CN109983021B - Production technology of carboxyl metal phthalocyanine for producing dyes and pigments - Google Patents

Abstract

This application relates to an innovative process for the production of carboxylated metallophthalocyanines for the production of dyes and pigments in the textile industry and other fields, the molecule is produced at a lower cost, it has a higher efficiency and its waste yield is very low; its procedure includes Five steps, the first step is the cyclization reaction and the formation of the intermediate iron tetrasubphthalocyanine (TI-FePc), the yield rate is about 35%; the second step is to use the recovered HCl solution in the fifth step to purify the insoluble TI-FePc ; The third step is to use the solution recovered in the fourth step to carry out alkaline hydrolysis reaction to generate the intermediate octacarboxyphthalocyanine iron (OC-FePc); the fourth step is a calcium ion precipitation step, which separates the pigment CaOC-FePc and reclaims the The NaOH solution reused in the three steps; the fifth step is an acidification step with hydrochloric acid to convert CaOC-FePc into the product HOC-FePc and recover the acid solution in the second and fifth steps for reuse.

Description

Production technology of carboxyl metal phthalocyanine for producing dyes and pigments

Application field

The patent requirement of the present invention is a production process based on the dye and pigment functions of carboxyl metal phthalocyanine, which is used in the textile industry and other fields.

foreword

The patent requirement of the present invention is about an innovative production process of carboxyl metal phthalocyanine to produce dyes and pigments, and how carboxyl metal phthalocyanine is obtained.

existing technology

Phthalocyanine is a planar macrocyclic aromatic compound with 18π free electrons in carbon and nitrogen atoms. ^1.3 It is organized in a square shape and is formed by four isoindole units (-N=) connected by imine bridges, forming a cavity ring containing four nitrogens. The cavity centers of such macrocycles are capable of accepting 2H ⁺ (phthalocyanine free base) or linking metal ions, especially transition metal ions in various oxidation states, to produce metallophthalocyanine derivatives (MPcs). These macrocyclic compounds can form complexes with most of the metal elements in the periodic table. ⁴

This unique electronic and molecular structure makes them photochemical, electrochemical and catalytic, and this property can be controlled/tuned with the central metal ion and its oxidation state and the substituents on the surrounding rings, as well as scientific and The different properties brought about by the way and degree of association between molecules that science and technology are exploring. For example, the strong intermolecular interactions resulting from the π cloud (π stacking) of such aggregates tend to form stacked structures, which can become very good electrical conductors when participating impurities. In addition, phthalocyanine free base and its metal compounds have strong coloring, thermal stability and photochemical stability, making them widely used in dyes and pigments for textile products and printing and paint ink industries. Due to their electronic and redox properties, phthalocyanines and their metal derivatives are materials used in various technical fields such as molecular electronics, solar cells, photovoltaics, photonic devices, electrochromic displays, gas sensors, nonlinear optics, Photodynamic therapy, liquid crystals, catalysis and electrocatalysis and nanotechnology. ¹

In this way, the mass production of phthalocyanines not replaced by iron, nickel, cobalt, zinc, magnesium and other metal ions can supply the market demand, especially for pigment enterprises, in view of the simplicity and high efficiency of its cyclization reaction. However, the efficiency of this reaction depends on the type and amount of substituents present at the periphery of the ring, but in the reaction of substituents carboxylic acids/carboxylates the efficiency is significantly lower. In fact, since the number of carboxylate species attached to the ring reduces efficiency, it is not economically competitive. But these molecules have very good catalytic properties, especially for reactions involving oxidation, and more specifically, reactions activated by molecular oxygen. There are many reports on the development of new uses and products for their antimicrobial properties and deodorizing functions. The cost reduction of higher efficiency production of carboxyl metal phthalocyanines in large quantities has brought feasibility to the development of new products and applications, especially dyes, pigments and functional additives for various industries, including the textile industry. Phthalocyanines can be formulated from many concentrates such as 1,2-dicyanobenzene (phthalonitrile), benzene-1,2-dicarboxylic acid, carboxylic anhydride, 1,2-dicarboxyamidobenzene, o-phthalonitrile Dicarboximide and 1,3-diiminoisoindoline. ^1,5,6 Preparation of free base phthalocyanine can be produced by heating phthalonitrile with strong base in alcohol. ⁵ Free base phthalocyanine can also be heated in phthalonitrile, and in the presence of metal magnesium, it can be demetallated in MgPc concentrated strong acid. ⁵ MPcs, where M = metal ion, can be obtained by heating phthalonitrile (Figure 1) with anhydrous metal salts in a suitable solvent with a high boiling point. When using carboxylic acid derivatives as reagents, such as anhydrides and amides, as well as phthalimide and 1,3-diiminoisoindoline, when metal phthalocyanines are heated by nitrobenzene derivatives, in Catalysts and urea with a melting point of 133° C. in the presence of respective metal salts are high-boiling solvents, and in some cases can also be used as a source of nitrogen atoms. ⁵

The production of Pcs and MPcs substituted by carboxylic acid groups (carboxymetallophthalocyanines) is by replacing the above compounds with carboxylic acids and their derivatives, or nitrides in place. In the cyclization process, imide derivatives are produced to increase the reaction efficiency, and the corresponding carboxylic acid derivatives are produced by hydrolysis in alkaline medium. ^2.7.8 For example: the four-substituted MPc of the imide group (Figure 2) is composed of acid anhydride or trimellitic acid (1,2,4-tricarboxybenzoic acid) with the desired metal salt, urea and a temperature of about Catalyst reaction at 200°C. The imide group is then hydrolyzed by a strong base to generate the corresponding metallated octacarboxyphthalocyanines (OC-MPcs).

In the process for the preparation of metallated octacarboxyphthalocyanines, thermally induced pyromellitic dianhydride or 1,2,4,5-tetrahydrocyanocyanide is used with the required metal salt and catalyst, usually ammonium molybdate Or DBU (1,8-diazabicyclo[5.4.0]undec-7-ene, a solvent with a high boiling point, high efficiency), for the reaction. Four groups of phthalimides are substituted for MPc in a symmetrical formula, and then hydrolyzed with a strong base, and eight strong basic carboxylate groups are finally converted into carboxylic acid groups by acidification and precipitation, as shown in Figure 3 shown.

The carboxylate group provides negative charge and solubility to OC-MPc. These functional groups can be used to attach to the fiber and, with appropriate features, to attach the substituent sites. Thus, the addition of a strong mineral acid resulted in the production of poorly soluble carboxylic acid derivatives by neutralizing the negative charge by protonation, as shown in FIG. 3 . ^2.9.10

The production process of MPc four-substitution or eight-substitution is divided into two stages, as shown in Figure 2 and Figure 3. The first stage is involved in the cyclization reaction, resulting in the formation of a macrocycle, resulting in a black solid, a result of a mixture of MPc (insolubles) and impurities in the process. The second stage is hydrolysis, the chemical reaction of phthalimide groups with a concentrated aqueous base solution, about 50% by mass of sodium hydroxide or potassium hydroxide to release carboxylate groups. This high concentration is necessary because of the need to enhance solvency and eliminate organic impurities from the first stage. ^7.11 Finally, acidify the solution to pH 2.0 to precipitate the dye.

In 1998, Orient Chemical Co., Osaka, Japan registered Japanese Patent No. 10-101673. The solvent used in the first stage of the production process, the stage of cyclization reaction and macrocycle formation, is polyethylene glycol dialkyl ether, according to The patent does not need to be removed by evaporation after the reaction is complete. In a safe and simple way, it is possible to obtain high-efficiency and low-cost production of metallophthalocyanines using urea. The second stage of the flow process of the process removes the solvent and its decomposition products, which belong to most of the organic load in the sodium hydroxide residual solution.

However, the large amount and high concentration of alkali used in the hydrolysis step, and the large consumption in the acidification stage, in addition to producing a large amount of salt precipitated with the desired product to form octacarboxylic and tetracarboxylic phthalate derivatives, the by-products of this chemical reaction Difficulty separating. Since carboxyphthalocyanine co-precipitates with sodium chloride to form very small particles, even using water to dissolve the salt (most of the mixture) is difficult to separate by conventional filtration or precipitation methods. It should be emphasized that these two factors make it difficult to produce metallated tetracarboxylic and octacarboxylic phthalocyanine mixtures with transition metal ions on a large scale. This is due to higher production costs and the generation of low-value polluting waste that needs to be treated and discarded. In addition, although sodium chloride and potassium chloride are not poisonous, if they are discarded in large quantities in freshwater lakes or streams, even in salt water, they will have unacceptable impact on the environment and will be inspected by environmental protection agencies. It is necessary to develop a production process that reduces or does not generate salt and waste in the process of product production, so as to reduce costs and minimize the impact on the environment, resulting in a sustainable production process. This can be achieved by developing new process flows and optimizing individual parameters of the manufacturing process

Problems with today's technology

The scheme of producing octacarboxylic iron phthalocyanine (HOC-FePc) by the Japanese method is shown in Figure 4. The first stage is the cyclization reaction and the formation of the phthalocyanine ring. The reactants are iron (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 Alcohol dialkyl ethers are mixed and heated to 180°C. Tetrasubphthalocyanine (TI-FeP), the precursor of HOC-FePc, is produced at this stage, with urea as the donor of nitrogen atoms, converting anhydrous acid groups into imide groups. A large amount of impurities is produced in this first stage, the efficiency of the chemical reaction is relatively low (<50%), and a large amount of solid by-products are produced, including urea, catalyst, solvent and reactant. It is important to note that the semi-product tetrasubphthalocyanine (TI-FePc) obtained in this step is a solid insoluble in most organic solvents and water, and contains a large number of contaminants, including insoluble oxide-hydroxide or Insoluble in alkaline media, such as iron. Even if concentrated sodium hydroxide solution (41.6 g NaOH/g HOC-FePc is used in the Japanese process, see Figure 4) at 100 °C is used in the second stage of the process, the hydrolysis of the imide group and the generation of carboxylate groups, yielding soluble OC-FePc, but may not be sufficient to remove these types of contaminants. If these iron oxide-hydroxide contaminants were to be removed in the subsequent hydrochloric acid treatment, the carboxylate groups were acidified and protonated to carboxylic acids, yielding insoluble HOC-FePc, followed by physical separation. Excess NaOH must be neutralized during this process, and excess hydrochloric acid should be added to reduce the pH to about 1, which is suitable for the precipitation of the product, producing a large amount of sodium chloride (about 61gNaCl per gram of HOC-FePc), and The desired product co-precipitates to give a blue paste. Use 102.75 grams of 37% HCl solution/gram to produce HOC-FePc, but the consumption of hydrochloric acid is very large. The product in salt was extracted using NaOH solution and reprecipitated in HCl solution.

Another related aspect that must be improved is the profitability of the process. Spectrophotometric studies comparing the commercial product and the product produced according to this patent application clearly show that the commercially available dark blue solid contains a significant amount of impurities. The percentage of impurities reaches more than 2/3, and the reported yield is 42% (according to Japanese Patent No. 10-101673 in 1998), which is far from the actual situation. If the pure product content is corrected, the yield will decrease to around 14%. Alternatives proposed in this patent application make the process more efficient and sustainable, and also produce insoluble products suitable for use as pigments.

Summary

As mentioned earlier, it is necessary to minimize the formation of by-products and waste in the production process of iron octacarboxyphthalocyanate (HOC-FePc). The vast majority of methods described in the literature and Japanese Patent No. 10-101673 from 1998 use high volumes of 50% by weight sodium hydroxide or potassium hydroxide solutions, which require large volumes of hydrochloric acid solution to neutralize the solution and isolate the product, Thereby, a large amount of sodium chloride or potassium chloride is produced as a residue. ^7.11 Therefore, using the structural and chemical properties of this molecule, a new more efficient synthetic route was developed to produce a product with high purity at a lower cost, compared to traditional methods and the method of Japanese Patent No. 10-101673 in 1998 In comparison, almost no waste is generated (mainly salt), making the process more ecologically sustainable. This innovation was achieved by adding two strategic steps to the process: a) Purification of iron tetrasubphthalocyanine (TI-FePc) using hydrochloric acid solution for cyclization, which eliminates most of the iron oxide-hydroxide impurities , b) Hydrolysis of dilute aqueous sodium hydroxide solution to hydrolyze the isolated product using a calcium salt such as calcium chloride as a precipitating agent, thereby allowing the reuse of alkaline NaOH solution in the hydrolysis step and avoiding the unwanted generation of sodium chloride. Combining the above strategic steps entails base and acid consumption in addition to preventing salt formation and prevents undesired by-products from hampering the separation of the HOC-FePc product. In addition, another insoluble 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, producing raw materials for dyes and pigments.

Purpose

The subject of the present application has been developed in view of the prior art, one of the aims of which is to provide a process for the production of carboxymetalloprotein phthalocyanines, providing high production efficiency, this molecule has a lower cost and, compared to conventional processes, waste Yields are very low.

Another object of the present application is to prepare high purity carboxymetallophthalocyanines and insoluble derivatives suitable for use as pigments.

Description of drawings

The content of this invention relates to the production process for the production of dyes and pigments carboxy-metal phthalocyanine and the carboxy-metal phthalocyanine production details are described in detail in the following drawings:

Figure 1 shows the organic materials used in the preparation of metallophthalocyanines, phthalonitrile (a), benzene-1,2-dicarboxylic acid (b) phthalic anhydride (c) and 1,3-dicarboxylate Aminoisoindolin (d).

Figure 2 shows the organic materials used to prepare tetracarboxylic phthalocyanine, HTC-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(II) or Mn(III) or Cr(II) or Cr(III) or Mg(II) and other metal elements.

Figure 3 shows the organic materials used to prepare octacarboxyphthalocyanine, 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(II) or Mn(III) or Cr(II) or Cr(III) or Mg(II) and other metal elements.

Figure 4 shows the traditional synthetic route to produce OC-FePc and HOC-FePc.

Figure 5 shows a new synthetic route to produce TI-FePc, OC-FePc, HOC-FePc and CaOC-FePc.

Figure 6 depicts the electronic absorption spectra of two samples of OC-FePc in 0.1 mol L-1 NaOH solution. The solid line represents the spectrum of a commercial sample, generated by the methodology of the Japanese patent. Dashed lines show spectra of samples produced by the new method.

Description of drawings

Figure 4:

4.1 - "Phase One"

4.2 - "Impurities"

4.3 - "Excess"

4.4 - "Second Stage - Hydrolysis"

4.5 - "Excess"

4.6 - "Excess"

4.7 - "Excess"

4.8 - "Impurities"

4.9 - "Phase III - Precipitation"

4.10 - "Phase 4 - Repurification"

4.11 - "Impurities"

Figure 5:

5.1 - "Diphenyl ether"

5.2 - "Phase One"

5.3 - "Diphenyl ether"

5.4 - "Impurities"

5.5 - "Second Stage - Purification"

5.6 - "Third stage - Hydrolysis"

5.7 - "Excess"

5.8 - "Phase Four - Precipitation"

5.9 - "Filtering"

5.10 - "Excess"

5.11 - "Phase V - Substitution of Ca ²⁺ "

Detailed description of the invention

The innovation of the production process is the implementation of two strategic steps in the overall flow of the general method described in the literature and in Japanese Patent No. 10-101673 of 1998: a) from the material of iron tetrasubphthalocyanine (TI-FePc) through hydrochloric acid solution The cyclization reaction obtains, eliminates most of the iron oxide-hydroxide impurities, and b) uses the calcium salt of calcium chloride as a precipitating agent to hydrolyze the isolated product with dilute aqueous sodium hydroxide solution, while being able to reuse the base in the hydrolysis step neutral NaOH solution, while preventing the generation of undesired large amounts of sodium chloride. The purification of the material for the production of iron tetrasubphthalocyanine (TI-FePc) with hydrochloric acid solution, and the separation of the product CaOC-FePc with calcium chloride precipitant, and the recycling of acid and alkali solutions are shown in Figure 5 and detailed below describe. The new process can be divided into 5 steps:

Step 1: Cyclization reaction and production of semi-finished iron tetrasubphthalocyanine (TI-FePc), the efficiency is about 35%;

Step 2: In the fifth step, the HCl solution is used to purify the insoluble TI-FePc;

Step 3: carry out alkaline hydrolysis with the solution recovered in the fourth step to produce semi-finished iron octacarboxyphthalocyanine (OC-FePc);

Step 4: Precipitate with calcium ions, separate the CaOC-FePc pigment and recycle the NaOH solution reused in the third step;

Step 5: acidify with hydrochloric acid and convert CaOC-FePc into product HOC-FePc, and 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 (FeCl3), urea (CH4N2O), ammonium molybdate tetrahydrate ((NH46Mo7O24.4H2O) and pyromellitic dianhydride are intimately mixed And heat up to 180 ℃ in diphenyl ether to promote the cyclization reaction. In view of its low reaction yield, about 35%, in addition to producing iron tetrasubphthalocyanine precursor TI-FePc, there are also several solid by-products, mainly Iron oxide-hydroxides, molybdenum compounds and urea decomposition products and diphenyl ether solvents. Due to the low yield efficiency, the use of traditional methods is not sufficient to remove a large amount of solid impurities impregnated in the product.

The use of diphenyl ether in place of the polyethylene glycol dialkyl ether solvent (of this patent application) is highly advantageous, allowing the production of metallophthalocyanines compared to the method described in Japanese Patent No. 10-101673, 1998 The yield in the reaction was as high as 150%. Additionally, in order to increase the purity of the final product and minimize the amount of sodium hydroxide used, a purification (second step) was performed to remove most of the solid impurities produced in the first step. In fact, impurities may cover the Ti-FePc particles to reduce the hydrolysis reaction rate of the derivatives. The purification process (second step) treats the solids produced in the first step, and the hydrochloric acid solution dissolves the organic and inorganic substances formed in the reaction medium. During the purification process, TI-FePc remained in solid form, which facilitated its separation from the hydrochloric acid solution. Importantly, this solution does not require neutralization, and the HCl solution can be treated and reused for the purification of TI-FePc. However, we have to keep in mind that the fifth step brings up options that produce less pollution and apply this process. The reagent reuse process is shown in Figure 5 with dashed arrows.

In the third step, the purified TI-FePc was hydrolyzed with sodium hydroxide. Due to its higher purity, this step is carried out with a more dilute alkaline solution than traditional methods. In this new method, only 2.0 grams of sodium hydroxide is used to produce 1 gram of dye, which brings about an economical efficiency of about 95% compared to the method described in Japanese Patent No. 10-101673 in 1998. At the end of this step, a soluble OC-FePc solution is obtained from the reaction medium due to eight negative electrons. In the subsequent fourth step, calcium chloride solution is added as a precipitating agent to separate CaOC-FePc without adding mineral acid to neutralize the carboxylate group molecules. Therefore, instead of using mineral acid for protonation, OC-FePc molecules were linked using cation-selective binding, thereby promoting CaOC-FePc to form an insoluble solid, which enabled the separation of iron phthalocyanine without the need for neutralization of NaOH solution. In this way, sodium hydroxide (Na ₂ SO ₄ , responsible for the precipitation of CaSO ₄ (s) and the separation of Ca ²⁺ ions) in the recovery solution was added in the third step and used for the hydrolysis of the intermediate TI-FePc. The solid obtained in this step can be used as a functional pigment. Finally, it is necessary to replace Ca ions with ^H ions to generate the ^carboxylic acid derivative HOC-FePc. This is accomplished by chemical reaction of solid CaOC-FePc with HCl solution. In this way the desired product is isolated from an acidic solution of calcium chloride, which can be used again at this same stage to give another batch of protonation/displacement of Ca ²⁺ ions, or used in a second Step Purification of intermediate TI-FePc. Before, however, the solution should be treated with sulfuric acid and the precipitate of CaSO4 separated. All acid and base solutions used in the new process are reused, resulting in high reagent economy.

This new method can save about 95% of alkali (NaOH) and acid. The consumption of hydrochloric acid solution in this method is used for the purification of the precursor and protonation of OC-FePc. It is estimated that each batch of 15g of 37% HCl solution brings an economic efficiency of 85% compared with the Japanese method. In addition, important parts are replaced by cheaper sulfuric acid. Since the sodium hydroxide and hydrochloric acid solutions are reused in the next batch, no unwanted 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 salt as a precipitant does not lead to an increase in process cost because this is an inexpensive reagent (its price is about one-fifth of the price of hydrochloric acid) and non-toxic.

As mentioned earlier, all reagent savings are a result of the use of calcium chloride in the production process making it possible to recover and reuse the sodium hydroxide solution as hydrochloric acid, avoiding the large formation of unwanted substances such as sodium chloride. If 2 grams of HOC-FePc products are produced in two batches, the savings of sodium hydroxide and hydrochloric acid are 97% and 92% respectively.

In addition to the more economical and feasible synthetic route, high-purity products are obtained. The purity of the sample can be easily verified by techniques such as absorption spectroscopy of ultraviolet (UV) and visible light (vis). Metallophthalocyanines exhibit very characteristic electronic spectra in the visible and ultraviolet regions, ^1.5 which allow the use of these molecules as dyes and pigments in the textile industry. Its electronic spectrum has strong absorption bands, the region between 600 and 700 nanometers called the Q-band, and a second band of lower intensity around 600nm. In the ultraviolet region, the medium-intensity band around 350 nm is called the Soret band (Soret). The electronic absorption spectra of two OC-FePc samples, one commercial product and one produced following this procedure, are shown in Fig. 6. This graph is presented as molar absorptance (ε) 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 654 nm, bands of maximum intensity are observed in the visible region at 682 and 620 nm, which are unusual in metallophthalocyanine spectra. There is also a UV band at 344nm, which is more intense than the band at 682nm. The dashed line represents the sample spectrum obtained by the new production process (this patent). The similarity between the two spectra, with absorption maxima at 682 and 620 nm, suggests that it is the same compound. However, the Solet band at 351 nm is less intense than that at 682 nm, as expected for metallophthalocyanines. ^1.5 This is important in phthalocyanine derivatives, the bands in the 600 to 700 nm range are generally more intense than those in the UV. ^1.5 This finding is a strong indication of the presence of impurities in the samples 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 sample produced by the method of this patent application has a higher molar absorbance (ε) in all absorption bands (dashed line). The molar absorptivity ε is an intrinsic property of every substance and is determined by the following formula:

A＝εbC

where: A is the absorbance of the sample at one wavelength, ε is the molar absorptivity (L mol ⁻¹ cm ⁻¹ ) at said wavelength, C is the concentration of the solution (molL −1 ) and b is the optical path of the sample, Generally 1.00 cm.

It can be seen from Figure 6 that the molar absorptivity (dotted line) at 682 nm of the product prepared by the new method is about 3.34 times higher than that of the material prepared by the Japanese process. Although ε 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 decrease in the relative amount of ε in the sample. Therefore, lower ε values are the result of lower masses in the compounds. In other words, compared with the material produced by the method of the present patent application, the samples produced by the method of the Japanese patent showed a large amount of impurities, about 70%. That is, in order to have the same mass of HOC-FePc, Japanese method No. 10-101673 of 1998 produced three times the mass of the material. Due to the presence of impurities, the efficiency of Japanese Patent Application No. 10-101673 in 1998 is about 12% and the yield of the new process is about 36%. In this way the new process is more economically viable and efficiently produces products of higher purity, thus making the production of these materials (dyes and pigments) more competitive.

A comparison of the Japanese process and the new process scheme herein is shown in Figures 4 and 5, respectively. The following is a typical example of preparing HOC-FePc.

example

example 1:

2.8 grams of FeCl ₂ 4H ₂ O, 10.0 grams of pyromellitic dianhydride, 1.4 g of ammonium molybdate and 22.9 g of urea, carefully ground, adding 40 grams of diphenyl ether to the solid mixture, and raising the temperature of the mixture to 180 °C, 4 hours. The dark solid was filtered, washed with ethanol, extracted with 100 mL of 1.5M NaOH solution at reflux for 6 hours and diluted with 300 mL of water. Then, a solution of _CaCl2 (4.8 g in 30 mL of water) was added and the precipitate was isolated by filtration. The filtered solid was then treated with 100 mL of 3.0M HCl with stirring for 30 minutes, filtered, washed with water and dried. Yield: 3.0 g of HOC-FePc.

Example 2:

7.40 g of FeCl ₃ , 10.0 g of pyromellitic dianhydride, 1.4 g of ammonium molybdate and 22.9 g of urea, carefully grind, add 40 g of diphenyl ether to the solid mixture, and raise the temperature of the mixture to 180°C for 4 hours while stirring . The dark solid was filtered, washed with ethanol, treated with 100 mL of 3M HCl solution, shaken for 6 hours, filtered and reflux extracted with 100 mL of 1.5M NaOH for 6 hours. Then, a solution of _CaCl2 (4.8 g in 300 mL of water) was added and the precipitate was isolated by filtration. The filtered solid was then treated with 100 mL of 3.0M HCl with shaking for 30 minutes with stirring, the solid was filtered then washed with water and dried. Yield: 4.0 g of HOC-FePc.

Example 3:

3.70 g of FeCl ₃ , 10.0 g of pyromellitic dianhydride, 1.4 g of ammonium molybdate and 22.9 g of urea, carefully grind, add 40 g of diphenyl ether to the solid mixture, and raise the temperature of the mixture to 180°C for 4 hours while stirring . The dark solid was filtered, washed with ethanol, treated with 100 mL of 3M HCl solution, shaken for 6 hours, filtered and reflux extracted with 100 mL of 1.5M NaOH for 6 hours. Then, a solution of _CaCl2 (4.8 g in 300 mL of water) was added and the precipitate was isolated by filtration. The filtered solid was then treated with 100 mL of 3.0M HCl with shaking for 30 minutes with stirring, the solid was filtered then washed with water and dried. Purity can be increased by repeated washing procedures. Yield: 1.5 g of HOC-FePc.

Example 4:

5.45 grams of CoCl ₂ ·6H ₂ O, 10.0 grams of pyromellitic dianhydride, 1.4 g of ammonium molybdate and 22.9 g of urea, carefully ground, adding 40 grams of diphenyl ether to the solid mixture, and raising the temperature of the mixture to 180 °C, 4 hours. The dark solid was filtered, washed with ethanol, treated with 100 mL of 3M HCl solution, shaken for 6 hours, filtered and refluxed with 100 mL of 1.5M NaOH for 6 hours. 3M HCl solution, treated with shaking for 6 hours, filtration and reflux extraction with 100 mL of 1.5M NaOH for 6 hours. Then, a solution of _CaCl2 (4.8 g in 300 mL of water) was added and the precipitate was isolated by filtration. The filtered solid was then treated with 100 mL of 3.0M HCl with shaking for 30 minutes with stirring, the solid was filtered then washed with water and dried. Purity can be increased by repeated washing procedures. Yield: 4.0 g of HOC-CoPc.

Example 5:

5.0 grams of Zn (CH ₃ CO ₂ ) 2 H ₂ O, 10.0 grams of pyromellitic dianhydride, 1.4 g of ammonium molybdate and 22.9 g of urea, carefully ground, adding 40 grams of diphenyl ether to the solid mixture, stirring the mixture The temperature was raised to 180°C for 4 hours. The dark solid was filtered, washed with ethanol, treated with 100 mL of 3M HCl solution, shaken for 6 hours, filtered and reflux extracted with 100 mL of 1.5M NaOH for 6 hours. Then, a solution of _CaCl2 (4.8 g in 300 mL of water) was added and the precipitate was isolated by filtration. The filtered solid was then treated with 100 mL of 3.0M HCl with shaking for 30 minutes with stirring, the solid was filtered then washed with water and dried. Purity can be increased by repeated washing procedures.

Yield: 2.0 g of HOC-ZnP.

The procedures of Examples 1, 2, 3, 4 and 5 may undergo some changes which will be mentioned below, which may affect the reaction yield and the purity of the final product. It is clear that the exchange of the metal ion salt by another metal element in this process will result in metallated octacarboxyphthalocyanines with different metals and produce different dyes and pigments.

In example 1,2,3,4 and 5, the ratio of reactant is based on the molar quantity of catalyst (ammonium molybdate), or 1 mole of ammonium molybdate; Add 12.43 moles of iron chloride (II) tetrahydrate in example 1; Example 40.47 mol FeCl ₃ in 2; 20.23 mol FeCl ₃ in Example 3; 20.23 mol CoCl ₂ 6H ₂ O in Example 4 and 20.23 mol Zn(CH ₃ CO ₂ ) 2H ₂ O in Example 5; 40.47 moles of tetracarboxylic dianhydride, 336.58 moles of urea and 207.45 moles of diphenyl ether. Regarding iron (II) chloride tetrahydrate, the ratio between the reactants can be in the range of 1 to 50 moles and other salts used in examples 2 to 5; pyromellitic dianhydride is 1 to 162 moles; 1 Up to 1500 moles of urea and 0-2000 moles of diphenyl ether to produce a reaction mixture suitable for the composition of the production of TI-FePc intermediates.

In example 1 to example 5, ammonium molybdate can be 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]nonane -5-ene (DBN), triethylamine, 2-aminoethanol, diethanolamine or triethanolamine instead.

In Examples 1 to 5, iron(II) chloride tetrahydrate can be replaced by other metal salts, usually transition metal salts (anhydrous or hydrated) such as Fe(II), Fe(III), Co(II), Co(III), Cu(II), Ni(II), Mn(II), Mn(III), Cr(II), Cr(III), Zn(II), and typically Mg(II), Li (I), which include anions such as halides, carboxylate (formate, acetate, oxalate), nitrate, sulfate, perchlorate, trifluoroacetate, trifluoromethanesulfonate , tetrafluoroborate and hexafluorophosphate and so on.

In Example 1 to Example 5, pyromellitic dianhydride can be 1,2,4,5-tetracyanobenzene, benzene-1,2,4,5-tetracarboxylic acid, 1,2,4,5- Tetracarboxy amidobenzene and pyromellitic diimide substitution.

In Example 1 to Example 5, pyromellitic dianhydride can be replaced by trimellitic anhydride (1,2,4-tricarboxybenzoic acid-1,2-anhydride or 1,2,4-tricarboxybenzoic acid 1,2-anhydride) (Figure 2) or 1,2,4-tricarboxybenzoic acid or 1,2-anhydrotrimellitic acid chloride or 1,2,4-tricarboxyamidobenzene instead.

In Examples 1 to 5, the reaction temperature may be in the range of 50-250°C.

In Examples 1 to 5, the reaction time can vary from 1 to 12 hours.

In example 1 to example 5, diphenyl ether solvent can be replaced by other high boiling point solvents such as dimethyl formamide, diethyl formamide, nitrobenzene, 2-aminoethanol, diethanolamine, triethanolamine, ethylene glycol, di Substituted by glycol, polyol, dialkyl ester of polyol, polyethylene glycol dialkyl ether, etc.

In Examples 1 to 5, solvents such as methanol, acetone, acetonitrile, propanol, isopropanol, butanol, diethyl ether, etc. can be used for the cleaning step.

In Examples 1 to 5, the volume of the hydrochloric acid solution used for the treatment may range from 10 to 3000 ml and its concentration may vary between 0.001 and 12M. Hydrochloric acid can be replaced by strong acids such as sulfuric acid, nitric acid, perchloric acid, hydrobromic acid, hydroiodic acid, and trifluoroacetic acid. Reaction times can vary from 30 minutes to 12 hours. In Examples 1 to 5, the concentration of the base can be from 0.001 to 25M sodium hydroxide or potassium hydroxide or the like.

In Examples 1 to 5, the hydrolysis temperature range is 50-120° C., and the reaction time is 0.1-24 hours.

In Examples 1 to 5, the mass of _CaCl2 can be in the range of 0.1 to 10.0 g, and the volume used to dissolve the salt can be in the range of 1 to 1000 ml.

In examples 1 to 5, calcium chloride can be replaced by salts (anhydrous or hydrated), such as nitrates, bromides, formates, acetates and triflate, or by Ca(II), Ba(II), Mg(II), Sr(II), etc. hydroxides (anhydrous or hydrated) or transition metal or lanthanide salts.

In Example 1 to Example 5, the precipitation agent can be replaced by strong acid, such as hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, perchloric acid, trifluoroacetic acid, trifluoromethanesulfonic acid and the like.

In Example 1 to Example 5, the volume change of hydrochloric acid (or other acid) is between 10.0 and 1000 mL, and its concentration range is a solution of 0.001-16M.

In Examples 1 to 5, the acid treatment time may be in the range of 0.1 to 6 hours.

refer to

1. Mack, J.; Kobayashi, N., Low Symmetry Phthalocyanines and Their Analogues. Chemical Reviews, 2011.111(2): p.281-321.

M.；Ahsen,V.；Nyokong,T.,Synthetic pathways towater-soluble phthalocyanines and close analogs.Coordination ChemistryReviews,2010.254(23–24):p.2792-2847.2. Dumoulin, F.;

M.; Ahsen, V.; Nyokong, T., Synthetic pathways towater-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.

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10. Shirai, H.; Maruyama, A.; Kobayashi, K.; Hojo, N.; well as Co(II)-4,4′,4″,4″′-tetracarboxyphthalocyanine and their catalase-like activity. Die Makromolekulare Chemie,1980.181(3):p.575-584.

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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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