CN109400614A - A kind of preparation method of Phthalocyanine Zinc - Google Patents
A kind of preparation method of Phthalocyanine Zinc Download PDFInfo
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- CN109400614A CN109400614A CN201811494730.6A CN201811494730A CN109400614A CN 109400614 A CN109400614 A CN 109400614A CN 201811494730 A CN201811494730 A CN 201811494730A CN 109400614 A CN109400614 A CN 109400614A
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- zinc
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- phthalocyanine
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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 present invention provides a kind of preparation methods of Phthalocyanine Zinc, it successively comprises the steps of: and first phthalic nitrile is dissolved in solvent, it is stand-by in charging feedstock storage tank 1, zinc salt is put into agate again and grinds alms bowl, it is fine ground, a certain amount of zinc salt is taken to be dissolved in solvent, in charging feedstock storage tank 2, open temperature control and pressure system, reaction temperature and pressure are set, open microwave system, according to the molar ratio of phthalic nitrile and zinc acetate dihydrate, calculate the volume flow to feed intake, the flow of microprocessor pump drive 1 and microprocessor pump drive 2 is set, connection fluid discharge pump 1 and fluid discharge pump 2 are opened simultaneously, after the solution of storage tank 1 and storage tank 2 is mixed at Y type hybrid juction respectively, into micro passage reaction.Through stop reaction after a period of time, feed liquid is collected in collecting tank, the feed liquid in collecting tank is pumped into crystallizing tank, after liquid is reduced to room temperature, the water of 1:1 volume is added, mashing has a large amount of solids to be precipitated.Feed liquid is cooled to -5~0 DEG C, stirring and crystallizing 5 hours with ice salt bath again.Decompression filters, and filter cake is eluted with water, dries to obtain product Phthalocyanine Zinc.
Description
(1) technical field
The invention belongs to organic and metal complexes to synthesize field, and in particular to a kind of preparation method of Phthalocyanine Zinc.
(2) background technique
Phthalocyanine is a kind of nitrogenous macrocyclic compound.Phthalocyanine ring is the big ring conjugated system comprising 18 pi-electrons, is had
Visibly homogeneous electron density, this makes 4 phenyl ring in its molecule be difficult to deform, and all C-N key lengths are approximately equal,
So phthalocyanine has extraordinary stability, it is heat-resisting, fast light, water-fast, and acid and alkali resistance and the erosion of a variety of organic solvents；And
And having hole in phthalocyanine ring, hole radius is 0.135nm, can accommodate many metals such as cobalt, iron, copper, nickel and zinc and transition metal
Element forms phthalocyanine metal chemical combination object.The structural formula of titanium cyanines metallic compound is shown in (1) that phthalocyanine metal chemical combination object has very wide
General purposes, especially in terms of new material, raw catelyst.It not only has unique light, sound, electricity, magnetic property, but also to certain
The catalyst still haveing excellent performance is reacted a bit.
Currently, the study on the synthesis report of monokaryon phthalocyanine metal is more, it is mainly the following method:
Xia Xuewei etc. (colleges and universities' chemical engineering journal, 2007,21 (1): 131-134.) reports the preparation of Cobalt Phthalocyanine (II)
Method: using α-chloro-naphthol as solvent, by phthalic anhydride, the finely ground mixing of urea, a certain amount of chlorination cobalt powder is added after reacting a period of time
Continue to react after end, anhydrous sodium sulfate, ammonium chloride and ammonium molybdate, crude product can be obtained through processing after reaction.Use salt
Sodium chloride saturated solution, ethyl alcohol, acetone and the chloroform of acid handle crude product, obtain purer product, yield is up to 94%.It adopts
More pure Cobalt Phthalocyanine can be obtained with higher yields with this method, but is operated relatively complicated.
The method of currently used synthetic phthalocyanine iron (II) are as follows: ferrous hydroxide is added to trichloro-benzenes (containing 10% quinoline)
In, heating adds people's phthalic nitrile, reacts at 217 DEG C.It can be obtained FePC (II), receive through purification process such as filterings after reaction
Rate is 73%.If a small amount of ammonium molybdate is added in the reaction, yield is up to 89%.FePC is reacted with thionyl chloride can be obtained dichloro
For FePC.
(Shanghai environmental science, 2001,20 (10): 480-481.) such as the lifes of king's stove report a kind of more easy FePC
Synthetic method: being heated to reflux at 200~210 DEG C after a certain amount of iron chloride and phthalic nitrile are mixed, and becomes deep in solid phase
Stop heating when green liquid phase, be cooled to room temperature, purified reaction object, more pure FePC can be obtained.Later, Li Jiqing etc.
(University Of Ji'nan's journal, 2009,23 (2): 159-161.) carry out in ionic liquid 1-butyl-3-methyl imidazolium tetrafluoroborate
The reaction of iron chloride and phthalic nitrile, has synthesized FePC, avoids toxic, volatile when other organic solvents are liquid phase
The disadvantages of, and ionic liquid is reusable, and activity does not reduce.
The composition principle and synthetic route of Nickel Phthalocyanine are identical as Cobalt Phthalocyanine, FePC.Zhan Hongbing etc. (silicate journal,
2002,30 (4): 496-499.) using the new method of in-situ chemical synthesis, using phthalonitrile as raw material, in SiO2 xerogel
Nickel Phthalocyanine is prepared for by the heat treatment under certain temperature in matrix.Find only have phthalocyanine in synthesized product by characterization
Nickel monomer exists, and illustrates the inorganic base and doped phthalocyanine metal chemical combination object that can synthesize function admirable using this method.
Uchida etc. (ARKIVOC, 2005,11:17-23.) reports a kind of side of synthetic phthalocyanine copper in a mild condition
Then plus people's trifluoro method: using phthalamide or phthalic anhydride as raw material, being heated in the presence of hexamethyldisilazane,
Copper methane sulfonate and dimethylformamide can obtain the CuPc (II) of yield 71% at a lower temperature.Later, Li et al.
(Inorg.Chem., 2008,47 (4): 1255-1257.) have synthesized CuPc by hydration method, which, which had both avoided use, has
Pollution problem of the solvent to environment, and a kind of new approaches of monocrystalline CuPc for synthesizing nanostructure are developed, this is for it
The low pollution synthesis of his nanostructure organic matter has important reference.
Reporting microwave radiation from Gedye etc. (Tetrahedron Lett.1996,27 (41): 4945-4958.) can promote
Into after organic reaction, microwave technology has become common method in the field of chemical synthesis.In recent years, phthalocyanine metal microwave process for synthesizing
Also certain progress is achieved, He Xiaomei etc. (synthesis chemistry, 2002,10 (1): 87-90.) is successfully prepared using microwave solid source
CuPc.Yin Huanshun etc. (dyestuff and dyeing, 2007,44 (5): 10-12.) reports the microwave synthesis process of Cobalt Phthalocyanine: with benzene
Acid anhydride, urea, ammonium molybdate and cobalt acetate are raw material, and urea dissolution, after being sufficiently mixed, the spoke in micro-wave oven are heated to after grinding uniformly
According to certain time, carrying out purification to crude product after completion of the reaction can be obtained Cobalt Phthalocyanine (II).Relative to solid-phase synthesis, this method
Great advantage be the time required to it is shorter, but due to the limitation that microwave uses, plant-scale life is difficult to realize in the short time
It produces.
The synthetic method and principle of Phthalocyanine Zinc mainly have following three kinds with the synthesis of other metal phthalocyanines: ammonium molybdate solid phase
Catalysis method, atent solvent method and DBU liquid catalytic.But three kinds of methods be not only required to be added catalyst, reaction temperature compared with
Height, reaction time are longer, and method of purification is complicated, and therefore, this project passes through pipeline using phthalic nitrile and zinc acetate as raw material
Mode carry out synthetic phthalocyanine zinc.
(3) summary of the invention
In view of the above problems, the present invention is quasi- to provide a kind of preparation method of Phthalocyanine Zinc.
To achieve the above object, The technical solution adopted by the invention is as follows:
A kind of preparation method of Phthalocyanine Zinc, which is characterized in that the preparation method carries out as follows:
1. phthalic nitrile is dissolved in solvent, it is stand-by in charging feedstock storage tank 1；
2. zinc salt, which is put into agate, grinds alms bowl, fine ground, a certain amount of zinc salt is taken to be dissolved in solvent, in charging feedstock storage tank 2；
3. opening temperature control and pressure system, reaction temperature and pressure are set, open microwave system.
4. calculating the volume flow to feed intake according to the molar ratio of phthalic nitrile and zinc acetate dihydrate, microprocessor pump drive 1 is set
With the flow of microprocessor pump drive 2, while connection fluid discharge pump 1 and fluid discharge pump 2 is opened, respectively by storage tank 1 and storage tank 2
After solution mixes at Y type hybrid juction, into micro passage reaction.Through stop reaction after a period of time, feed liquid is collected in
In collecting tank；.
5. the feed liquid in collecting tank is pumped into crystallizing tank, after liquid is reduced to room temperature, the water of 1:1 volume is added, is beaten,
There are a large amount of solids to be precipitated.Feed liquid is cooled to -5~0 DEG C, stirring and crystallizing 5 hours with ice salt bath again.Decompression filters, filter cake water
Elution, dries to obtain product Phthalocyanine Zinc.
The preparation method of a kind of Phthalocyanine Zinc, which is characterized in that 1. 2. the solvent is N, N- to step with step
Dimethylformamide, DMAC N,N' dimethyl acetamide, N, one of protonic solvents such as N- dimethylpropionamide, N-methylmorpholine
Or it is a variety of, preferably step 1. with step 2. in solvent it is identical, and be n,N-Dimethylformamide；Solvent is relative to adjacent benzene
The volumetric usage of dintrile quality is 5~20mL/g, is preferable over 10~12mL/g, more preferably step 1. with step 2. in it is molten
Agent dosage is equal.
The preparation method of a kind of Phthalocyanine Zinc, which is characterized in that the zinc salt is zinc chloride, zinc acetate, trifluoro
Methanesulfonic acid zinc, bis- (triphenyl phosphorus) zinc dichlorides etc., is preferable over zinc acetate.
The preparation method of a kind of Phthalocyanine Zinc, which is characterized in that the molar ratio of the phthalic nitrile and zinc salt is
4:0.9~1.15 are preferable over 4:1.05~1.1.
A kind of preparation method of the Phthalocyanine Zinc, which is characterized in that the step 3. in reaction temperature be 60~
150 DEG C, preferably 110~130 DEG C；Reaction pressure is 0~25bar, is preferable over 10~15bar；Microwave intensity is 500~900W,
It is preferable over 800W.
The preparation method of a kind of Phthalocyanine Zinc, which is characterized in that the stop reaction time is 10~30s, excellent
It selects in 20~25s.
The beneficial effects of the present invention are:
The present invention uses the dihydrate synthetic phthalocyanine of phthalic nitrile and zinc acetate, and raw material is simple and easy to get, at low cost.
The present invention using n,N-Dimethylformamide as high boiling protonic solvent, it is preferable to the dissolubility of raw material,
Meanwhile DMF has alkalinity, and negatively charged N atom is contained in structure, can be formed and is coordinated with metal, come promote reaction into
Row.
Microwave technology and microchannel are introduced simultaneously in the present invention, concise in technology is efficient, safely controllable, resulting product
Purity is high, excellent performance.
(4) Detailed description of the invention
Fig. 1 is process flow chart of the invention；
Fig. 2 is the equipment flowsheet that microchannel plate of the invention is answered.
(5) specific embodiment:
Below the technical scheme of the invention is illustrated by a specific example, but the scope of the present invention is not limited thereto:
Embodiment 1:
First 6g (0.047mol) phthalic nitrile is dissolved in 36mL n,N-Dimethylformamide (hereinafter referred to as DMF), is obtained
It is stand-by in 40mL solution charging feedstock storage tank 1, then 2.7g (0.012mol) zinc acetate dihydrate is put into agate and grinds alms bowl, it is fine ground, it is molten
In 16mL DMF, obtain in 17mL solution charging feedstock storage tank 2, setting reaction temperature be 110 DEG C, pressure 15bar, open
Microwave intensity is 800W, and microprocessor pump drive 1 is arranged and 2 flow velocity of microprocessor pump drive is respectively 120mL/min and 51mL/min, together
Shi Kaiqi connection fluid discharge pump 1 and fluid discharge pump 2 respectively mix the solution of storage tank 1 and storage tank 2 at Y type hybrid juction
After conjunction, into micro passage reaction.It stops and reacts by 20s, feed liquid is collected in collecting tank.Feed liquid in collecting tank is pumped into
In crystallizing tank, after liquid is reduced to room temperature, the water of 1:1 volume is added, mashing there are a large amount of solids to be precipitated.Again by feed liquid ice salt bath
It is cooled to -5~0 DEG C, stirring and crystallizing 5 hours.Decompression filters, and filter cake is eluted with water, dries to obtain product Phthalocyanine Zinc.Yield is 90%
(in terms of phthalic nitrile, similarly hereinafter).
Embodiment 2:
First 6g (0.047mol) phthalic nitrile is dissolved in 36mL DMF, is obtained in 40mL solution charging feedstock storage tank 1 for use,
2.7g (0.012mol) zinc acetate dihydrate is put into agate again and grinds alms bowl, it is fine ground, it is dissolved in 16mL DMF, obtains 17mL solution and be packed into original
Expect storage tank 2 in, setting reaction temperature be 110 DEG C, pressure 10bar, unlatchings microwave intensity be 800W, setting microprocessor pump drive 1
Being with 2 flow velocity of microprocessor pump drive is respectively 96mL/min and 41mL/min, while opening connection fluid discharge pump 1 and fluid flow
Pump 2, after respectively mixing the solution of storage tank 1 and storage tank 2 at Y type hybrid juction, into micro passage reaction.Stop by 25s
Reaction is stayed, feed liquid is collected in collecting tank.Post-processing is the same as embodiment 1, yield 92%.
Embodiment 3:
First 6g (0.047mol) phthalic nitrile is dissolved in 30mL DMF, is obtained in 34mL solution charging feedstock storage tank 1 for use,
2.7g (0.012mol) zinc acetate dihydrate is put into agate again and grinds alms bowl, it is fine ground, it is dissolved in 13.5mL DMF, obtains the loading of 14mL solution
In raw material storage tank 2, setting reaction temperature be 110 DEG C, pressure 15bar, unlatchings microwave intensity be 800W, setting microprocessor pump drive
1 and 2 flow velocity of microprocessor pump drive be respectively 102mL/min and 42mL/min, while opening connection fluid discharge pump 1 and liquid flow
Amount pump 2, after respectively mixing the solution of storage tank 1 and storage tank 2 at Y type hybrid juction, into micro passage reaction.By 20s
Reaction is stopped, feed liquid is collected in collecting tank.Post-processing is the same as embodiment 1, yield 87%.
Embodiment 4:
First 6g (0.047mol) phthalic nitrile is dissolved in 36mL DMF, is obtained in 40mL solution charging feedstock storage tank 1 for use,
2.8g (0.013mol) zinc acetate dihydrate is put into agate again and grinds alms bowl, it is fine ground, it is dissolved in 17mL DMF, obtains 17mL solution and be packed into original
Expect storage tank 2 in, setting reaction temperature be 110 DEG C, pressure 10bar, unlatchings microwave intensity be 800W, setting microprocessor pump drive 1
Being with 2 flow velocity of microprocessor pump drive is respectively 120mL/min and 54mL/min, while opening connection fluid discharge pump 1 and liquid flow
Amount pump 2, after respectively mixing the solution of storage tank 1 and storage tank 2 at Y type hybrid juction, into micro passage reaction.By 20s
Reaction is stopped, feed liquid is collected in collecting tank.Post-processing is the same as embodiment 1, yield 86%.
Embodiment 5:
First 6g (0.047mol) phthalic nitrile is dissolved in 36mL DMF, is obtained in 40mL solution charging feedstock storage tank 1 for use,
2.7g (0.012mol) zinc acetate dihydrate is put into agate again and grinds alms bowl, it is fine ground, it is dissolved in 16mL DMF, obtains 18mL solution and be packed into original
Expect storage tank 2 in, setting reaction temperature be 110 DEG C, pressure 10bar, unlatchings microwave intensity be 800W, setting microprocessor pump drive 1
Being with 2 flow velocity of microprocessor pump drive is respectively 120mL/min and 51mL/min, while opening connection fluid discharge pump 1 and liquid flow
Amount pump 2, after respectively mixing the solution of storage tank 1 and storage tank 2 at Y type hybrid juction, into micro passage reaction.By 20s
Reaction is stopped, feed liquid is collected in collecting tank.Post-processing is the same as embodiment 1, yield 92%.
Embodiment 6:
First 6g (0.047mol) phthalic nitrile is dissolved in 36mL DMF, is obtained in 40mL solution charging feedstock storage tank 1 for use,
2.7g (0.012mol) zinc acetate dihydrate is put into agate again and grinds alms bowl, it is fine ground, it is dissolved in 16mL DMF, obtains 17mL solution and be packed into original
Expect storage tank 2 in, setting reaction temperature be 110 DEG C, pressure 15bar, unlatchings microwave intensity be 800W, setting microprocessor pump drive 1
Being with 2 flow velocity of microprocessor pump drive is respectively 96mL/min and 41mL/min, while opening connection fluid discharge pump 1 and fluid flow
Pump 2, after respectively mixing the solution of storage tank 1 and storage tank 2 at Y type hybrid juction, into micro passage reaction.Stop by 25s
Reaction is stayed, feed liquid is collected in collecting tank.Post-processing is the same as embodiment 1, yield 90%.
Claims (6)
1. a kind of preparation method of Phthalocyanine Zinc, which is characterized in that the preparation method carries out as follows:
1. phthalic nitrile is dissolved in solvent, it is stand-by in charging feedstock storage tank 1；
2. zinc salt, which is put into agate, grinds alms bowl, fine ground, a certain amount of zinc salt is taken to be dissolved in solvent, in charging feedstock storage tank 2；
3. opening temperature control and pressure system, reaction temperature and pressure are set, open microwave system.
4. calculating the volume flow to feed intake according to the molar ratio of phthalic nitrile and zinc acetate dihydrate, microprocessor pump drive 1 and liquid are set
The flow of body metering pump 2, while connection fluid discharge pump 1 and fluid discharge pump 2 are opened, respectively by the solution of storage tank 1 and storage tank 2
After being mixed at Y type hybrid juction, into micro passage reaction.Through stop reaction after a period of time, feed liquid is collected in collection
In tank；
5. the feed liquid in collecting tank is pumped into crystallizing tank, after liquid is reduced to room temperature, the water of 1:1 volume is added, mashing has a large amount of
Solid is precipitated.Feed liquid is cooled to -5~0 DEG C, stirring and crystallizing 5 hours with ice salt bath again.Decompression filters, and filter cake is eluted with water, dries
Do to obtain product Phthalocyanine Zinc.
2. a kind of preparation method of Phthalocyanine Zinc as described in claim 1, which is characterized in that step is 1. 2. described molten with step
Agent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N, the protonic solvents such as N- dimethylpropionamide, N-methylmorpholine
One of or it is a variety of, preferably step 1. with step 2. in solvent it is identical, and be n,N-Dimethylformamide；Solvent phase
1. and the step of volumetric usage to(for) phthalic nitrile quality is 5~20mL/g, is preferable over 10~12mL/g, and more preferably step
2. solvent usage in is equal.
3. a kind of preparation method of Phthalocyanine Zinc as described in claim 1, which is characterized in that the zinc salt is zinc chloride, vinegar
Sour zinc, trifluoromethanesulfonic acid zinc, bis- (triphenyl phosphorus) zinc dichlorides etc., are preferable over zinc acetate.
4. a kind of preparation method of Phthalocyanine Zinc as described in claim 1, which is characterized in that the phthalic nitrile and zinc salt
Molar ratio is 4:0.9~1.15, is preferable over 4:1.05~1.1.
5. a kind of preparation method of Phthalocyanine Zinc as described in claim 1, which is characterized in that the step 3. in reaction temperature
Degree is 60~150 DEG C, preferably 110~130 DEG C；Reaction pressure is 0~25bar, is preferable over 10~15bar；Microwave intensity is 500
~900W, is preferable over 800W.
6. a kind of preparation method of Phthalocyanine Zinc as described in claim 1, which is characterized in that the stop reaction time is 10
~30s, is preferable over 20~25s.
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Citations (4)
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|---|---|---|---|---|
| CN102887541A (en) * | 2011-07-21 | 2013-01-23 | 北京化工大学 | Preparation method of phthalocyanine sensitized TiO2 nano-particle by microwave-hydrothermal method |
| CN103145717A (en) * | 2013-01-28 | 2013-06-12 | 河北科技大学 | Preparation method for phthalocyanine compound |
| CN105131001A (en) * | 2015-08-25 | 2015-12-09 | 辽宁大学 | Synthetic method of unsubstituted zinc phthalocyanine |
| CN105777764A (en) * | 2016-04-13 | 2016-07-20 | 南京工业大学 | Method for preparing tetraphenylporphyrin through micro reaction device |
-
2018
- 2018-12-07 CN CN201811494730.6A patent/CN109400614A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102887541A (en) * | 2011-07-21 | 2013-01-23 | 北京化工大学 | Preparation method of phthalocyanine sensitized TiO2 nano-particle by microwave-hydrothermal method |
| CN103145717A (en) * | 2013-01-28 | 2013-06-12 | 河北科技大学 | Preparation method for phthalocyanine compound |
| CN105131001A (en) * | 2015-08-25 | 2015-12-09 | 辽宁大学 | Synthetic method of unsubstituted zinc phthalocyanine |
| CN105777764A (en) * | 2016-04-13 | 2016-07-20 | 南京工业大学 | Method for preparing tetraphenylporphyrin through micro reaction device |
Non-Patent Citations (1)
| Title |
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| 黄长干等: "《有机合成化学》", 31 August 2017, 合肥工业大学出版社 * |
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Application publication date: 20190301 |