4- nitro phthalic nitriles, 0.19mmol zinc chloride, 4.33mg ammonium molybdate is once added to above-mentioned molten
In liquid, mixed solution stirs half an hour under the conditions of magnetic agitation, after stirring, instills 0.5ml, 0.01mmolL-1Adjacent benzene two
The phenol aqueous solution is stirred 2 minutes, and mixed liquor is transferred in polytetrafluoroethylkettle kettle core afterwards.Reactor is sealed and placed in 170 DEG C of perseverance
Heated in warm baking oven, taken out after 9 hours, be naturally cooling to room temperature.Drive kettle and take out reaction bottoms, resulting royal purple color substance
1M HCl solutions, distilled water are used respectively, and ethanol is cleaned, is finally put in 60 DEG C of baking ovens and dries, that is, obtain uniform particle diameter
ZnPc hollow ball material, yield is up to 97.9%.
Embodiment 7
0.5mg polyethylene glycol (PEG, molecular weight 4000) is added in 14ml distilled water, 60 DEG C of stirrings to dissolving, room temperature
Under, by 0.8mmol 4- nitro phthalic nitriles, 0.226mmol zinc chloride, 5.14mg ammonium molybdate is once added to above-mentioned molten
In liquid, mixed solution stirs half an hour under the conditions of magnetic agitation, after stirring, instills 0.5ml, 0.01mmolL-1Adjacent benzene two
The phenol aqueous solution is stirred 2 minutes, and mixed liquor is transferred in polytetrafluoroethylkettle kettle core afterwards.Reactor is sealed and placed in 172 DEG C of perseverance
Heated in warm baking oven, taken out after 9 hours, be naturally cooling to room temperature.Drive kettle and take out reaction bottoms, resulting royal purple color substance
1M HCl solutions, distilled water are used respectively, and ethanol is cleaned, is finally put in 58 DEG C of baking ovens and dries, that is, obtain uniform particle diameter
ZnPc hollow ball material, yield is up to 96.5%.
Embodiment 8
0.5mg polyethylene glycol (PEG, molecular weight 4000) is added in 15ml distilled water, 60 DEG C of stirrings to dissolving, room temperature
Under, by 0.8mmol 4- nitro phthalic nitriles, 0.191mmol zinc chloride, 4.41mg ammonium molybdate is once added to above-mentioned molten
In liquid, mixed solution stirs half an hour under the conditions of magnetic agitation, after stirring, instills 0.5ml, 0.01mmolL-1Adjacent benzene two
The phenol aqueous solution is stirred 2 minutes, and mixed liquor is transferred in polytetrafluoroethylkettle kettle core afterwards.Reactor is sealed and placed in 170 DEG C of perseverance
Heated in warm baking oven, taken out after 8.5 hours, be naturally cooling to room temperature.Drive kettle and take out reaction bottoms, resulting bluish violet thing
Matter uses 1M HCl solutions, distilled water respectively, and ethanol is cleaned, is finally put in 63 DEG C of baking ovens and dries, that is, obtain uniform particle diameter
ZnPc hollow ball material, yield is up to 96.8%.
Embodiment 9
0.5mg polyethylene glycol (PEG, molecular weight 4000) is added in 15ml distilled water, 60 DEG C of stirrings to dissolving, room temperature
Under, by 0.8mmol 4- nitro phthalic nitriles, 0.162mmol zinc chloride, 3.68mg ammonium molybdate is once added to above-mentioned molten
In liquid, mixed solution stirs half an hour under the conditions of magnetic agitation, after stirring, instills 0.5ml, 0.01mmolL-1Adjacent benzene two
The phenol aqueous solution is stirred 2 minutes, and mixed liquor is transferred in polytetrafluoroethylkettle kettle core afterwards.Reactor is sealed and placed in 178 DEG C of perseverance
Heated in warm baking oven, taken out after 9.6 hours, be naturally cooling to room temperature.Drive kettle and take out reaction bottoms, resulting bluish violet thing
Matter uses 1M HCl solutions, distilled water respectively, and ethanol is cleaned, is finally put in 63 DEG C of baking ovens and dries, that is, obtain uniform particle diameter
ZnPc hollow ball material, yield is up to 97.3%.
Embodiment 10
0.5mg polyethylene glycol (PEG, molecular weight 4000) is added in 15ml distilled water, 60 DEG C of stirrings to dissolving, room temperature
Under, by 0.8mmol 4- nitro phthalic nitriles, 0.196mmol zinc chloride, 4.44mg ammonium molybdate is once added to above-mentioned molten
In liquid, mixed solution stirs half an hour under the conditions of magnetic agitation, after stirring, instills 0.5ml, 0.01mmolL-1Adjacent benzene two
The phenol aqueous solution is stirred 2 minutes, and mixed liquor is transferred in polytetrafluoroethylkettle kettle core afterwards.Reactor is sealed and placed in 175 DEG C of perseverance
Heated in warm baking oven, taken out after 9 hours, be naturally cooling to room temperature.Drive kettle and take out reaction bottoms, resulting royal purple color substance
1M HCl solutions, distilled water are used respectively, and ethanol is cleaned, is finally put in 65 DEG C of baking ovens and dries, that is, obtain uniform particle diameter
ZnPc hollow ball material, yield is up to 96.8%.
The above-mentioned ZnPc hollow ball prepared by this method is scanned Electronic Speculum test, as a result as shown in Figure 1-2, from figure
It can be seen that being spherical, spheroid soilless sticking phenomenon by the ZnPc obtained by this method in 1, and it can be seen that spheroid seems
For hollow-core construction；As can be seen from Figure 2 obtained ZnPc spheroid is hollow-core construction, and sphere size is 4-6 microns,
Therefore the material can improve the effective rate of utilization of ZnPc surface area.
The above-mentioned ZnPc hollow ball prepared by this method is subjected to X-ray diffraction test, sample is obtained for inspection institute
Phase purity, as a result as shown in figure 3, the XRD that Fig. 3 is obtained contrasts with standard card JCPDS 21-1985, as a result show this hair
Bright obtained sample is β-ZnPc, and without other dephasign diffraction maximums are found, this just illustrates that products therefrom is well
Pure β-ZnPc crystal formations.
The above-mentioned ZnPc hollow ball prepared by this method is subjected to UV absorption experiment, as a result as shown in figure 4, from Fig. 4
As can be seen that there is two main absorption bands, one is located at 550-750nm, and another is located at 300-450nm, is belonging respectively to zinc
The Q band characteristic absorptions and B band characteristic absorptions of phthalocyanine, at 669 and 604nm, this should be attributed to Pc-2Ring is single by HOMO to LUMO
π-π * transformation between body, in addition, also there is an apparent 641nm peak between two characteristic peaks of Q bands, this is by list
Caused by electronic vibration band between aggressiveness and polymer.The figure illustrates that ZnPc has stronger absorption in visible light wave range, and this makes
Obtaining metal phthalocyanine can be by the use of visible ray as light source degradable organic pollutant, and is widely used in sewage disposal.This is special
Point, which also compensate for conventional semiconductors metal oxide photocatalyst, can only utilize wavelength<400 nanometers of ultraviolet light, and for wavelength
The deficiency that visible ray more than 400nm does not respond to, improve utilization rate of the photochemical catalyst to sunshine.
The existing method for preparing ZnPc, as DBU liquid phase methods prepare ZnPc, each reactant will generally at 140 DEG C
It is heated to reflux 48 hours, is extracted with dichloromethane, cleaned with water afterwards, then solvent is removed through being evaporated under reduced pressure, obtains crude zinc phthalein
Cyanines product, finally also to pass through column chromatography, the ZnPc yield nonetheless obtained is only 15%, and the random shape of product
Looks.And each reactant is directly transferred in polytetrafluoroethylkettle kettle core by the present invention, reactor is sealed and placed in 160 DEG C of constant temperature oven
Middle heating, reacted through 8 hours, 1M HCl solutions, distilled water, ethanol cleaning can be prepared by ZnPc hollow ball, and yield for several times
Up to 96-98%；Meanwhile this method adds catechol and polyethylene glycol in reaction system can obtain having special empty chou
The ZnPc of structure.
Claims (7)
1. a kind of preparation method of ZnPc hollow ball, using 4- nitros phthalic nitrile and zinc salt as raw material, ammonium molybdate is catalyst
Prepared, it is characterised in that comprise the following steps：
(1) polyethylene glycol is mixed with distilled water, stirring extremely dissolving, obtains mixed solvent at 60 DEG C；
(2) at room temperature, 4- nitros phthalic nitrile, zinc chloride and ammonium molybdate are added to above-mentioned in the mixed solvent, magnetic agitation
30-40min, mixed liquor is obtained, the catechol aqueous solution is then instilled into mixed liquor, after stirring 2-4min, mixed liquor is turned
Enter into reactor, seal；
(3) reactor is placed in 160-180 DEG C of constant temperature oven and heats 8-10h, take out reactor afterwards, be cooled to room temperature,
Drive kettle and take out bottom reactant, wash, drying, obtain ZnPc hollow ball；
The volume ratio of the catechol aqueous solution and distilled water is 0.1:(2.8-3.2).
A kind of 2. preparation method of ZnPc hollow ball according to claim 1, it is characterised in that 4- nitro phthalic nitriles
Mol ratio with 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 zinc chloride and ammonium molybdate
Mass ratio be (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 polyethylene glycol and distillation
The weight ratio of water is 1 × 10-4：(2.8-3.2).
A kind of 5. preparation method of ZnPc hollow ball according to claim 1, it is characterised in that described catechol
The concentration of the 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 used during washing
1mol/L hydrochloric acid solution cleaning once, is then cleaned twice with ethanol, finally cleaned 2 times with distilled water again again.
7. the preparation method of a kind of ZnPc hollow ball according to claim 1, it is characterised in that described in step (3)
Drying, is dried in 50-70 DEG C of baking oven.
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| 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 |
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| JPH0641137A (en) * | 1992-02-08 | 1994-02-15 | Nippon Nohyaku Co Ltd | Phthalocyanine derivative and its production and production of its intermediate |
| DE102004001457A1 (en) * | 2004-01-08 | 2005-09-01 | Basf Ag | Process for the preparation of phthaloxyanines |
| CN103992327B (en) * | 2014-04-08 | 2016-06-01 | 许昌学院 | Solvent thermal reaction one step prepares the method for manganese phthalocyanine crystal |
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