CN109983021B - Process for producing carboxyl metal phthalocyanine for producing dye and pigment - Google Patents
Process for producing carboxyl metal phthalocyanine for producing dye and pigment Download PDFInfo
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- CN109983021B CN109983021B CN201780024094.8A CN201780024094A CN109983021B CN 109983021 B CN109983021 B CN 109983021B CN 201780024094 A CN201780024094 A CN 201780024094A CN 109983021 B CN109983021 B CN 109983021B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
- C07D209/12—Radicals substituted by oxygen atoms
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- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
- C09B47/08—Preparation from other phthalocyanine compounds, e.g. cobaltphthalocyanineamine complex
- C09B47/24—Obtaining compounds having —COOH or —SO3H radicals, or derivatives thereof, directly bound to the phthalocyanine radical
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Abstract
The present application relates to an innovative process for the production of carboxymetal phthalocyanines, for the production of dyes and pigments in the textile industry and other fields, for the production of molecules at lower cost, with higher efficiency and with very low waste yields; the process comprises five steps, wherein the first step is cyclization reaction and formation of intermediate iron tetra subphthalocyanine (TI-FePc), and the yield is about 35%; the second step is to purify insoluble TI-FePc using the HCl solution recovered in the fifth step; thirdly, performing alkaline hydrolysis reaction by using the solution recovered in the fourth step to generate an intermediate iron octacarboxylate (OC-FePc); the fourth step is a calcium ion precipitation step, separating the pigment CaOC-FePc and recovering the NaOH solution reused in the third step; the fifth step is an acidification step with hydrochloric acid to convert the CaOC-FePc to product HOC-FePc and recovering the acid solution in the second and fifth steps for reuse.
Description
Application field
The present invention relates to a production process based on the functions of carboxyl metal phthalocyanine dye and pigment, which is used in textile industry and other fields.
Introduction to the invention
The patent requirements of the invention relate to an innovative production process of carboxyl metal phthalocyanine for producing dyes and pigments and how the carboxyl metal phthalocyanine is obtained.
Prior art
Phthalocyanines are compounds belonging to the class of planar macrocyclic aromatics having 18 pi free electrons in carbon and nitrogen atoms. 1.3 The structure of the compound is square and is formed by four isoindole units (-N=) connected by imine bridges, so that a cavity ring is formed, and four nitrogen atoms are contained. The cavity center of such macrocyclic compounds is capable of accepting 2H + (phthalocyanine free base) or linked metal ions, in particular transition metal ions in various oxidation states, to produce derivatives of metal phthalocyanines (MPcs). These macrocyclic compounds can form complexes with most of the metallic elements of the periodic table. 4
This unique electronic and molecular structure renders them photochemically, electrochemically and catalytically active, which properties can be controlled/tuned by the substitution of central metal ions for their oxidized state and their surrounding rings, as well as by the manner and degree of intermolecular association that is being explored by science and technology. For example, the strong intermolecular interactions of pi clouds (pi stacking) of such aggregates tend to form stacked structures, which can become very good electrical conductors when participating impurities. In addition, the phthalocyanine free base and its metal compounds have strong coloration as well as thermal and photochemical stability, which makes them useful in large amounts in textile products and in dyes and pigments for the printing and paint-ink industry. Phthalocyanines and their metal derivatives are materials used in various technical fields, such as molecular electronics, solar cells, photovoltaics, photonics, electrochromic displays, gas sensors, nonlinear optics, photodynamic therapy, liquid crystals, catalysis and electrocatalysis and nanotechnology, due to their electronic and redox properties. 1
Thus, mass production of phthalocyanines not substituted with metal ions of iron, nickel, cobalt, zinc, magnesium, etc. is in demand for the market, especially for pigment enterprises, in view of the simplicity and high efficiency of their cyclization reactions. However, the efficiency of this reaction is based on the type and amount of substituents present at the periphery of the ring, but the efficiency in reacting the substituents carboxylic acid/carboxylate is significantly lower. In fact, the number of carboxylic ester species attached to the ring is not economically competitive because of its reduced efficiency. However, these molecules have very good catalytic properties, in particular with respect to oxidation reactions, more particularly molecular oxygen-activated reactions. There are many reports on new uses and products for their antimicrobial properties and development of deodorizing functions. The cost of the higher efficiency production of mass production of carboxyl metal phthalocyanine is reduced, which brings feasibility to the development of new products and applications, especially dyes, pigments and functional additives suitable for various industries, including textile industry. Phthalocyanines can be formulated from a number of concentrates, such as 1, 2-dicyanobenzene (phthalonitrile), benzene-1, 2-dicarboxylic acid, carboxylic anhydride, 1, 2-dicarboxamide benzene, phthalimide and 1, 3-diiminoisoindoline. 1，5，6 The preparation of the free base phthalocyanine can be produced by heating phthalonitrile with a strong base in an alcohol. 5 The free base phthalocyanine can also be demetallized in a strong acid concentrated in MgPc in the presence of magnesium metal by heating in phthalonitrile. 5 MPcs, where m=metal ion, can be obtained by heating phthalonitrile (fig. 1) with anhydrous metal salt in a suitable solvent with high boiling point. In the case of carboxylic acid derivatives as reagents, such as anhydrides and amides and phthalimides and 1, 3-diiminoisoindolines, when the metal phthalocyanines are heated by nitrobenzene derivatives, catalysts in the presence of the respective metal salts and with a melting point of 133℃and urea as high-boiling solvent, in some cases also as source of nitrogen atoms. 5
The pivot of the Pcs and MPcs substituted with carboxylic acid groups (carboxyl metal phthalocyanine) is obtained by substituting the above-mentioned compounds with carboxylic acids and derivatives thereof, or by substituting nitrides at suitable positions. The imide derivative is synthesized during cyclization, the reaction efficiency is increased,hydrolysis in an alkaline medium yields the corresponding carboxylic acid derivative. 2.7.8 Such as: tetra-substituted MPc (FIG. 2) of imide groups is obtained by reacting anhydride or trimellitic acid (1, 2, 4-tricarboxybenzoic acid) with the desired metal salt, urea and a catalyst having a temperature of about 200deg.C. The imide group is then hydrolyzed by a strong base to yield the corresponding metallized octacarboxyphthalocyanine (OC-MPcs).
In the process for preparing metallized octacarboxyl phthalocyanines, the reaction is carried out using thermally induced pyromellitic dianhydride or 1,2,4, 5-tetrahydrobenzene cyano, usually ammonium molybdate or DBU (1, 8-diazabicyclo [5.4.0] undec-7-ene, a high boiling solvent, high efficiency) in the presence of the desired metal salt and catalyst. The 4 groups of phthalimides are substituted symmetrically for the MPc, followed by hydrolysis with a strong base, eight strongly basic carboxylate groups, and finally converted to carboxylic acid groups by acidification and precipitation, as shown in FIG. 3.
The carboxylate groups provide negative charge and solubility to the OC-MPc. These functional groups can be used in conjunction with fibers and with appropriate features to attach the position of substituents. Thus, the addition of a strong mineral acid results in the production of a poorly soluble carboxylic acid derivative by protonation to neutralize the negative charge, as shown in fig. 3. 2.9.10
The MPc tetra-substituted or octasubstituted process is performed in two stages as shown in FIGS. 2 and 3. The first stage takes part in the cyclization reaction, resulting in the formation of a macrocycle, resulting in the production of a black solid, a mixture of MPc (insoluble matter) and impurities in the process. The second stage is the chemical reaction of the phthalimide groups with concentrated aqueous alkali, with approximately 50% by mass of sodium hydroxide or potassium hydroxide releasing carboxylate groups. This high concentration is necessary because of the need to enhance the dissolving power and the function of eliminating organic impurities from the first stage. 7.11 Finally, the solution was acidified to pH 2.0 to precipitate the dye.
Japanese patent No. 10-101673, registered by Orient Chemical Co., ltd., osaka, 1998, the solvent used in the first stage of the production flow, the cyclization reaction and macrocyclic formation stage, are polyethylene glycol dialkyl ethers, and according to the patent need not be removed by evaporation after completion of the reaction. In a safe and simple way, it is possible to obtain a high-efficiency and low-cost production of metal phthalocyanines using urea. The second stage of the process removes the solvent and its decomposition products, which are the majority of the organic load in the sodium hydroxide residual solution.
However, the large amount and high concentration of the base used in the hydrolysis step, the large consumption in the acidification stage, in addition to the large amount of salt produced to precipitate with the desired product, causes octacarboxyl and tetracarboxylic phthalate derivatives, which are difficult to separate by-products of the chemical reaction. Since the carboxyphthalocyanine co-precipitates with sodium chloride to form very small particles, even if water is used to dissolve the salt (most of the mixture), it is difficult to separate by conventional filtration or precipitation methods. It is emphasized that these two factors present difficulties in the large-scale production of metallized tetracarboxylic and octacarboxylic phthalocyanine mixtures and transition metal ions. This is due to the high production costs and the need to dispose of and discard the waste to produce low value pollution. In addition, sodium chloride and potassium chloride, although not toxic, are largely disposed of in freshwater lakes or streams, even in salt water, can have unacceptable environmental impact and can be inspected by environmental authorities. There is a need to develop a production process that reduces or does not produce salts and waste during the production of the product, resulting in a production process that reduces costs and affects the environment as much as possible, resulting in sustainability. This can be achieved by developing new process flows and optimizing various parameters of the manufacturing process
Problems in the art today
The scheme for producing iron octacarboxylate phthalocyanine (HOC-FePc) by the Japanese method is shown in FIG. 4. The first stage is the cyclization reaction and the formation of the phthalocyanine ring. Reactant ferric (III) chloride (FeCl) 3 ) Pyromellitic dianhydride, urea (CH) 4 N 2 O), ammonium molybdate (NH) 4 ) 6 Mo 7 O 24 .4H 2 O) and polyethylene glycol dialkyl ether are mixed and heated to 180 ℃. In this stage tetra-subphthalocyanine (TI-FeP) is produced, precursors of HOC-FePc, urea being the donor of the nitrogen atom, converting the anhydrous acid groups into imide groups. In this first stage, a large amount of impurities are generatedThe chemical reaction efficiency is relatively low<50%) produce a large amount of solid byproducts including urea, catalyst, solvent, and reactants. It is important that the semi-product tetra sub-phthalocyanine (TI-FePc) obtained in this step is a solid insoluble in most organic solvents and water and contains a large amount of contaminants including oxide-hydroxides which are insoluble or poorly soluble in alkaline media such as iron. Even if concentrated sodium hydroxide solution (41.6 g NaOH per g HOC-FePc in the japanese process, see fig. 4) is used at 100 ℃, the hydrolysis of imide groups and the generation of carboxylate groups are used in the second stage of the scheme, resulting in soluble OC-FePc, but may not be sufficient to remove these types of contaminants. If these iron oxide-hydroxide contaminants are to be removed in a subsequent hydrochloric acid treatment, the carboxylate groups are acidified and protonated to carboxylic acids, yielding poorly soluble HOC-FePc, which are then physically separated. In this process, excess NaOH must be neutralized and excess hydrochloric acid should be added to reduce the pH to about 1, suitable for precipitation of the product, yielding a large amount of sodium chloride (about 61g NaCl per gram HOC-FePc) to precipitate with the desired product yielding a blue paste. 102.75 g of 37% HCl solution per g of HOC-FePc produced was used, but the consumption of hydrochloric acid was very large. The product in salt was extracted with NaOH solution and then reprecipitated in HCl solution.
Another related aspect that must be improved is the profitability of the process. A spectrophotometric study of the commercial product and the product produced according to the present patent application clearly showed that the commercially available dark blue solid contains a significant amount of impurities. The percentage of impurities reaches over 2/3, and the reported yield is 42% (according to Japanese patent No. 10-101673 in 1998) which is far from the actual situation, and if the pure product content is corrected, the yield is reduced to about 14%. The present patent application proposes alternatives to make the process more efficient and sustainable, and also to produce insoluble products suitable for use as pigments.
Abstract
As previously mentioned, it is desirable to minimize the formation of by-products and waste in the process stream iron octacarboxyphthalocyanine (HOC-FePc). Most of the descriptions in the literatureSeveral methods and japanese patent No. 10-101673 in 1998 use a high volume of 50% by weight sodium hydroxide or potassium hydroxide solution, which requires a large amount of hydrochloric acid solution to neutralize the solution and separate the product, thereby producing a large amount of sodium chloride or potassium chloride as a residue. 7.11 Therefore, by utilizing the structural and chemical characteristics of this molecule, a new and more efficient synthetic route has been developed, producing a product with high purity at a lower cost, with little waste (mainly salt) generated when compared with the conventional method and the method of Japanese patent No. 10-101673 in 1998, making the process more ecologically sustainable. This innovation is achieved by adding two strategic steps to this flow: a) Purification of iron tetra-subphthalocyanine (TI-FePc) the cyclization reaction is carried out using hydrochloric acid solution, eliminating most of the iron oxide-hydroxide impurities, b) hydrolysis of the dilute aqueous sodium hydroxide hydrolysis separation product using a calcium salt such as calcium chloride as a precipitant, thereby allowing reuse of the alkaline NaOH solution in the hydrolysis step, avoiding the undesired generation of sodium chloride. The combination of the above strategic steps prevents the formation of salts and the consumption of alkali and acid and the undesired by-products from impeding the separation of the HOC-FePc product. In addition, another poorly soluble CaOC-FePc product can be produced. Iron ions are easily replaced by other metal ions, just as calcium ions can be replaced by other divalent cations, resulting in a raw material for dyes and pigments.
Purpose(s)
The subject matter of the present application has been developed in view of the prior art, one of its objects being to provide a process for the production of carboxymetalloprotease phthalocyanines, providing a high productivity, such molecules having a low cost and a very low waste yield compared to traditional processes.
It is another object of the present application to prepare high purity carboxyl metal phthalocyanines and insoluble derivatives suitable for use as pigments.
Drawings
The content of this invention relates to a process for the production of carboxyl metal phthalocyanines for dyes and pigments, the details of which are illustrated in the following figures:
FIG. 1 shows organic materials for the preparation of metal phthalocyanines, phthalonitrile (a), benzene-1, 2-dicarboxylic acid (b) phthalic anhydride (c) and 1, 3-diiminoisoindoline (d).
Fig. 2 shows an organic material for preparing tetracarboxylic phthalocyanine, HTC-MPc and m=fe (II) or Fe (III) or Co (II) or Co (III) or Cu (I) or Cu (II) or Zn (II) or Ni (II) or Mn (III) or Cr (II) or Cr (III) or Mg (II) and other metal elements.
Fig. 3 shows an organic material for preparing octacarboxyphthalocyanine acid, HOC-MPc with m=fe (II) or Fe (III) or Co (II) or Co (III) or Cu (I) or Cu (II) or Zn (II) or Ni (II) or Mn (III) or Cr (II) or Cr (III) or Mg (II) and other metal elements.
FIG. 4 shows a conventional synthetic route for the production of OC-FePc and HOC-FePc.
FIG. 5 shows the novel synthetic routes for producing TI-FePc, OC-FePc, HOC-FePc and CaOC-FePc.
FIG. 6 depicts electron absorption spectra of two samples of OC-FePc in a 0.1mol L-1 NaOH solution. The solid line represents the spectrum of a commercial sample, produced by the methodology of the japanese patent. The dashed line shows the spectrum of the sample produced by the new method.
Drawings
Fig. 4:
4.1- "first stage"
4.2- "impurity"
4.3- "excessive"
4.4- "second stage-hydrolysis"
4.5- "excessive"
4.6- "excessive"
4.7- "excessive"
4.8- "impurity"
4.9- "third stage-precipitation"
4.10- "stage 4-Re-purification"
4.11- "impurity"
Fig. 5:
5.1- "diphenyl ether"
5.2- "first stage"
5.3- "diphenyl ether"
5.4- "impurity"
5.5- "second stage-purification"
5.6- "third stage-hydrolysis"
5.7- "excessive"
5.8- "fourth stage-precipitation"
5.9- "Filter"
5.10- "excessive"
5.11- "fifth stage-substitution Ca 2+ ”
Detailed Description
The innovation of the production process is to implement two strategic steps throughout the process of the general method described in the literature and in 1998 japanese patent No. 10-101673: a) The material from iron tetra sub-phthalocyanine (TI-FePc) is obtained by cyclisation with hydrochloric acid solution, eliminating most of the iron oxide-hydroxide impurities, and b) the product is separated by hydrolysis with dilute aqueous sodium hydroxide solution using the calcium salt of calcium chloride as precipitant, enabling the reuse of alkaline NaOH solution in the hydrolysis step, while preventing the generation of undesirably large amounts of sodium chloride. The purification of materials for the production of iron tetra-sub-phthalocyanine (TI-FePc) with hydrochloric acid solution, and the separation of the product CaOC-FePc with calcium chloride precipitant, and the recycling of the acid and base solutions are shown in fig. 5 and described in detail below. The new process can be divided into 5 steps:
step one: the cyclization reaction and the production of semi-finished iron tetra-subphthalocyanine (TI-FePc) have an efficiency of about 35%;
step two: recovering the insoluble TI-FePc purified with HCl solution in a fifth step;
step three: alkaline hydrolysis is carried out on the solution recovered in the fourth step to produce semi-finished product iron octacarboxyphthalocyanine (OC-FePc);
step four: precipitating with calcium ions, separating the CaOC-FePc pigment and recovering the NaOH solution reused in the third step;
step five: acidification with hydrochloric acid and conversion of CaOC-FePc to product HOC-FePc, the recovered acid solution is reused in the second and fifth steps.
In the first step of forming the metal phthalocyanine ring, the reactants iron (III) chloride (FeCl 3), urea (CH 4N 2O), ammonium molybdate tetrahydrate ((NH46Mo7O24.4H2O) and pyromellitic dianhydride are intimately mixed and warmed to 180℃in diphenyl ether to promote the cyclization reaction, in view of the lower reaction yield, about 35%, there are several solid by-products, mainly iron oxide-hydroxides, molybdenum compounds and urea decomposition products and diphenyl ether solvents, in addition to the iron tetra-subphthalocyanine precursor TI-FePc.
The use of diphenyl ether instead of polyethylene glycol dialkyl ether solvent (of the present patent application) is very advantageous, and allows the productivity in the production reaction of metal phthalocyanine to be as high as 150% compared with the method described in japanese patent No. 10-101673 in 1998. In addition, in order to increase the purity of the final product and minimize the amount of sodium hydroxide used, purification (second step) is performed to remove most of the solid impurities generated in the first step. In fact, the impurity may coat the Ti-FePc particles reducing the hydrolysis reaction rate of the derivative. The purification process (second step) deals with the solids produced in the first step, the hydrochloric acid solution dissolving the organic and inorganic substances formed in the reaction medium. During purification, TI-FePc remains in solid form, which facilitates its separation from the hydrochloric acid solution. Importantly, this solution does not require neutralization and the hydrochloric acid solution can be treated for reuse in the purification of TI-FePc. However, we have to remember that the fifth step brings about a solution that generates less pollution and is suitable for this procedure. The reagent reuse flow is shown in FIG. 5 by the dashed arrow.
In a third step, the purified TI-FePc is hydrolyzed with sodium hydroxide. This step is carried out with a more dilute alkaline solution than the conventional method due to its higher purity. In this new process, only 2.0 g of sodium hydroxide was used to produce 1g of dye, resulting in an economic efficiency of about 95% compared with the process described in Japanese patent No. 10-101673 of 1998. At the end of this step, a solution of soluble OC-FePc was obtained from the reaction medium due to the eight negative electrons. In the fourth step, the CaOC-FePc is separated by adding a calcium chloride solution as a precipitant without adding a non-aqueous solutionThe organic acid neutralizes the molecules of the carboxylate group. Thus, instead of protonation with mineral acids, selective binding of cations is used to attach the OC-FePc molecules, thereby promoting the formation of insoluble solids from CaOC-FePc, which allows iron phthalocyanine to be separated without the need to neutralize NaOH solution. Thus, sodium hydroxide (Na 2 SO 4 Responsible for CaSO 4 Precipitation of(s) and Ca 2+ Ion separation) and used for hydrolysis of intermediate TI-FePc. The solid obtained in this step can be used as a functional pigment. Finally, the production of the carboxylic acid derivative HOC-FePc is necessary with H + Instead of Ca 2+ Ions. This is accomplished by chemical reaction of solid CaOC-FePc with HCl solution. In this way the desired product is separated from the acid solution of calcium chloride, which can be reused in this same stage for feeding another batch of Ca 2+ Protonation/replacement of the ion, or purification of the intermediate TI-FePc in the second step. However, before, the solution should be treated with sulfuric acid and a precipitate of CaSO4 isolated. All of the acid and base solutions used in the new process are reused, resulting in high reagent economy.
This new process can save about 95% of alkali (NaOH) and acid. The consumption of the hydrochloric acid solution in the present process is used for purification of the precursor and protonation of OC-FePc. It was estimated that 15g of 37% HCl solution per batch resulted in an economic efficiency of 85% compared to the Japanese method. In addition, an important part is replaced by cheaper sulfuric acid. Since the sodium hydroxide and hydrochloric acid solution are reused in the next batch, no undesirable sodium chloride is produced in the process. The only salt formed in the process is a small amount of calcium chloride or calcium sulfate itself. The strategy of using calcium salts as precipitants does not lead to an increase in process costs, since this is an inexpensive reagent (which is about one fifth the price of hydrochloric acid) and is non-toxic.
As mentioned before, all reagent savings are a result of the use of calcium chloride in the production process, which makes possible the recovery and reuse of sodium hydroxide solution as hydrochloric acid, avoiding the formation of large amounts of unwanted substances such as sodium chloride. If 2 g of HOC-FePc product were produced in two batches, the sodium hydroxide and hydrochloric acid savings were 97% and 92%, respectively.
In addition to the more economically viable synthetic route, high purity products are obtained. The purity of the sample can be readily verified by techniques such as Ultraviolet (UV) and visible (vis) absorption spectroscopy. Metal phthalocyanines exhibit very characteristic electron spectra in the visible and ultraviolet regions, 1.5 this allows the use of these molecules as dyes and pigments in the textile industry. The electron spectrum has a strong absorption band, a region between 600 and 700 nanometers called the Q-band, and a second band of lower intensity around 600 nm. In the ultraviolet region, the medium intensity band around 350 nm is called the Soret band (Soret). The electron absorption spectra of two OC-FePc samples, one commercial and one produced according to the present procedure, are shown in fig. 6. This plot is presented as molar absorptivity (epsilon) as a function of wavelength to facilitate comparison of the purity of the two samples. The continuous line is the spectrum of a commercial sample produced by the method of Japanese patent No. 10-101673 in 1998. In addition to the shoulder at 654nm, the band of maximum intensity was observed in the visible region of 682 and 620nm, which is not common in the metal phthalocyanine spectrum. There is also a UV band at 344nm, which is more intense than the band at 682 nm. The dashed line represents the sample spectrum obtained from the new production run (this patent). The similarity between the two spectra, with absorption maxima at 682 and 620nm, indicates that it is the same compound. However, the Soxhlet band at 351 nm is less intense than the band at 682nm, just as the expected metal phthalocyanine. 1.5 This is important in phthalocyanine derivatives, where the band in the 600 to 700 nm range is generally more intense than in the uv range. 1.5 This was found to be a strong indication of the presence of impurities in the sample produced by the method of Japanese patent No. 10-101673 in 1998. The most obvious difference between the spectra of the two samples is that the method of the present application produces samples with higher molar absorbance (epsilon) in all absorption bands (dashed line). The molar absorptivity epsilon is an inherent property of each substance and is determined by the following formula:
A＝εb C
wherein: a is the absorbance of the sample at one wavelength, ε is the molar absorptivity (Lmol -1 cm -1 ) At this wavelength, C is the concentration of the solution (molL-1) and b is the optical path length of the sample, typically 1.00 cm.
As can be seen from fig. 6, the molar absorptivity (dotted line) of the product of the new process at 682nm is about 3.34 times higher than that of the material prepared by the japanese process. While epsilon is an inherent property of each substance, the actual concentration of a compound in solution is directly affected by its purity. Impurities can cause a relative amount of epsilon proportion in the sample to decrease. Thus, the lower epsilon value is due to the lower mass in the compound. In other words, the sample produced by the japanese patent method showed a large amount of impurities, about 70%, as compared to the material produced by the method of the present patent application. That is, to have the same mass of HOC-FePc, japanese method No. 10-101673 in 1998 produced a material of three times the mass. The efficiency of Japanese patent application No. 10-101673 in 1998 was about 12% and the yield of the new process was about 36% due to the presence of impurities. In this way the new procedure is more economically viable and effectively produces higher purity products, thus making the production of these materials (dyes and pigments) more competitive.
The ratio of the japanese process locations to the new process locations schemes herein is shown in fig. 4 and 5, respectively. The following is a typical example of the preparation of HOC-FePc.
Example
Example 1:
2.8 g FeCl 2 ·4H 2 O,10.0 g of pyromellitic dianhydride, 1.4g of ammonium molybdate and 22.9g of urea, the solid mixture was carefully ground, 40 g of diphenyl ether was added to the mixture, and the temperature of the mixture was raised to 180℃with stirring for 4 hours. The dark solid was filtered, washed with ethanol, extracted with 100mL of 1.5M NaOH solution over 6 hours under reflux and diluted with 300mL of water. Then CaCl is added 2 (4.8 g in 30mL of water) was filtered to separate the precipitate. The filtered solid was then treated with 100mL of 3.0M HCl for 30 minutes with stirring, filtered, washed with water and dried. Yield: 3.0 g HOC-FePc.
Example 2:
7.40 g FeCl 3 10.0g of pyromellitic dianhydride, 14g ammonium molybdate and 22.9g urea, the solid mixture was carefully ground, 40 g diphenyl ether was added, and the temperature of the mixture was raised to 180℃with stirring for 4 hours. The dark solid was filtered, washed with ethanol, treated with 100mL of 3M HCl solution, shaken for 6 hours, filtered, and extracted with 100mL of 1.5M NaOH for 6 hours under reflux. Then CaCl is added 2 (4.8 g in 300mL of water) was filtered to separate the precipitate. The filtered solid was then shaken with 100mL of 3.0M HCl for 30 minutes with stirring, the solid filtered and then washed with water and dried. Yield: 4.0 g HOC-FePc.
Example 3:
3.70 g FeCl 3 10.0g of pyromellitic dianhydride, 1.4g of ammonium molybdate and 22.9g of urea, and the solid mixture was carefully ground, 40 g of diphenyl ether was added to the mixture, and the temperature of the mixture was raised to 180℃with stirring for 4 hours. The dark solid was filtered, washed with ethanol, treated with 100mL of 3M HCl solution, shaken for 6 hours, filtered, and extracted with 100mL of 1.5M NaOH for 6 hours under reflux. Then CaCl is added 2 (4.8 g in 300mL of water) was filtered to separate the precipitate. The filtered solid was then shaken with 100mL of 3.0M HCl for 30 minutes with stirring, the solid filtered and then washed with water and dried. Purity can be increased by repeating the washing procedure. Yield: 1.5 g HOC-FePc.
Example 4:
5.45 g CoCl 2 ·6H 2 O,10.0 g of pyromellitic dianhydride, 1.4g of ammonium molybdate and 22.9g of urea, the solid mixture was carefully ground, 40 g of diphenyl ether was added to the mixture, and the temperature of the mixture was raised to 180℃with stirring for 4 hours. The dark solid was filtered, washed with ethanol, treated with 100mL of 3M HCl solution, shaken for 6 hours, filtered, and refluxed for 100mL of 1.5M NaOH for 6 hours. Is treated with shaking for 6 hours, filtered and 100mL of 1.5M NaOH is extracted under reflux for 6 hours. Then CaCl is added 2 (4.8 g in 300mL of water) was filtered to separate the precipitate. The filtered solid was then shaken with 100mL of 3.0M HCl for 30 minutes with stirring, the solid filtered and then washed with water and dried. Purity can be increased by repeating the washing procedure. Yield: 4.0 g HOC-CoPc.
Example 5:
5.0 g Zn (CH) 3 CO 2 )2H 2 O,10.0 g of pyromellitic dianhydride, 1.4g of ammonium molybdate and 22.9g of urea, the solid mixture was carefully ground, 40 g of diphenyl ether was added to the mixture, and the temperature of the mixture was raised to 180℃with stirring for 4 hours. The dark solid was filtered, washed with ethanol, treated with 100mL of 3M HCl solution, shaken for 6 hours, filtered, and extracted with 100mL of 1.5M NaOH for 6 hours under reflux. Then CaCl is added 2 (4.8 g in 300mL of water) was filtered to separate the precipitate. The filtered solid was then shaken with 100mL of 3.0M HCl for 30 minutes with stirring, the solid filtered and then washed with water and dried. Purity can be increased by repeating the washing procedure.
Yield: 2.0 g HOC-ZnP.
The processes of examples 1,2,3,4 and 5 may undergo some variations, which will be mentioned below, and which may affect the reaction yield and purity of the final product. It is evident that in this process the exchange of a metal ion salt by another metal element will result in a metallized octacarboxyphthalocyanine with a different metal and in a different dye and pigment.
The proportions of reactants in examples 1,2,3,4 and 5 are based on the molar amount of catalyst (ammonium molybdate), or 1 mole of ammonium molybdate; 12.43 mol of iron (II) chloride tetrahydrate are added in example 1; 40.47 mol FeCl in example 2 3 The method comprises the steps of carrying out a first treatment on the surface of the 20.23 moles FeCl in example 3 3 The method comprises the steps of carrying out a first treatment on the surface of the 20.23mol CoCl in example 4 2 ·6H 2 O and 20.23mol of Zn (CH) in example 5 3 CO 2 )·2H 2 O; pyromellitic dianhydride 40.47 moles, 336.58 moles of urea and 207.45 moles of diphenyl ether. Regarding iron (II) chloride tetrahydrate, the ratio between reactants may be in the range of 1 to 50 moles and other salts used in examples 2 to 5; 1 to 162 moles of pyromellitic dianhydride; 1 to 1500 moles of urea and 0-2000 moles of diphenyl ether to produce a reaction mixture suitable for use in producing a composition of TI-FePc intermediate.
In examples 1 to 5, ammonium molybdate may be replaced by 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU), 1, 5-diazabicyclo [4.3.0] non-5-ene (DBN), triethylamine, 2-aminoethanol, diethanolamine or triethanolamine.
In examples 1 to 5, iron (II) chloride tetrahydrate may be substituted with other metal salts, typically transition metal salts (anhydrous or hydrated) such as Fe (II), fe (III), co (II), co (III), cu (II), ni (II), mn (III), cr (II), cr (III), zn (II), and representatively Mg (II), li (I), including anions such as halides, carboxylates, acetates, oxalates, nitrates, sulfates, perchlorates, trifluoroacetates, trifluoromethane sulfonates, tetrafluoroborates, hexafluorophosphates, and the like.
In examples 1 to 5, pyromellitic dianhydride may be substituted with 1,2,4, 5-tetracyanobenzene, benzene-1, 2,4, 5-tetracarboxylic acid, 1,2,4, 5-tetracarboxylic acid amide benzene and pyromellitic diimide.
In examples 1 to 5, pyromellitic dianhydride may be replaced with trimellitic anhydride (1, 2, 4-tricarboxybenzoic acid-1, 2-anhydride or 1,2, 4-tricarboxybenzoic acid 1, 2-anhydride) (FIG. 2) or 1,2, 4-tricarboxybenzoic acid or 1, 2-anhydrotrimellitic acid chloride or 1,2, 4-tricarboxamide benzene.
In examples 1 to 5, the reaction temperature may be in the range of 50 to 250 ℃.
In examples 1 to 5, the reaction time may vary from 1 to 12 hours.
In examples 1 to 5, the diphenyl ether solvent may be substituted with other high boiling point solvents such as dimethylformamide, diethylformamide, nitrobenzene, 2-aminoethanol, diethanolamine, triethanolamine, ethylene glycol, diethylene glycol, polyhydric alcohols, dialkyl esters of polyhydric alcohols, polyethylene glycol dialkyl ethers and the like.
In examples 1 to 5, solvents such as methanol, acetone, acetonitrile, propanol, isopropanol, butanol, diethyl ether, etc. may be used for the washing step.
In examples 1 to 5, the volume of the hydrochloric acid solution used for the treatment may be in the range of 10 to 3000 ml and the concentration thereof may be varied between 0.001 and 12M. Hydrochloric acid may be replaced by strong acids such as sulfuric acid, nitric acid, perchloric acid, hydrobromic acid, hydroiodic acid and trifluoroacetic acid. The reaction time can vary between 30 minutes and 12 hours. In examples 1 to 5, the concentration of the alkali may be from 0.001 to 25M sodium hydroxide or potassium hydroxide, or the like.
In examples 1 to 5, the hydrolysis temperature was 50 to 120℃and the reaction time was 0.1 to 24 hours.
In examples 1 to 5, caCl 2 The mass of (2) may be in the range of 0.1 to 10.0g and the volume for dissolving the salt may be in the range of 1 to 1000 ml.
In examples 1 to 5, the calcium chloride may be replaced by salts (anhydrous or hydrated) such as nitrates, bromides, formates, acetates and triflates, or by hydroxides (anhydrous or hydrated) of Ca (II), ba (II), mg (II), sr (II) and the like or transition metal or lanthanide salts.
In examples 1 to 5, the precipitant may be replaced with a strong acid such as hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, perchloric acid, trifluoroacetic acid, trifluoromethanesulfonic acid and the like.
In examples 1 to 5, the volume of hydrochloric acid (or other acid) varied between 10.0 and 1000mL, with a concentration in the range of 0.001-16M solution.
In examples 1 to 5, the acid treatment time may be in the range of 0.1 to 6 hours.
Reference to
1.Mack,J.；Kobayashi,N.,Low Symmetry Phthalocyanines and Their Analogues.Chemical Reviews,2011.111(2):p.281-321.
2.Dumoulin,F.；
M.；Ahsen,V.；Nyokong,T.,Synthetic pathways to water-soluble phthalocyanines and close analogs.Coordination Chemistry Reviews,2010.254(23–24):p.2792-2847.
3.Rio,Y.；Salome Rodriguez-Morgade,M.；Torres,T.,Modulating the electronic properties of porphyrinoids:a voyage from the violet to the infrared regions of the electromagnetic spectrum.Organic&Biomolecular Chemistry,2008.6(11):p.1877-1894.
4.Sorokin,A.B.,Phthalocyanine Metal Complexes in Catalysis.Chemical Reviews,2013.113(10):p.8152-8191.
5.Kudrevich,S.V.；van Lier,J.E.,Azaanalogs of phthalocyanine:syntheses and properties.Coordination Chemistry Reviews,1996.156:p.163-182.
6.Nemykin,V.N.；Lukyanets,E.A.,Synthesis of substituted phthalocyanines.Arkivoc,2010.2010(1):p.136-208.
7.Boston,D.R.；Bailar,J.C.,Phthalocyanine derivatives from 1,2,4,5-30tetracyanobenzene or pyromellitic dianhydride and metal salts.Inorganic Chemistry,1972.11(7):p.1578-1583.
8.Nackiewicz,J.；Kliber,M.,Synthesis and selected properties of metallo and metal-free 2,3,9,10,16,17,23,24–octacarboxyphthalocyanines.Arkivoc,2015.2015(1):p.269-299.
9.Shaposhnikov,G.P.；Maizlish,V.E.；Kulinich,V.P.,Carboxy-substituted Phthalocyanine Metal Complexes.Russ J Gen Chem,2005.75(9):p.1480-1488.
10.Shirai,H.；Maruyama,A.；Kobayashi,K.；Hojo,N.；Urushido,K.,Functional metal-porphyrazine derivatives and their polymers,4.Synthesis of poly(styrene)bonded Fe(III)-as well as Co(II)-4,4′,4″,4″′-tetracarboxyphthalocyanine and their catalase-like activity.Die Makromolekulare Chemie,1980.181(3):p.575-584.
11.Sakamoto,K.；Ohno,E.,Synthesis of cobalt phthalocyanine derivatives and their cyclic voltammograms.Dyes and Pigments,1997.35(4):p.375-386.
Claims (12)
1. Method for producing octacarboxymetal-phthalocyanine M 'OC-MPc for the production of dyes and pigments, wherein M' is H + Or Ca 2+ Ion, and M is a metal ion selected from the group consisting of Fe (II), fe (III), co (II), co (III), ni (II), mn (II), cr (II) or Zn (II), characterized in that the first step is the formation of a metal phthalocyanine ring by reacting a salt of the element M with urea and pyromellitic dianhydride in the presence of a catalyst, wherein all the components are intimately mixed, and when the temperature is raised to 180 in a high boiling solvent, promote the cyclization reaction which yields, in addition to the macrocyclic precursor metallized tetra-imide phthalocyanine TI-MPc, various solid by-products, mainly oxides of the M metal-hydroxide, molybdenum compound and urea and solvent decomposition products; removing these byproducts in a second step, treating the solid produced in the first step with organic and inorganic substances formed by dissolving the reaction medium in a hydrochloric acid solution, while the TI-MPc precursor remains in solid form; then in a third step, hydrolyzing with sodium hydroxide solution, generating a soluble octacarboxyl metal phthalocyanine OC-MPc solution due to the eight negative electrons; in the fourth step, it interacts with the calcium chloride solution to promote the precipitation and separation of the octacarboxy metal phthalocyanine calcium salt CaOC-MPc; and in a fourth step enables recovery of the resulting sodium hydroxide-containing solution by adding sodium sulfate to enable Ca 2+ Ions are precipitated and isolated from the solution used in the hydrolysis of the TI-MPc intermediate as insoluble calcium sulfate; the fifth step is to add hydrochloric acid with 2H + Substitution of Ca 2+ Converting CaOC-MPc to octacarboxylic acid metal phthalocyanine HOC-MPc product and recovering excess acid for reuse in the second or fifth step, wherein the catalyst is selected from 1, 8-diazabicyclo [5.4.0]Undec-7-ene, 1, 5-diazabicyclo [4.3.0]Non-5-ene, or ammonium molybdate tetrahydrate (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O。
2. The process for the production of octacarboxymetal-phthalocyanine M' OC-MPc for use in the production of dyes and pigments according to claim 1, characterized in that the element M in the salt is selected from iron, zinc or cobalt, yielding the corresponding metallized carboxyphthalocyanine.
3. The process for the production of octacarboxymetal-phthalocyanine M' OC-MPc for use in the production of dyes and pigments according to claim 2, characterized in that the element M in the salt is iron and cobalt.
4. The process for the production of octacarboxymetal-phthalocyanine M' OC-MPc for use in the production of dyes and pigments according to claim 1, characterized in that the metallized tetraimide phthalocyanines are TI-FePc and TI-CoPc.
5. A production method of octacarboxy metal-phthalocyanine M' OC-MPc for use in the production of dyes and pigments according to any of claims 1 to 3, characterized in that the high boiling solvent is diphenyl ether.
6. A process for the production of octacarboxymetal-phthalocyanine M' OC-MPc for use in the production of dyes and pigments according to any one of claims 1 to 3, characterized in that the high boiling solvent is dimethylformamide, diethylformamide, nitrobenzene, 2-aminoethanol, diethanolamine, triethanolamine, ethylene glycol and diethylene glycol.
7. A process for the production of octacarboxymetal-phthalocyanine M' OC-MPc for use in the production of dyes and pigments according to any one of claims 1 to 3, characterized in that HOC-MPc is obtained from the reaction of solid CaOC-MPc with an acid solution by the use of 2H + Instead of Ca 2+ The ions convert CaOC-MPc to HOC-MPc; the neutral desired product is separated from the acid calcium chloride solution which is capable of another batch of Ca at the same step 2+ The ion is reused in the protonation/substitution or in the second step of purification of the TI-MPc intermediate, in which case the solution is treated beforehand with sulfuric acid and precipitated to isolate CaSO 4 。
8. The process for producing octacarboxyl metal-phthalocyanine M' OC-MPc for dyes and pigments according to claim 7, characterized in that the acid solution is a hydrochloric acid solution.
9. A process for the production of octacarboxy metal-phthalocyanine M' OC-MPc for use in the production of dyes and pigments according to any of claims 1 to 3, characterized in that the solid obtained in the fifth step of the process is used as a functional pigment.
10. A production method for octacarboxy metal-phthalocyanine M' OC-MPc for use in the production of dyes and pigments according to any of claims 1 to 3, characterized in that the hydrochloric acid solution used in the fifth step is treated and reused for purifying TI-MPc.
11. A production method for octacarboxy metal-phthalocyanine M' OC-MPc for use in the production of dyes and pigments according to any of claims 1 to 3, characterized in that the sodium hydroxide solution used in the third step is treated and reused for the hydrolysis of TI-MPc.
12. A process for producing octacarboxymetal-phthalocyanine M ' OC-MPc for use in the production of dyes and pigments according to any one of claims 1 to 3, characterized in that the element M ' in M ' OC-MPc is Ca 2+ Ions.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH101673A (en) * | 1996-06-14 | 1998-01-06 | Seiko Epson Corp | Liquid crystal display element |
| CN1583748A (en) * | 2004-06-14 | 2005-02-23 | 浙江理工大学 | Metalphthalocyanine derivative, salt and preparing method thereof |
| CN102241681A (en) * | 2011-04-28 | 2011-11-16 | 山东大学威海分校 | Preparation method of carboxyl-substituted metal phthalocyanine |
| CN102675625A (en) * | 2012-04-27 | 2012-09-19 | 东华大学 | Preparation method for water-solubility metal phthalocyanine derivative |
| CN105583009A (en) * | 2016-01-21 | 2016-05-18 | 浙江理工大学 | FePc(COOH)8 sensitized TiO2 catalyst and synthetic method thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS535329B1 (en) * | 1970-07-24 | 1978-02-25 | ||
| JPS62111985A (en) * | 1979-10-31 | 1987-05-22 | Hiroyoshi Shirai | Metal phthalocyaniepolycarboxylic acid |
| JP2798285B2 (en) * | 1989-12-25 | 1998-09-17 | 日清製粉株式会社 | Purification and isolation method of metal phthalocyanine derivative |
| JP4057080B2 (en) * | 1996-10-02 | 2008-03-05 | オリヱント化学工業株式会社 | Method for producing metal phthalocyanine compound |
| GB9817236D0 (en) * | 1998-08-08 | 1998-10-07 | Zeneca Ltd | Compound,composition and use |
| JP2002097497A (en) | 2000-09-22 | 2002-04-02 | Berubikku:Kk | Solid soap |
| JP6263168B2 (en) * | 2013-04-24 | 2018-01-17 | クミアイ化学工業株式会社 | Metal phthalocyanine polymer, electrocatalyst using the same, and production method thereof |
-
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH101673A (en) * | 1996-06-14 | 1998-01-06 | Seiko Epson Corp | Liquid crystal display element |
| CN1583748A (en) * | 2004-06-14 | 2005-02-23 | 浙江理工大学 | Metalphthalocyanine derivative, salt and preparing method thereof |
| CN102241681A (en) * | 2011-04-28 | 2011-11-16 | 山东大学威海分校 | Preparation method of carboxyl-substituted metal phthalocyanine |
| CN102675625A (en) * | 2012-04-27 | 2012-09-19 | 东华大学 | Preparation method for water-solubility metal phthalocyanine derivative |
| CN105583009A (en) * | 2016-01-21 | 2016-05-18 | 浙江理工大学 | FePc(COOH)8 sensitized TiO2 catalyst and synthetic method thereof |
Non-Patent Citations (4)
| Title |
|---|
| 八羧基酞菁铜的合成研究;唐志辉等;《化学工程师》;20101231(第6期);第08-09页 * |
| 含羧基酞菁锌及其白蛋白共价结合物的制备与光谱性质;肖荣平;《中国博士学位论文全文数据库 工程科技I辑》;20140531(第5期);第8-9页 * |
| 昆士兰氧化铝厂赤泥处置方法和复垦实验效果;殷德洪等;《轻金属》;19951231;第24页左栏 * |
| 黄山秀等.1.3.5 其他脱碱方法.《赤泥性质与利用研究》.2015, * |
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