A method for preparing phthalocyanine green complex

Abstract

The invention discloses a method for preparing a phthalocyanine green complex, in the field of chemical synthesis technology, the method for preparing the phthalocyanine green complex: add aluminum chloride, sodium chloride and sodium bromide alternately in a reactor, add copper phthalocyanine and copper chloride in sequence; add o-dichlorobenzene, add rosin and emulsion, add phthalocyanine green derivatives, keep warm at 70-85°C, add 0.25-5.0% auxiliary agent for heat preservation, feed into a filter press for washing, wash the solid phase with water until neutral, and dry to obtain a phthalocyanine green complex. The beneficial effects of the present invention are: using the phthalocyanine green preparation method provided by the present invention, a high-purity, high-quality phthalocyanine green complex product with fine particles, uniform particle size distribution, excellent color light and strong tinting power can be obtained. Using the phthalocyanine green preparation method provided by the present invention, a yellow phase, low viscosity product is produced, which can be applied to high-end automotive primers, high-end coatings, high-end metal decorative inks, and high-end liquid crystal inks.

Description

Technical field:

[0001] The invention belongs to the technical field of chemical synthesis, and more specifically relates to organic pigment synthesis technology. Background technology:

[0002] Phthalocyanine green is a fully chlorinated copper phthalocyanine, containing an average of 14 to 15 chlorine atoms per molecule, and its color is blue-green. Phthalocyanine green has excellent various application properties, for example, its light resistance, heat resistance, weather resistance and solubility resistance are quite excellent. Although green can be obtained by properly mixing blue pigment and yellow pigment, the green pigment obtained by this color combination cannot be compared with the pigment phthalocyanine green in terms of color and application performance. At the same time, since most yellow pigments are more or less toxic, the pigment obtained by mixing blue and yellow pigments cannot be used for coloring food packaging materials.

[0003] There are two main methods for preparing phthalocyanine green: chlorosulfonic acid method and aluminum chloride molten salt method. The chlorosulfonic acid method is specifically as follows: using chlorosulfonic acid as the reaction medium, iodine, antimony chloride, etc. as catalysts, passing chlorine gas at 90-100°C to react with copper phthalocyanine to synthesize crude phthalocyanine green, and then pigmenting to obtain the finished product. The pigment particles of this process product are fine and the processing performance is good, but the yield is low and the color is dark. In addition, this process produces a large amount of mixed acid sulfuric acid and hydrochloric acid mixture, which is difficult to handle; and chlorosulfonic acid is highly dangerous and is not suitable for large-scale use as a basic raw material. The specific operation of the aluminum chloride-sodium chloride method is: using aluminum chloride-sodium chloride eutectic as solvent, cuprous chloride or cupric chloride as catalyst, passing chlorine gas at 160-200 degrees to react with copper phthalocyanine to synthesize crude phthalocyanine green. The pigment particles of this process product are coarse and the processing performance is slightly poor, but the color is bright and the yield is slightly higher. In addition, this process produces a large amount of acidic solution containing aluminum salts and sodium salts, which is difficult to handle and requires high processing costs. Therefore, developing an environmentally friendly and low-cost method for preparing phthalocyanine green has become an urgent problem to be solved.

[0004] The national invention patent CN108084730A previously applied by the inventor discloses an environmentally friendly preparation method of phthalocyanine green, which utilizes emulsion pigmentation to prepare phthalocyanine green pigment with high tinting power. However, the obtained product has a blue phase and high viscosity and cannot be used in high-end automotive primers, high-end powder coatings, high-end metal decorative inks, and high-end liquid crystal inks. Summary of the invention:

[0005] In order to solve the above problems and overcome the shortcomings of the prior art, the present invention provides a method for preparing a phthalocyanine green complex, thereby obtaining a product with a yellowish shade, high color strength and low viscosity, which can well solve the application problems in high-end automotive primers, high-end coatings, high-end metal decorative inks, and high-end liquid crystal inks.

[0006] The specific technical solution of the present invention to solve the above technical problems is:

[0007] The method for preparing a phthalocyanine green complex is characterized by comprising the following steps:

[0008] (1) Alternately add aluminum chloride, sodium chloride and sodium bromide into a reaction kettle, raise the temperature to 155-170° C., stir until all the materials in the reaction kettle are dissolved, stop heating, and add copper phthalocyanine and copper chloride in sequence;

[0009] (2) After the addition of copper phthalocyanine and copper chloride, the reaction was continued by passing chlorine gas for 12-16 hours at a temperature of 155° C. to 160° C., until no hydrogen chloride was produced by tail gas detection, stirring was stopped, and the passing of chlorine was stopped to obtain a reaction solution;

[0010] (3) The reaction solution is placed in a dilution tank while hot and stirred until the material temperature in the dilution tank drops to 70° C. The material is then placed in a filter press and washed with water until the washing liquid is neutral to obtain a filter cake;

[0011] (4) After the filter cake is evenly slurried with water, o-dichlorobenzene is added, liquid alkali is added to adjust the pH to 13-14, rosin and emulsion are added, and the mass ratio of filter cake, rosin and calcium chloride is 100:9-12; the temperature is raised for emulsification for 2-5 hours, and then the temperature is raised and pressurized for 5-10 hours, and the pressure is between 0.1-0.6MPa. After the pressure is maintained, o-dichlorobenzene is distilled out, and 30-50% of calcium chloride is added based on the amount of rosin added, the temperature is raised to 70-85°C for insulation, 0.5-5.0% of phthalocyanine green derivative is added, and the temperature is maintained at 70-85°C. 0.25-5.0% of auxiliary agent is added for insulation, and the material is fed into a filter press for water washing, the solid phase is washed with water until neutral, and the phthalocyanine green complex is obtained after drying.

[0012] Furthermore, in step (1), aluminum chloride, sodium chloride, sodium bromide, copper phthalocyanine and copper chloride are added in sequence in a mass ratio of (5-8):1:(0.1-0.5):(0.5-2.0):(0.1-0.5).

[0013] Furthermore, the rate of passing chlorine in step (2) is 70-75 kg / h.

[0014] Furthermore, the auxiliary agent is an alkylamine or an alkylammonium chloride.

[0015] Furthermore, the mass of the emulsion is 13-30 times the mass of the filter cake, and the emulsion is composed of xylene, an emulsifier and water in a mass ratio of (15-20):1:(1-20), the xylene is at least one of o-xylene, m-xylene and p-xylene, the emulsifier is phenethylphenol polyoxypropylene polyoxyethylene ether or phenethylphenol polyoxyethylene ether; the o-dichlorobenzene is 1-3 times the mass of the filter cake.

[0016] Furthermore, the preparation method of the phthalocyanine green derivative includes a chlorination process and a sulfonation process.

[0017] The chlorination process:

[0018] ① Add aluminum chloride and sodium chloride into the reactor, heat the jacket until the materials in the reactor are completely dissolved, slowly start the stirring paddle to start stirring, stop heating when all the materials in the reactor are dissolved, and add copper phthalocyanine and copper chloride in sequence;

[0019] ② After adding copper chloride and stirring, start to introduce chlorine gas for reaction. The chlorination reaction time is 4-6 hours, the temperature is controlled between 155-160°C, and the amount of chlorine gas introduced is about 400 kg. Stop introducing chlorine gas when the reaction reaches the end point;

[0020] ③ Add bottom water to the reactor in advance, put the reacted chlorinated materials into the bottom water, and send the diluted materials into the filter press for water washing until neutral, and dry to obtain reactant A.

[0021] The sulfonation process:

[0022] ①Put fuming sulfuric acid into the reactor and add reactant A, control the temperature of the materials in the reactor to be lower than 50℃, and stir evenly;

[0023] ② Raise the temperature of the jacket to 60-70℃ in the kettle and keep the temperature to react until the end point

[0024] ③ Add water to the dilution kettle, put the sulfonated material into the dilution kettle after 60 minutes, raise the temperature to 80-95℃, keep warm and filter to obtain the phthalocyanine green derivative.

[0025] In the chlorination process, the mass ratio of aluminum chloride, sodium chloride, copper phthalocyanine and copper chloride is (3-5):1:(0.8-0.9):(0.1-0.15).

[0026] The beneficial effects of the present invention are:

[0027] 1. The method for preparing phthalocyanine green provided by the present invention can produce a high-purity, high-quality phthalocyanine green composite product with fine particles, uniform particle size distribution, excellent color and strong tinting power.

[0028] 2. The phthalocyanine green preparation method provided by the present invention can produce a yellow-phase, low-viscosity product that can be applied to high-end automobile primers, high-end coatings, high-end metal decorative inks, and high-end liquid crystal inks. Description of the drawings:

[0029] Attached Figure 1 is a color difference detection diagram of the phthalocyanine green complex prepared in Example 1 of the present invention;

[0030] Attached Figure 2 is a color difference detection diagram of the phthalocyanine green complex prepared in Example 2 of the present invention;

[0031] Attached Figure 3 is a color difference detection diagram of the phthalocyanine green complex prepared in Example 3 of the present invention;

[0032] Attached Figure 4 is a color difference detection diagram of the phthalocyanine green complex prepared in Comparative Example 1 of the present invention;

[0033] Attached Figure 5 This is a color difference detection diagram of the phthalocyanine green complex prepared in Comparative Example 2 of the present invention;

[0034] Attached Figure 6 is a color difference detection diagram of the phthalocyanine green complex prepared in Comparative Example 3 of the present invention;

[0035] Attached Figure 7 is a color difference detection diagram of the phthalocyanine green complex prepared in Comparative Example 4 of the present invention;

[0036] Attached Figure 8 is a color difference detection diagram of the phthalocyanine green complex prepared in Comparative Example 5 of the present invention;

[0037] Attached Fig. 9 is a color difference detection diagram of the phthalocyanine green composite prepared in Comparative Example 6 of the present invention;

[0038] Attached Fig.10 is a color difference detection diagram of the phthalocyanine green composite prepared in Comparative Example 7 of the present invention;

[0039] Attached Fig.11 This is a color difference detection diagram of the phthalocyanine green complex prepared in Comparative Example 8 of the present invention; Specific implementation method:

[0040] In the description of the present invention, specific details are only for a full understanding of the embodiments of the present invention, but those skilled in the art should know that the implementation of the present invention is not limited to these details. In addition, well-known structures and functions are not described or shown in detail to avoid blurring the key points of the embodiments of the present invention. For those of ordinary skill in the art, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.

[0041] Specific implementation of the present invention:

[0042] In order to better understand the present invention, a specific embodiment is used for illustration. It is worth emphasizing that the effect of this embodiment is not substantially different from the various embodiments within the protection scope of the present invention, including the respective reagents and the content ratio of the reagents, and all of them can achieve the effects described in the present invention and solve the above-mentioned problems. Other combinations are not described here.

[0043] Embodiment 1:

[0044] 1. Preparation method of phthalocyanine green derivatives:

[0045] (1) Chlorination process

[0046] ① Put 2000 kg aluminum chloride and 370 kg sodium chloride into the reactor, heat the jacket to 165°C until the materials in the reactor are completely dissolved, slowly start the stirring paddle to stir, confirm that all the materials in the reactor are dissolved, stop heating, and add 420 kg copper phthalocyanine and 29 kg copper chloride in turn.

[0047] ② After adding cupric chloride, stir for 15 minutes, start to introduce chlorine gas for reaction, the chlorination reaction time is 4 hours, the temperature is controlled between 155℃--160℃, and the amount of chlorine gas introduced is about 400 kg. Stop introducing chlorine gas when the reaction reaches the end point.

[0048] ③ 15,000 kg of bottom water is added to the reactor in advance, and the reacted chlorinated materials are placed in the bottom water. The diluted materials are fed into the filter press for washing. The filter cake is washed until neutral, and then dried to obtain the reactant A.

[0049] (2) Sulfonation process

[0050] ① Put 3600 kg of fuming sulfuric acid into the reactor, add 300 kg of reactant A, control the temperature of the material in the reactor below 50°C, and stir for 15 minutes after the feeding is completed.

[0051] ② Raise the temperature of the jacket to 65℃ in the kettle and keep the reaction for 8 hours until the end point

[0052] ③ Add 15,000 kg of water into the dilution kettle, put the sulfonated material into the dilution kettle after 60 minutes, raise the temperature to 90°C, keep it warm for 1 hour, filter and obtain the phthalocyanine green derivative.

[0053] 2. Preparation method of phthalocyanine green complex:

[0054] Step 1: Add 2000 kg of aluminum chloride, 290 kg of sodium chloride, and 80 kg of sodium bromide into the reactor. Heat the jacket to 165°C until the materials in the reactor are completely dissolved. Slowly start the stirring paddle to stir. Confirm that all the materials in the reactor are dissolved. Stop heating and add 420 kg of copper phthalocyanine and 29 kg of copper chloride in sequence.

[0055] Step 2: After adding cupric chloride, stir for 15 minutes, start to introduce chlorine gas for reaction, the chlorination reaction time is between 12-16 hours, the temperature is controlled between 155℃-160℃, and about 1100 kg of chlorine gas is introduced. The reaction ends when no hydrogen chloride is produced, and then stop introducing chlorine gas.

[0056] Step 3: Add 15,000 liters of bottom water to the diluter in advance, put the reacted chlorinated material into the bottom water, and the diluted material is fed into the filter press for washing until it is neutral to obtain a filter cake.

[0057] Step 4: After the filter cake is evenly slurried with water, 1,300 kg of o-dichlorobenzene is added, liquid alkali is added to adjust the pH to 13-14, 75 kg of polymerized rosin is added, the temperature is raised for emulsification for 5 hours, and then the temperature is continued to be raised and pressurized to 0.35 MPa for 7 hours. After the pressure is maintained, o-dichlorobenzene is distilled out, 30 kg of calcium chloride is added, the temperature is raised to 80°C and maintained for 1 hour, 8.4 kg (dry) of derivative A filter cake is added, and the temperature is maintained at 80°C for 60 minutes. 3.9 kg of auxiliary agent octadecylamine is added and maintained for 3 hours, and the material is fed into a filter press for washing, and the filter cake is washed with water until neutral, and the phthalocyanine green complex is obtained after drying.

[0058] Embodiment 2:

[0059] 1. Preparation method of phthalocyanine green derivatives:

[0060] (1) Chlorination process

[0061] ① Put 2000 kg aluminum chloride and 370 kg sodium chloride into the reactor, heat the jacket to 165°C until the materials in the reactor are completely dissolved, slowly start the stirring paddle to stir, confirm that all the materials in the reactor are dissolved, stop heating, and add 420 kg copper phthalocyanine and 29 kg copper chloride in turn.

[0062] ②After adding cupric chloride, stir for 15 minutes, and start to introduce chlorine gas for reaction. The chlorination reaction time is 4--6 hours. The temperature is controlled between 155℃--160℃. About 400 kg of chlorine gas is introduced. Stop introducing chlorine gas when the reaction reaches the end point.

[0063] ③ 15,000 kg of bottom water is added to the device in advance, and the reacted chlorinated materials are placed in the bottom water. The diluted materials are fed into the filter press for washing. The filter cake is washed until neutral, and dried to obtain the reactant A.

[0064] (2) Sulfonation process

[0065] ① Put 3600 kg of fuming sulfuric acid into the reactor, add 300 kg of reactant A, control the temperature of the material in the reactor below 50°C, and stir for 15 minutes after the feeding is completed.

[0066] ② Raise the temperature of the jacket to 65℃ in the kettle and keep the reaction for 8 hours until the end point

[0067] ③ Add 15,000 kg of water into the dilution kettle, put the sulfonated material into the dilution kettle after 60 minutes, raise the temperature to 90°C, keep it warm for 1 hour, filter and obtain the phthalocyanine green derivative.

[0068] 2. Preparation method of phthalocyanine green complex:

[0069] Step 1, put 2000 kg of aluminum chloride, 290 kg of sodium chloride, and 80 kg of sodium bromide into the reactor, heat the jacket to 165 ° C until the materials in the reactor are completely dissolved, slowly start the stirring paddle to start stirring, confirm that all the materials in the reactor are dissolved, stop heating, and add 420 kg of copper phthalocyanine and 29 kg of cupric chloride in sequence;

[0070] Step 2, after adding cupric chloride, stir for 15 minutes, start to introduce chlorine gas for reaction, the chlorination reaction time is between 12-16 hours, the temperature is controlled between 155°C-160°C, about 1100 kg of chlorine gas is introduced, and the reaction is terminated when no hydrogen chloride is produced, then stop introducing chlorine gas;

[0071] Step 3: 15,000 liters of bottom water is added to the diluter in advance, and the reacted chlorinated material is placed in the bottom water. The diluted material is fed into the filter press for washing until it is neutral to obtain a filter cake;

[0072] Step 4: After the filter cake is slurried evenly with water, 1,300 kg of o-dichlorobenzene is added, liquid alkali is added to adjust the pH to 13-14, 75 kg of polymerized rosin is added, the temperature is raised for emulsification for 5 hours, and then the temperature is continued to be raised and pressurized to 0.35 MPa for 7 hours. After the pressure is maintained, o-dichlorobenzene is distilled out, 30 kg of calcium chloride is added, the temperature is raised to 80°C and maintained for 1 hour, 8.4 kg (dry) of derivative A filter cake is added, and the temperature is maintained at 80°C for 60 minutes. 3.9 kg of additive dodecyl ammonium chloride is added and maintained for 3 hours, and the material is fed into a filter press for washing, and the filter cake is washed with water until neutral, and the phthalocyanine green complex is obtained after drying.

[0073] Embodiment 3:

[0074] 1. Preparation method of phthalocyanine green derivatives:

[0075] (1) Chlorination process

[0076] ① Put 2000 kg aluminum chloride and 370 kg sodium chloride into the reactor, heat the jacket to 165°C until the materials in the reactor are completely dissolved, slowly start the stirring paddle to stir, confirm that all the materials in the reactor are dissolved, stop heating, and add 420 kg copper phthalocyanine and 29 kg copper chloride in turn.

[0077] ②After adding cupric chloride, stir for 15 minutes, and start to introduce chlorine gas for reaction. The chlorination reaction time is 4--6 hours. The temperature is controlled between 155℃--160℃. About 400 kg of chlorine gas is introduced. Stop introducing chlorine gas when the reaction reaches the end point.

[0078] ③ 15,000 kg of bottom water is added to the device in advance, and the reacted chlorinated materials are placed in the bottom water. The diluted materials are fed into the filter press for washing. The filter cake is washed until neutral, and dried to obtain the reactant A.

[0079] (2) Sulfonation process

[0080] ① Put 3600 kg of fuming sulfuric acid into the reactor, add 300 kg of reactant A, control the temperature of the material in the reactor below 50°C, and stir for 15 minutes after the feeding is completed.

[0081] ② Raise the temperature of the jacket to 65℃ in the kettle and keep the reaction for 8 hours until the end point

[0082] ③ Add 15,000 kg of water into the dilution kettle, put the sulfonated material into the dilution kettle after 60 minutes, raise the temperature to 90°C, keep it warm for 1 hour, filter and obtain the phthalocyanine green derivative.

[0083] 2. Preparation method of phthalocyanine green:

[0084] Step 1: Add 2000 kg of aluminum chloride, 290 kg of sodium chloride, and 80 kg of sodium bromide into the reactor. Heat the jacket to 165°C until the materials in the reactor are completely dissolved. Slowly start the stirring paddle to stir. Confirm that all the materials in the reactor are dissolved. Stop heating and add 420 kg of copper phthalocyanine and 29 kg of copper chloride in sequence.

[0085] Step 2: After adding cupric chloride, stir for 15 minutes, start to introduce chlorine gas for reaction, the chlorination reaction time is between 12-16 hours, the temperature is controlled between 155℃-160℃, and about 1100 kg of chlorine gas is introduced. The reaction ends when no hydrogen chloride is produced, and then stop introducing chlorine gas.

[0086] Step 3: Add 15,000 liters of bottom water to the diluter in advance, put the reacted chlorinated material into the bottom water, and the diluted material is fed into the filter press for washing until it is neutral to obtain a filter cake.

[0087] Step 4: After the filter cake is slurried evenly with water, 1,300 kg of o-dichlorobenzene is added, liquid alkali is added to adjust the pH to 13-14, 75 kg of polymerized rosin is added, the temperature is raised for emulsification for 5 hours, and then the temperature is continued to be raised and pressurized to 0.35 MPa for 7 hours. After the pressure is maintained, o-dichlorobenzene is distilled out, 30 kg of calcium chloride is added, the temperature is raised to 80°C and maintained for 1 hour, 8.4 kg (dry) of derivative A filter cake is added, and the temperature is maintained at 80°C for 60 minutes. 3.9 kg of additive dodecyl ammonium chloride is added and maintained for 3 hours, and the material is fed into a filter press for washing, and the filter cake is washed with water until neutral, and the phthalocyanine green complex is obtained after drying.

[0088] In order to more intuitively demonstrate the process advantages of the present invention, the preparation method of phthalocyanine green using the present invention is compared with the method using equivalent replacement using the same process.

[0089] In order to more intuitively demonstrate the process advantages of the present invention, the preparation method of phthalocyanine green using the present invention is compared with the method using equivalent replacement using the same process.

[0090] Comparative Example 1:

[0091] The preparation method is the same as that of Example 2, except that: in the preparation process of this comparative example, no auxiliary agent is added; no phthalocyanine green derivative is added;

[0092] Comparative Example 2:

[0093] The preparation method is the same as that of Example 2, except that no auxiliary agent is added during the preparation of this comparative example;

[0094] Comparative Example 3:

[0095] The preparation method is the same as that of Example 2, except that in the preparation process of this comparative example, the auxiliary agent is replaced with alkylphenol polyoxyethylene ether;

[0096] Comparative Example 4:

[0097] The preparation method is the same as that of Example 2, except that in the preparation process of this comparative example, the auxiliary agent is replaced with sodium alkyl sulfonate, specifically sodium dodecyl sulfonate;

[0098] Comparative Example 5:

[0099] The preparation method is the same as that of Example 2, except that: in the preparation process of this comparative example, no phthalocyanine green derivative is added;

[0100] Comparative Example 6:

[0101] The preparation method is the same as that of Example 1, except that: in the preparation process of this comparative example, no phthalocyanine green derivative is added;

[0102] Comparative Example 7: Phthalocyanine green derivatives

[0103] The color difference detection of the phthalocyanine green derivative prepared by the present invention; the above examples and comparative examples are subjected to color difference detection according to the following method, and the detection results are shown in Table 1-2;

[0104] Melamine coating detection method:

[0105] Preparation of thick slurry: According to the glass beads 90 parts of melamine resin, 70 parts of melamine resin and 5 parts of pigment are mixed in a 150ml glass bottle, and then dispersed in a SHH-1VH disperser for 60 minutes to obtain a thick slurry.

[0106] Preparation of white paste: According to the glass beads 90 parts of melamine resin, 60 parts of melamine resin and 15 parts of pigment are mixed in a 150ml glass bottle, and then dispersed in a SHH-1VH disperser for 60 minutes to obtain white paste. Preparation of diluted color paste: 20 parts of the prepared white paste and 1 part of the thick paste are mixed evenly for later use

[0107] Proofing: Use a 150μm film applicator to prepare a thick color card and a diluted color card, let them level naturally for 15 minutes, put them in a 120℃ oven for 30 minutes, and take out the color card Datacolor Spectro 750 for color difference test

[0108] How to use Datacolor Spectro 750 colorimeter:

[0109] Correction:

[0110] 1. Place the black tube on the spectrometer and press Ready to calibrate the black tube.

[0111] 2. Replace the white board and place it on the spectrometer, then press Ready to perform white board calibration.

[0112] 3. Replace the green board and place it on the spectrometer, then press Ready to perform green board calibration.

[0113] Determination: Measure the standard sample first, then measure the batch sample (usually measure 3 points).

[0114] Measurement results: The results are based on the data of D65 light source;

[0115] Table 1: Effects of different additives and phthalocyanine green derivatives on the quality of phthalocyanine green products

[0116]

[0117] From the data analysis in Table 1, we can see that:

[0118] (1) In Examples 1-3 of the present invention, the product has a yellowish color, high color strength and low viscosity; the above characteristics of the product can be applied to high-end automotive primers, high-end powder coatings, high-end metal decorative inks, high-end spinning and liquid crystal inks;

[0119] (2) The data of Comparative Example 1 show that: the difference of Comparative Example 1 is that no additives and no phthalocyanine green derivatives are added, the detection index is blue, the color strength is low, and the viscosity is high.

[0120] (3) The data of Comparative Example 2 show that: the difference of Comparative Example 2 is that no auxiliary agent is added.

[0121] The yellow phase, high color strength and low viscosity in the test indicators all decreased to a certain extent, especially the yellow phase and viscosity. There was no significant difference between the product of Comparative Example 2 and the product of Comparative Example 1.

[0122] (4) The data of Comparative Examples 3-4 show that: the difference between Comparative Examples 3-4 is that the auxiliary agent is replaced with alkylphenol polyoxyethylene ether or sodium dodecyl sulfate;

[0123] Analysis of the test data: the hue is yellowish, the color strength is high, but the viscosity is high.

[0124] (5) The data of Comparative Examples 5-6 show that: the difference between Comparative Examples 5-6 is that no phthalocyanine green derivative is added and the additives are different;

[0125] Analyzing from the test data: the hue is yellowish, the color strength is slightly increased, but the viscosity is high.

[0126] (6) From the data of comparative example 7, it can be seen that as a phthalocyanine green derivative, its own detection index shows that the phthalocyanine green derivative itself has a certain effect on yellowness, high color strength and reduced viscosity, but does not have a more positive effect.

[0127] In order to more intuitively demonstrate the process advantages of the addition sequence of the additives of the present invention, a comparison is made between the preparation method of phthalocyanine green of the present invention and the method of equivalent replacement of the same process.

[0128] Comparative Example 8:

[0129] The preparation method is the same as that of Example 1, except that: in the preparation process of this comparative example, the auxiliary agent is added before the phthalocyanine green derivative and after the calcium chloride;

[0130] Table 2: Effect of additive addition order on phthalocyanine green product quality

[0131]

[0132] From the data analysis in Table 2, we can see that:

[0133] Comparison between Example 1 and Comparative Example 8 shows that:

[0134] The additive dodecyl ammonium chloride was added before derivative A and after calcium chloride, which resulted in a decrease in blue phase and color strength and an increase in viscosity. Therefore, the order of adding additives has an impact on the synergistic effect of phthalocyanine green derivatives, especially the impact on yellow phase, color strength and viscosity is more obvious.

[0135] In summary:

[0136] 1. The method for preparing phthalocyanine green provided by the present invention can produce a high-purity, high-quality phthalocyanine green composite product with fine particles, uniform particle size distribution, excellent color and strong tinting power.

[0137] 2. The phthalocyanine green preparation method provided by the present invention can produce a yellow-phase, low-viscosity product that can be used in high-end automobile primers, high-end coatings, high-end metal decorative inks, and high-end liquid crystal inks.

Claims

1. A method for preparing a phthalocyanine green complex, characterized in that The method comprises the following steps: (1) Alternately add aluminum chloride, sodium chloride and sodium bromide into a reaction kettle, raise the temperature to 155-170° C., stir until all the materials in the reaction kettle are dissolved, stop heating, and add copper phthalocyanine and copper chloride in sequence; (2) After the addition of copper phthalocyanine and copper chloride, the reaction was continued by passing chlorine gas for 12-16 hours at a temperature of 155° C. to 160° C., until no hydrogen chloride was produced by tail gas detection, stirring was stopped, and the passing of chlorine was stopped to obtain a reaction solution; (3) The reaction solution is placed in a dilution tank while hot and stirred until the material temperature in the dilution tank drops to 70° C. The material is then placed in a filter press and washed with water until the washing liquid is neutral to obtain a filter cake; (4) After the filter cake is evenly slurried with water, o-dichlorobenzene is added, liquid alkali is added to adjust the pH to 13-14, rosin and emulsion are added, and the mass ratio of filter cake, rosin and calcium chloride is 100:9-12; the temperature is raised for emulsification for 2-5 hours, and then the temperature is raised and pressurized for 5-10 hours, and the pressure is between 0.1-0.6MPa. After the pressure is maintained, o-dichlorobenzene is distilled out, and 30-50% of calcium chloride is added based on the amount of rosin added, the temperature is raised to 70-85°C for insulation, 0.5-5.0% of phthalocyanine green derivative is added, and the temperature is maintained at 70-85°C. 0.25-5.0% of auxiliary agent is added for insulation, and the material is fed into a filter press for water washing, the solid phase is washed with water until neutral, and the phthalocyanine green complex is obtained after drying.

2. The method for preparing the phthalocyanine green complex according to claim 1, characterized in that In step (1), aluminum chloride, sodium chloride, sodium bromide, copper phthalocyanine and copper chloride are added in sequence in a mass ratio of (5-8):1:(0.1-0.5):(0.5-2.0):(0.1-0.5).

3. The method for preparing the phthalocyanine green complex according to claim 1, characterized in that The rate of passing chlorine in step (2) is 70-75 kg / h.

4. The method for preparing the phthalocyanine green complex according to claim 1, characterized in that The auxiliary agent B is an alkylamine or an alkylammonium chloride.

5. The method for preparing the phthalocyanine green complex according to claim 1, characterized in that The mass of the emulsion is 13-30 times the mass of the filter cake. The emulsion is composed of xylene, an emulsifier and water in a mass ratio of (15-20):1:(1-20). The xylene is at least one of o-xylene, m-xylene and p-xylene. The emulsifier is phenethylphenol polyoxypropylene polyoxyethylene ether or phenethylphenol polyoxyethylene ether. The o-dichlorobenzene is 1-3 times the mass of the filter cake.

6. The method for preparing the phthalocyanine green complex according to claim 1, characterized in that The method for preparing the phthalocyanine green derivative comprises: a chlorination process and a sulfonation process; The chlorination process: ① Add aluminum chloride and sodium chloride into the reactor, heat the jacket until the materials in the reactor are completely dissolved, slowly start the stirring paddle to start stirring, stop heating when all the materials in the reactor are dissolved, and add copper phthalocyanine and copper chloride in sequence; ② After adding copper chloride and stirring, start to introduce chlorine gas for reaction. The chlorination reaction time is 4-6 hours. The temperature is controlled between 155℃-160℃. About 400 kg of chlorine gas is introduced. Stop introducing chlorine gas when the reaction reaches the end point. ③ Add bottom water to the reactor in advance, put the reacted chlorinated materials into the bottom water, and the diluted materials are fed into the filter press for washing. Wash with water until neutral to obtain filter cake, and dry to obtain reactant A. The sulfonation process: ①Put fuming sulfuric acid into the reactor and add reactant A, control the temperature of the materials in the reactor to be lower than 50℃, and stir evenly; ② Raise the temperature of the jacket to 60-70℃ in the kettle and keep the temperature to react until the end point ③ Add water to the dilution kettle, put the sulfonated material into the dilution kettle after 60 minutes, raise the temperature to 80-95℃, keep warm and filter to obtain the phthalocyanine green derivative.

7. The method for preparing the phthalocyanine green complex according to claim 6, characterized in that: In the chlorination process, the mass ratio of aluminum chloride, sodium chloride, copper phthalocyanine and copper chloride is (3-5):1:(0.8-0.9):(0.1-0.15).

Images