CN103772396B - A kind of preparation method of tetracarboxylic substituted metal phthalocyanine - Google Patents
A kind of preparation method of tetracarboxylic substituted metal phthalocyanine Download PDFInfo
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- CN103772396B CN103772396B CN201410000123.5A CN201410000123A CN103772396B CN 103772396 B CN103772396 B CN 103772396B CN 201410000123 A CN201410000123 A CN 201410000123A CN 103772396 B CN103772396 B CN 103772396B
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- metal phthalocyanine
- substituted metal
- gained
- tetracarboxylic
- tetraamido
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- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 91
- 239000002184 metal Substances 0.000 title claims abstract description 91
- 125000006158 tetracarboxylic acid group Chemical group 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000012043 crude product Substances 0.000 claims abstract description 36
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 24
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims abstract description 20
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims abstract description 17
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 13
- 239000011609 ammonium molybdate Substances 0.000 claims abstract description 12
- 235000018660 ammonium molybdate Nutrition 0.000 claims abstract description 12
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims abstract description 12
- 229940010552 ammonium molybdate Drugs 0.000 claims abstract description 12
- 235000013877 carbamide Nutrition 0.000 claims abstract description 12
- 239000004202 carbamide Substances 0.000 claims abstract description 12
- -1 slaine Chemical compound 0.000 claims abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 33
- 239000007864 aqueous solution Substances 0.000 claims description 33
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 230000007062 hydrolysis Effects 0.000 claims description 17
- 238000006460 hydrolysis reaction Methods 0.000 claims description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000003786 synthesis reaction Methods 0.000 claims description 14
- 230000015572 biosynthetic process Effects 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 10
- 150000001408 amides Chemical class 0.000 claims description 9
- 239000000706 filtrate Substances 0.000 claims description 9
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical group OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 claims description 5
- 239000012065 filter cake Substances 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 235000010288 sodium nitrite Nutrition 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- AZFNGPAYDKGCRB-XCPIVNJJSA-M [(1s,2s)-2-amino-1,2-diphenylethyl]-(4-methylphenyl)sulfonylazanide;chlororuthenium(1+);1-methyl-4-propan-2-ylbenzene Chemical compound [Ru+]Cl.CC(C)C1=CC=C(C)C=C1.C1=CC(C)=CC=C1S(=O)(=O)[N-][C@@H](C=1C=CC=CC=1)[C@@H](N)C1=CC=CC=C1 AZFNGPAYDKGCRB-XCPIVNJJSA-M 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical group O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 3
- 235000010289 potassium nitrite Nutrition 0.000 claims description 3
- 239000004304 potassium nitrite Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 229910052748 manganese Inorganic materials 0.000 claims 1
- 239000011572 manganese Substances 0.000 claims 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 7
- 125000003368 amide group Chemical group 0.000 abstract description 5
- FHIVAFMUCKRCQO-UHFFFAOYSA-N diazinon Chemical compound CCOP(=S)(OCC)OC1=CC(C)=NC(C(C)C)=N1 FHIVAFMUCKRCQO-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000047 product Substances 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 4
- 238000000746 purification Methods 0.000 abstract description 3
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 241001597008 Nomeidae Species 0.000 description 2
- 238000005903 acid hydrolysis reaction Methods 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- 244000061458 Solanum melongena Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000007777 multifunctional material Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000002428 photodynamic therapy Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
Abstract
The invention discloses the preparation method of a kind of tetracarboxylic substituted metal phthalocyanine, i.e. first with phthalic anhydride, slaine, ammonium molybdate, carbamide heat four is poly-that tetraamido substituted metal phthalocyanine solid crude product is synthesized；Then, after utilizing nitrite and the amino in amide groups to react generation diazol, then produce carboxyl through acid hydrolytic reaction, i.e. generate tetracarboxylic substituted metal phthalocyanine.The preparation method of the tetracarboxylic substituted metal phthalocyanine of the present invention has that efficiency height, low cost, response time is short, the easy purification of product, to producing the features such as equipment requirements is relatively low.
Description
Technical field
The invention belongs to organic compound preparation technical field, be specifically related to the preparation side of tetracarboxylic substituted metal phthalocyanine
Method.
Background technology
In research in early days, phthalocyanine and its derivant are mainly used as pigment or dyestuff.Nowadays, phthalocyanine and derivative
Thing is not only a kind of coloring agent, and is a kind of multi-functional material, such as the sensitive device in chemical sensor, electroluminescent
Polymer of electrocatalysis material, synthesis metal and conduction in device, nonlinear optical material, fuel cell etc., recent phthalein
Cyanines and derivant thereof are also commonly used for various catalytic reaction, particularly are just playing more to come in terms of the photodynamic therapy of cancer
The most important effect.
But the dissolubility of metal phthalocyanine is the most poor, concentrated sulphuric acid or intensive polar solvent typically can only be dissolved in, such as N, N-
In dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), dimethyl sulfoxide (DMSO) or acetonitrile, this limits significantly
Metal phthalocyanine is extensively applied in various catalytic reactions.So, the synthesis of water-soluble metal phthalocyanine, especially carboxyl substituted metal
Phthalocyanine, is paid close attention to widely.
At present, thick with the tetraamido metal phthalocyanine that slaine, ammonium molybdate, carbamide obtain after high temperature four is poly-by benzoic anhydride
Product is the main method preparing carboxyl substituted metal phthalocyanine through long-time high-temperature acidic or basic hydrolysis.But, this by force
The method of acid or highly basic hydrolysis is the longest, the most several days of reaction 8-24h, and easily etching apparatus.This phenomenon produces
Reason be owing to metal phthalocyanine macro ring has highly stable characteristic, its water logging acidproof, alkaline-resisting, resistance to, heat-resisting, fast light and resistance to
Various organic solvents, and therefore, it is very difficult to find the suitable solvent of searching to dissolve tetraamido substituted metal phthalocyanine.Simultaneously because four acyls
Amido substituted metal phthalocyanine sterically hindered relatively big, adds the difficulty of hydrolysis the most to a certain extent.
Record at present about the patent of invention such as CN that carboxyl substituted metal phthalocyanine purity is improved
201110118814.1, this patent is by being esterified carboxyl substituted metal phthalocyanine, and then the step such as hydrolysis improves purity, by
Tetraamido substituted metal phthalocyanine is prepared and is still that employing traditional strong acid or the hydrolysis of highly basic in tetracarboxylic substituted metal phthalocyanine
Method, according to this patent report, hydrolysis time is at most up to 96 hours.
Summary of the invention
The purpose of the present invention is in order to solve above-mentioned tetracarboxylic substituted metal phthalocyanine preparation process cycle length, preparation process pair
The more high technical problem of equipment requirements and the preparation method of a kind of tetracarboxylic substituted metal phthalocyanine is provided.The method is by amide
Amino carry out diazol reaction and prepare carboxyl, overcome sterically hindered impact, be effectively shortened response time, final gained
Product purity high.
The know-why of the present invention
A kind of preparation method of tetracarboxylic substituted metal phthalocyanine, its concrete chemical equation is as follows:
Wherein amide mechanism of hydrolysis after diazol reacts can be represented by the formula:
I.e. gather first with traditional phthalic anhydride heat four and tetraamido substituted metal phthalocyanine solid crude product is synthesized；
Then, nitrite and the amino in amide groups in tetraamido substituted metal phthalocyanine solid crude product is utilized to react raw
With N after one-tenth diazol2Form is left away, then produces carboxyl through acid hydrolytic reaction, i.e. generates tetracarboxylic substituted metal phthalocyanine.
Technical scheme
The preparation method of a kind of tetracarboxylic substituted metal phthalocyanine, specifically includes following steps:
(1), the synthesis of tetraamido substituted metal phthalocyanine crude product
Phthalic anhydride, slaine, ammonium molybdate, carbamide are sufficiently mixed, and mill uniformly, proceeds to there-necked flask, at 170～300 DEG C,
Heating 2～6h, obtains pitchy tetraamido substituted metal phthalocyanine solid crude product；
Wherein phthalic anhydride is 1:1～4:0.002～0.03:10～40 with slaine, ammonium molybdate, the mol ratio of carbamide；
Described phthalic anhydride is trimellitic anhydride；
Described slaine is hydrochlorate or the sulfate of cobalt, copper, zinc, ferrum or manganese, preferably cobalt chloride hexahydrate, zinc chloride
Or copper sulphate pentahydrate；
Concentration is that the concentrated hydrochloric acid of 1～10mol/L is by the tetraamido substituted metal phthalocyanine solid crude product of above-mentioned gained
Filtering after boiling, the filter cake of gained washs with absolute ether, absolute methanol successively, till filtrate is colourless, obtains four
Amide groups substituted metal phthalocyanine crude product；
(2), tetracarboxylic substituted metal phthalocyanine synthesis
Tetraamido substituted metal phthalocyanine crude product will be added to quality hundred at 0～10 DEG C obtained by step (1)
Proportion by subtraction concentration be 50～70% aqueous sulfuric acid in, then by 1～5mol/L nitrite aqueous solution with the speed of 5-20ml/min
Rate is slowly dropped to wherein；
Described nitrite aqueous solution is sodium nitrite in aqueous solution or potassium nitrite aqueous solution；
Wherein tetraamido substituted metal phthalocyanine crude product, mass percent concentration is 50～the aqueous sulfuric acid of 70%, 1～
The consumption of 5mol/L nitrite aqueous solution, by tetraamido substituted metal phthalocyanine: mass percent concentration is the sulfur of 50～70%
Aqueous acid: 1～5mol/L nitrite aqueous solution is 1g:20～60mL:1.0～6mL, preferably 1g:27.2～34mL:
The ratio of 1.12～5.6mL calculates；
Dripping complete, the mixed liquor of gained continues to stir 10～30min post-heating at 0～15 DEG C and carries out to 30～60 DEG C
Hydrolysis 1～3h, hydrolysis terminate after by the reactant liquor centrifugation of gained, go out the supernatant, the precipitation 1 of gained is used
Deionized water wash is neutrality to the aqueous solution pH flowed out, then with the NaOH aqueous dissolution washing of 2mol/L, filtration, gained
Filtrate with 2mol/L hydrochloric acid adjust pH value to 1～4, stand overnight, gained solution recentrifuge separate, the precipitation 2 of gained controls
Vacuum 0.07～0.10MPa, temperature 50～75 DEG C are dried 2～6h, i.e. obtain tetracarboxylic substituted metal phthalocyanine.
Beneficial effects of the present invention
The preparation method of a kind of tetracarboxylic substituted metal phthalocyanine of the present invention, i.e. first passes through tetraamido substituted metal
Amide on phthalocyanine crude carries out diazol reaction, then through acid hydrolysis, can prepare tetracarboxylic substituted metal phthalocyanine.The method
Overcome hydrolysis difficulty, the time caused by sterically hindered impact in tetraamido substituted metal phthalocyanine because of acyl group
The shortcoming such as long, impurity is many, energy consumption is high, uses the method to prepare tetracarboxylic substituted metal phthalocyanine and has that the response time is short, reaction temperature
Spend low, conversion ratio is high, by-product is few, product is easy to the advantages such as purification, particularly calculates it with trimellitic anhydride for raw material
The gross production rate of end-product tetracarboxylic replacement cobalt phthalocyanine is up to 26.92%, and the response time of amide hydrolysis is from the 8-96h of prior art
Taper to 1-3h, thus relative drastically increase combined coefficient.
Further, the preparation method of a kind of tetracarboxylic substituted metal phthalocyanine of the present invention, owing to the tetracarboxylic of synthesis replaces
Metal phthalocyanine reaction temperature is low, and the response time is short, therefore relatively low to producing equipment requirements, it is only necessary to simple organic synthesis sets
The standby preparation that can complete tetracarboxylic substituted metal phthalocyanine.
Detailed description of the invention
Below by specific embodiment, the present invention is expanded on further, but is not limiting as the present invention.
Embodiment 1
The preparation method of a kind of tetracarboxylic substituted metal phthalocyanine, specifically includes following steps:
(1), the synthesis of tetraamido substituted metal phthalocyanine crude product
0.05mol(9.5g) phthalic anhydride, 0.05ol(11.9g) slaine, 0.1mmol(0.12g) ammonium molybdate, 0.5mol
(30.0g) carbamide is sufficiently mixed in mortar, grinds uniformly, proceeds to there-necked flask, at 170 DEG C, heats 6h, obtains pitchy
Tetraamido substituted metal phthalocyanine solid crude product；
Wherein phthalic anhydride is 1:1:0.002:10 with slaine, ammonium molybdate, the mol ratio of carbamide；
Described phthalic anhydride is trimellitic anhydride；
Described slaine is cobalt chloride hexahydrate；
Concentration is that the tetraamido substituted metal phthalocyanine solid crude product of above-mentioned gained is boiled by the concentrated hydrochloric acid of 5mol/L
Rear filtration, the filter cake of gained washs with absolute ether, absolute methanol successively, till filtrate is colourless, obtains four amide
Base substituted metal phthalocyanine crude product；
(2), tetracarboxylic substituted metal phthalocyanine synthesis
5g tetraamido substituted metal phthalocyanine crude product obtained by step (1) is added to 170mL mass hundred at 5 DEG C
Proportion by subtraction concentration is in the aqueous sulfuric acid of 50%, then by the 2mol/L nitrite aqueous solution of 14mL with the speed of 5mL/min by
It is added dropwise to wherein；
Described nitrite aqueous solution is sodium nitrite in aqueous solution；
Wherein tetraamido substituted metal phthalocyanine crude product, mass percent concentration be 50% aqueous sulfuric acid, 2mol/L sub-
The consumption of nitrate aqueous solution is by tetraamido substituted metal phthalocyanine: mass percent concentration is the aqueous sulfuric acid of 50%:
2mol/L nitrite aqueous solution is that the ratio of 1g:34mL:2.8mL calculates；
After dropping, the mixed liquor of gained continues to stir 10min post-heating to 30 DEG C of reactions that are hydrolyzed at 0 DEG C
1h, hydrolysis terminate after by the reactant liquor centrifugation of gained, go out the supernatant, the precipitation 1 of gained is washed with deionized water
Washing to the aqueous solution pH flowed out is neutrality, then washs with the NaOH aqueous dissolution of the 2mol/L of 100mL, filters, gained
Filtrate adjusts pH value to 1～4 with 2mol/L hydrochloric acid, stands overnight, and gained solution recentrifuge separates, and the precipitation 2 of gained controls very
Reciprocal of duty cycle 0.07MPa, temperature 60 C is dried 6h, obtains atropurpureus tetracarboxylic and replaces cobalt phthalocyanine 2.5g.
The tetracarboxylic of above-mentioned final gained replaces cobalt phthalocyanine, calculates tetracarboxylic with trimellitic anhydride for raw material and replaces cobalt
The gross production rate of phthalocyanine is 26.92%.
Embodiment 2
The preparation method of a kind of tetracarboxylic substituted metal phthalocyanine, specifically includes following steps:
(1), the synthesis of tetraamido substituted metal phthalocyanine crude product
0.05 mol(9.5g) phthalic anhydride, 0.15mol(37.4g) slaine, 1.5mmol(1.8g) ammonium molybdate, 2mol
(120.0g) carbamide is sufficiently mixed in mortar, grinds uniformly, proceeds to there-necked flask, at 300 DEG C, heats 2h, obtains dark brown
Color tetraamido substituted metal phthalocyanine solid crude product；
Wherein phthalic anhydride is 1:3:0.03:40 with slaine, ammonium molybdate, the mol ratio of carbamide；
Described phthalic anhydride is trimellitic anhydride；
Described slaine is copper sulphate pentahydrate；
Concentration is that the tetraamido substituted metal phthalocyanine solid crude product of above-mentioned gained is boiled by the concentrated hydrochloric acid of 1mol/L
Rear filtration, the filter cake of gained washs with absolute ether, absolute methanol successively, till filtrate is colourless, obtains four amide
Base substituted metal phthalocyanine crude product；
(2), tetracarboxylic substituted metal phthalocyanine synthesis
The 5g tetraamido substituted metal phthalocyanine crude product of gained in step (1) is added to 145 mL mass hundred at 0 DEG C
Proportion by subtraction concentration is in the aqueous sulfuric acid of 60%, then by the 1mol/L nitrite aqueous solution of 28mL with the speed of 10 mL/min
It is added dropwise to wherein；
Described nitrite aqueous solution is potassium nitrite aqueous solution；
Wherein tetraamido substituted metal phthalocyanine crude product, mass percent concentration be 60% aqueous sulfuric acid, 1mol/L sub-
The consumption of nitrate aqueous solution is by tetraamido substituted metal phthalocyanine: mass percent concentration is the aqueous sulfuric acid of 60%:
1mol/L nitrite aqueous solution is that the ratio of 1g:29mL:5.6mL calculates；
Drip complete, the mixed liquor of gained continue at 15 DEG C stir 20min post-heating to 45 DEG C be hydrolyzed reaction 2h,
Hydrolysis terminate after by the reactant liquor centrifugation of gained, go out the supernatant, the precipitation 1 of gained be washed with deionized to
The aqueous solution pH flowed out is neutrality, then with the NaOH aqueous dissolution washing of the 2mol/L of 100mL, filtration, the filtrate of gained
Adjusting pH value to 1～4 with 2mol/L hydrochloric acid, stand overnight, gained solution recentrifuge separates, and the precipitation 2 of gained controls vacuum
0.10MPa, temperature 75 DEG C is dried 2h, obtains aubergine and has the tetracarboxylic of metallic luster to replace C.I. Pigment Blue 15 2.1g.
The tetracarboxylic of above-mentioned final gained replaces C.I. Pigment Blue 15, calculates tetracarboxylic with trimellitic anhydride for raw material and replaces copper
The gross production rate of phthalocyanine is 22.48%.
Embodiment 3
The preparation method of a kind of tetracarboxylic substituted metal phthalocyanine, specifically includes following steps:
(1), the synthesis of tetraamido substituted metal phthalocyanine crude product
0.05 mol(9.5g) phthalic anhydride, 0.2 mol(27.2g) slaine, 1.0mmol(1.2g) ammonium molybdate, 1.5mol
(90g) carbamide is sufficiently mixed in mortar, grinds uniformly, proceeds to there-necked flask, at 200 DEG C, heats 4h, obtains pitchy four
Amide groups substituted metal phthalocyanine solid crude product；
Wherein phthalic anhydride is 1:4:0.02:30 with slaine, ammonium molybdate, the mol ratio of carbamide；
Described phthalic anhydride is trimellitic anhydride；
Described slaine is zinc chloride；
Concentration is that the tetraamido substituted metal phthalocyanine solid crude product of above-mentioned gained is boiled by the concentrated hydrochloric acid of 10mol/L
Rear filtration, the filter cake of gained washs with absolute ether, absolute methanol successively, till filtrate is colourless, obtains four amide
Base substituted metal phthalocyanine crude product；
(2), tetracarboxylic substituted metal phthalocyanine synthesis
The 5g tetraamido substituted metal phthalocyanine crude product of gained in step (1) is added to 136ml mass hundred at 10 DEG C
Proportion by subtraction concentration is in the aqueous sulfuric acid of 70%, then by the 5mol/L nitrite aqueous solution of 5.6mL with the speed of 20ml/min
It is added dropwise to wherein；
Described nitrite aqueous solution is sodium nitrite in aqueous solution；
Wherein tetraamido substituted metal phthalocyanine crude product, mass percent concentration be 70% aqueous sulfuric acid, 5mol/L sub-
The consumption of nitrate aqueous solution, by tetraamido substituted metal phthalocyanine: mass percent concentration is the aqueous sulfuric acid of 70%:
5mol/L nitrite aqueous solution is that the ratio of 1g:27.2mL:1.12mL calculates；
Drip complete, the mixed liquor of gained continue at 10 DEG C stir 30min post-heating to 60 DEG C be hydrolyzed reaction 3h,
Hydrolysis terminate after by the reactant liquor centrifugation of gained, go out the supernatant, the precipitation 1 of gained be washed with deionized to
The aqueous solution pH flowed out is neutrality, then with the NaOH aqueous dissolution washing of the 2mol/L of 100mL, filtration, the filtrate of gained
Adjusting pH value to 1～4 with 2mol/L hydrochloric acid, stand overnight, gained solution recentrifuge separates, and the precipitation 2 of gained controls vacuum
0.08MPa, temperature 50 C is dried 4h, obtains light green tetracarboxylic and replaces ZnPc 2.1g.
The tetracarboxylic of above-mentioned final gained replaces ZnPc, calculates tetracarboxylic with trimellitic anhydride for raw material and replaces zinc
The gross production rate of phthalocyanine is 19.79%.
In sum, the invention provides the preparation method of a kind of tetracarboxylic substituted metal phthalocyanine, i.e. first pass through four
Amide on amide groups substituted metal phthalocyanine crude product carries out diazol reaction, then through acidic hydrolysis, can prepare tetracarboxylic and take
Substituting metal phthalocyanine.The method overcome in tetraamido substituted metal phthalocyanine because acyl group is caused by sterically hindered impact
Hydrolysis difficulty, the shortcomings such as time length, impurity are many, energy consumption is high.Use the method to prepare tetracarboxylic substituted metal phthalocyanine to have
Response time is short, reaction temperature is low, conversion ratio is high, by-product is few, product is easy to the advantages such as purification.Prominent effect is to make amide
The time of hydrolysis tapers to 1-3h from the 8-96h of prior art, drastically increases combined coefficient.
Foregoing is only the basic explanation under present inventive concept, and according to technical scheme made any etc.
Effect conversion, all should belong to protection scope of the present invention.
Claims (3)
1. the preparation method of a tetracarboxylic metal phthalocyanine, it is characterised in that specifically include following steps:
(1), the synthesis of tetraamido substituted metal phthalocyanine crude product
Phthalic anhydride, slaine, ammonium molybdate, carbamide are sufficiently mixed, grind uniformly, proceed to there-necked flask, at 170～300 DEG C, add
Heat 2～6h, obtains tetraamido substituted metal phthalocyanine solid crude product；
Wherein phthalic anhydride is 1:1～4:0.002～0.03:10～40 with slaine, ammonium molybdate, the mol ratio of carbamide；
Described phthalic anhydride is trimellitic anhydride；
Described slaine is hydrochlorate or the sulfate of cobalt, copper, zinc, ferrum or manganese；
Concentration be 1～10mol/L concentrated hydrochloric acid the tetraamido substituted metal phthalocyanine solid crude product of above-mentioned gained is boiled
Rear filtration, the filter cake of gained washs with absolute ether, absolute methanol successively, till filtrate is colourless, obtains four amide
Base substituted metal phthalocyanine crude product；
(2), tetracarboxylic substituted metal phthalocyanine synthesis
The tetraamido substituted metal phthalocyanine crude product of step (1) gained is added at 0～10 DEG C mass percent concentration is
50～70% aqueous sulfuric acid in, then 1～5mol/L nitrite aqueous solution is added drop-wise to it with the speed of 5-20ml/min
In；
Wherein tetraamido substituted metal phthalocyanine crude product, mass percent concentration be 50～the aqueous sulfuric acid of 70% and 1～
The consumption of 5mol/L nitrite aqueous solution, by tetraamido substituted metal phthalocyanine crude product: mass percent concentration is 50～70%
Aqueous sulfuric acid: 1～5mol/L nitrite aqueous solution be 1g:20～60mL:1.0～6mL ratio calculate；
Described nitrite aqueous solution is sodium nitrite in aqueous solution or potassium nitrite aqueous solution；
Dripping complete, the mixed liquor of gained continues to stir 10～30min post-heating at 0～15 DEG C and is hydrolyzed to 30～60 DEG C
Reaction 1～3h, hydrolysis terminate after by the reactant liquor centrifugation of gained, go out the supernatant, the precipitation 1 of gained spend from
The washing of sub-water is neutrality to the aqueous solution pH flowed out, and then washs with the NaOH aqueous dissolution of 2mol/L, filters, the filter of gained
Liquid 2mol/L hydrochloric acid adjusts pH value to 1～4, stands overnight, and gained solution recentrifuge separates, and the precipitation 2 of gained controls vacuum
Degree 0.07～0.10MPa, temperature 50～75 DEG C are dried 2～6h, i.e. obtain tetracarboxylic metal phthalocyanine.
The preparation method of a kind of tetracarboxylic metal phthalocyanine the most as claimed in claim 1, it is characterised in that described in step (1)
Slaine is cobalt chloride hexahydrate, zinc chloride or copper sulphate pentahydrate.
The preparation method of a kind of tetracarboxylic metal phthalocyanine the most as claimed in claim 2, it is characterised in that described in step (2)
Tetraamido substituted metal phthalocyanine crude product, mass percent concentration are 50～the aqueous sulfuric acid of 70%, 1～5mol/L nitrous acid
The consumption of saline solution, by tetraamido substituted metal phthalocyanine: mass percent concentration is the aqueous sulfuric acid of 50～70%: 1～
5mol/L nitrite aqueous solution is that the ratio of 1g:27.2～34mL:1.12～5.6mL calculates.
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| 金属四羧酸酞菁对烯烃的催化环氧化;黎林清等;《应用化学》;20111130;第28卷(第11期);1256-1262 * |
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