A kind of synthetic method of quinophthalone pigment

Abstract

The invention discloses a method for synthesizing a quinophthalone pigment, comprising the following steps: first, preparing modified quinophthalone; second, mixing and dispersing treatment; third, dissolving and adsorbing treatment; and fourth, mixing treatment of finished products. The invention uses titanium dioxide and a silane coupling agent to prepare the modified quinophthalone, so that the light resistance and stability of the modified quinophthalone can be improved, and the coloring ability can be improved, thereby effectively solving the problem that the traditional quinophthalone pigment has poor coloring ability. The modified quinophthalone mixed with a dispersant is loaded and adsorbed by using a gel filler to obtain a powder, which can be dissolved and mixed in various fields according to needs and then used, thereby effectively improving the applicable fields of the quinophthalone pigment. Moreover, green and environmentally friendly materials are used in the preparation process, and the reaction conditions are mild, so the quinophthalone pigment is applicable to industrialized mass production.

Description

Technical Field

[0001] The invention relates to the technical field of pigment synthesis, in particular to a method for synthesizing a quinophthalone pigment. Background Art

[0002] Pigments are widely used in human life, such as coatings, paints, paper, adhesives, latex, toners, fabrics, fibers, plastics, cosmetics and inks. Currently, there are a large number of organic and inorganic pigments on the market, which are different in color, transparency, color fastness and physiological properties, and these properties affect consumers' choice of pigments. Quinophthalone pigment is an organic pigment. At present, the high hiding power of quinophthalone pigment makes it occupy the mainstream market of pigments. Its weather resistance, light resistance and thermal stability are good, making it widely used in the fields of coatings, plastics, printing inks, etc., but the coloring ability of quinophthalone pigment is poorer than that of traditional pigments. These defects limit its application in other pigment fields such as dyeing. Therefore, the present invention proposes a synthesis method of quinophthalone pigment to solve the problems existing in the prior art. Summary of the invention

[0003] In view of the above problems, the purpose of the present invention is to provide a method for synthesizing quinophthalone pigment. The method for synthesizing quinophthalone pigment uses titanium dioxide and a silane coupling agent to prepare modified quinophthalone, which can improve its light resistance and stability, and at the same time improve its coloring ability, effectively solving the problem of poor coloring ability of traditional quinophthalone pigments. By using a gel filler to carry and adsorb the modified quinophthalone mixed with a dispersant and obtaining a powder, it can be dissolved and mixed in various fields according to needs and used, effectively improving the applicable fields of quinophthalone pigments, and the preparation process uses green and environmentally friendly materials, the reaction conditions are mild, and it is suitable for industrial mass production.

[0004] To achieve the purpose of the present invention, the present invention is achieved through the following technical scheme: a quinophthalone pigment, which includes a modified quinophthalone, a functional additive, a gel filler and a dispersant mixed in a mass ratio of 70-75:3-5:15-20:6-8; wherein the functional additive is a mixture of ferrocene-polyethylene glycol-thiol and a metal antibacterial agent mixed in a mass ratio of 1-2:0.4-1.

[0005] A further improvement is that the modified quinophthalone is prepared by mixing and modifying quinophthalone with titanium dioxide and a silane coupling agent, and the mass ratio of the quinophthalone, titanium dioxide and silane coupling agent is 1.5-2:3-5.

[0006] A further improvement is that the metal antibacterial agent is one of silver ions, copper ions, zinc ions, iron ions and titanium ions, and the gel filler is silicon-based aerogel.

[0007] A method for synthesizing a quinophthalone pigment comprises the following steps:

[0008] Step 1, preparation of modified quinophthalone: ​​firstly, quinaldine and pyromellitic anhydride are mixed to obtain an intermediate, then the intermediate is mixed with a bisamide bridge to obtain a quinophthalone pigment connected with a bisamide bridge, and titanium dioxide and a silane coupling agent are used to modify the pigment to obtain a modified quinophthalone;

[0009] Step 2: Mixing and dispersing: adding the modified quinophthalone, the functional additive and half of the dispersant into deionized water for mixing and stirring, then evaporating and drying the mixed solution to obtain a mixed solid, and finally adding the mixed solid into a nano-grinder for nano-grinding to obtain a nano-grade mixed powder;

[0010] Step 3: Dissolution and adsorption treatment: pre-treat the gel filler first, then mix it with the nano-scale mixed powder and add it into deionized water for stirring and adsorption, and finally evaporate, dry and crush to obtain a semi-finished pigment;

[0011] Step 4: Finished product mixing: The crushed semi-finished product pigment is mixed with the remaining dispersant and poured into a nano-grinder for grinding again to obtain a nano-grade quinophthalone pigment.

[0012] The further improvement is that: the step 1 is specifically as follows:

[0013] S1, mixing quinaldine and pyromellitic anhydride and adding them to an inert solvent, then adding a catalyst to carry out a condensation reaction for 4 hours to obtain an intermediate;

[0014] S2, purifying the intermediate, and then mixing it with a diamide bridge reagent to obtain a diamide bridge-connected quinophthalone pigment;

[0015] S3, filtering, washing, and drying the quinophthalone pigment connected with the diamide bridge to obtain quinophthalone pigment powder;

[0016] S4, mixing the quinophthalone pigment powder and titanium dioxide and homogenizing them, then adding a silane coupling agent, heating, mixing and stirring, and then drying and grinding to obtain modified quinophthalone.

[0017] A further improvement is that the inert solvent in S1 is xylene and the catalyst is zinc chloride.

[0018] Further improvements are: the mixing reaction in S2 is carried out at 80° C. for 2 hours, the reaction is washed with ethanol and then dried in S3; and the silane coupling agent is added in S4 and then the temperature is raised to 80-90° C. and mixed and stirred for 70-80 minutes.

[0019] The further improvement is that: the preparation method of the dispersant used in the step 2 is to first mix acrylic acid, butyl acrylate, vinyl acetate, zinc acetate, ethylene glycol and water in a mass ratio of 10:12:15:0.5:30:32.5 under a water bath heating condition of 65-70°C, then drop dimethylformamide and ammonium persulfate aqueous solution into the mixed solution and continue to stir, then add hydrogen peroxide and stir to react, finally adjust the pH value of the solution to between 7.5 and 7.8 with sodium carbonate after natural cooling, drop the solution into an acetone solution to obtain a precipitate, filter out the precipitate, wash, dry and grind to obtain the dispersant.

[0020] A further improvement is that the gel filler pretreatment in step 3 is to crush the aerogel and then grind it in a grinding machine and pass it through a 200-mesh sieve to obtain a powdered aerogel.

[0021] The beneficial effects of the present invention are as follows: the present invention prepares the modified quinophthalone through titanium dioxide and a silane coupling agent, so that the light resistance and stability of the modified quinophthalone can be improved, and the coloring ability can be improved, which effectively solves the problem that the traditional quinophthalone pigment has poor coloring ability; the modified quinophthalone mixed with a dispersant is carried and adsorbed by using a gel filler to obtain a powder, which can be dissolved and mixed in various fields according to needs and then used, which effectively improves the applicable fields of the quinophthalone pigment; and the preparation process uses green and environmentally friendly materials, and the reaction conditions are mild, which is suitable for industrial mass production. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 This is a flow chart of the method of Example 1 of the present invention. DETAILED DESCRIPTION

[0023] In order to deepen the understanding of the present invention, the present invention will be further described in detail below in conjunction with examples. The examples are only used to explain the present invention and do not constitute a limitation on the protection scope of the present invention.

[0024] Example 1

[0025] according to Figure 1 As shown, this embodiment provides a quinophthalone pigment, which includes modified quinophthalone, a functional additive, a gel filler and a dispersant mixed in a mass ratio of 70:5:17:8; wherein the functional additive is a mixture of ferrocene-polyethylene glycol-thiol and a metal antibacterial agent mixed in a mass ratio of 1:0.4.

[0026] The modified quinophthalone is prepared by mixing and modifying quinophthalone with titanium dioxide and a silane coupling agent, and the mass ratio of the quinophthalone, titanium dioxide and silane coupling agent is 1.5:3.

[0027] The metal antibacterial agent is silver ion, and the gel filler is silicon-based aerogel.

[0028] A method for synthesizing a quinophthalone pigment comprises the following steps:

[0029] Step 1, preparation of modified quinophthalone: ​​firstly, quinaldine and pyromellitic anhydride are mixed to obtain an intermediate, then the intermediate is mixed with a bisamide bridge to obtain a quinophthalone pigment connected with a bisamide bridge, and titanium dioxide and a silane coupling agent are used to modify the pigment to obtain a modified quinophthalone;

[0030] Specifically:

[0031] S1, 10 parts of quinaldine and 15 parts of pyromellitic anhydride are mixed and added to a xylene inert solvent, and then 0.5 parts of zinc chloride catalyst are added to carry out a condensation reaction for 4 hours to obtain an intermediate;

[0032] S2, purifying the intermediate, and then mixing it with a diamide bridge reagent at 80° C. for 2 h to obtain a diamide bridge-connected quinophthalone pigment;

[0033] Purification specifically comprises centrifuging the intermediate mixture to obtain a precipitate, then adding it again into a xylene inert solvent and adding a zinc chloride catalyst to react, and then centrifuging again to separate the precipitate, thereby obtaining a purified intermediate;

[0034] S3, filtering 5 parts of quinophthalone pigments connected by bisamide bridges, washing with ethanol and water, and drying to obtain quinophthalone pigment powder;

[0035] S4. 18 parts of quinophthalone pigment powder and 5 parts of titanium dioxide are mixed and homogenized, and then a silane coupling agent is added, and the mixture is heated to 80-90° C., and heated, mixed and stirred for 75 minutes, and then dried and ground to obtain modified quinophthalone.

[0036] Step 2, mixing and dispersing treatment: adding the modified quinophthalone, the functional additive and half of the dispersant into deionized water for mixing and stirring, then evaporating and drying the mixed solution to obtain a mixed solid, and finally adding the mixed solid into a nano-grinder for nano-grinding treatment to obtain a nano-grade mixed powder, wherein the nano-grinding uses a grinding ball of 0.06-0.1 mm, the stirring rotor speed is controlled at 15-18 m / sec, and the grinding temperature is controlled at 30-40°C;

[0037] The preparation method of the dispersant is as follows: first, acrylic acid, butyl acrylate, vinyl acetate, zinc acetate, ethylene glycol and water are mixed and stirred in a mass ratio of 10:12:15:0.5:30:32.5 in a water bath heating condition of 65-70°C, then 5 ml of dimethylformamide and 3.5 ml of ammonium persulfate aqueous solution are dripped into the mixed solution and stirred continuously, then 4 ml of hydrogen peroxide is added and stirred for reaction, finally, after natural cooling, the pH value of the solution is adjusted to between 7.5 and 7.8 using sodium carbonate, and the solution is dripped into an 80% acetone solution to obtain a precipitate, and the precipitate is filtered out, washed, dried and ground into powder to obtain the dispersant.

[0038] Step 3: Dissolution and adsorption treatment: pre-treat the silicon-based aerogel, then mix it with the nano-scale mixed powder and add it into deionized water for stirring and adsorption, and finally evaporate, dry and crush to obtain a semi-finished pigment;

[0039] The pretreatment specifically includes crushing the silicon-based aerogel, grinding it in a grinding machine, and passing it through a 200-mesh sieve to obtain a powdered silicon-based aerogel.

[0040] Step 4, finished product mixing treatment: the crushed semi-finished pigment is mixed with the remaining dispersant and poured into the nano-grinder for grinding again to obtain a nano-grade quinophthalone pigment. The nano-grinding uses a grinding ball of 0.1-0.3 mm, the stirring rotor speed is controlled at 13-15 m / sec, and the grinding temperature is controlled at 30-40 ° C.

[0041] Example 2

[0042] according to Figure 1 As shown, this embodiment provides a quinophthalone pigment, which includes modified quinophthalone, a functional additive, a gel filler and a dispersant mixed in a mass ratio of 75:3:15:7; wherein the functional additive is a mixture of ferrocene-polyethylene glycol-thiol and a metal antibacterial agent mixed in a mass ratio of 2:1.

[0043] The modified quinophthalone is prepared by mixing and modifying quinophthalone with titanium dioxide and a silane coupling agent, and the mass ratio of the quinophthalone, titanium dioxide and silane coupling agent is 1.5:4.

[0044] The metal antibacterial agent is silver ion, and the gel filler is silicon-based aerogel.

[0045] A method for synthesizing a quinophthalone pigment comprises the following steps:

[0046] Step 1, preparation of modified quinophthalone: ​​firstly, quinaldine and pyromellitic anhydride are mixed to obtain an intermediate, then the intermediate is mixed with a bisamide bridge to obtain a quinophthalone pigment connected with a bisamide bridge, and titanium dioxide and a silane coupling agent are used to modify the pigment to obtain a modified quinophthalone;

[0047] Specifically:

[0048] S1, 10 parts of quinaldine and 15 parts of pyromellitic anhydride are mixed and added to a xylene inert solvent, and then 0.5 parts of zinc chloride catalyst are added to carry out a condensation reaction for 4 hours to obtain an intermediate;

[0049] S2, purifying the intermediate, and then mixing it with a diamide bridge reagent at 80° C. for 2 h to obtain a diamide bridge-connected quinophthalone pigment;

[0050] Purification specifically comprises centrifuging the intermediate mixture to obtain a precipitate, then adding it again into a xylene inert solvent and adding a zinc chloride catalyst to react, and then centrifuging again to separate the precipitate, thereby obtaining a purified intermediate;

[0051] S3, filtering 5 parts of quinophthalone pigments connected by bisamide bridges, washing with ethanol and water, and drying to obtain quinophthalone pigment powder;

[0052] S4. 18 parts of quinophthalone pigment powder and 5 parts of titanium dioxide are mixed and homogenized, and then a silane coupling agent is added, and the mixture is heated to 80-90° C., and heated, mixed and stirred for 75 minutes, and then dried and ground to obtain modified quinophthalone.

[0053] Step 2, mixing and dispersing treatment: adding the modified quinophthalone, the functional additive and half of the dispersant into deionized water for mixing and stirring, then evaporating and drying the mixed solution to obtain a mixed solid, and finally adding the mixed solid into a nano-grinder for nano-grinding treatment to obtain a nano-grade mixed powder, wherein the nano-grinding uses a grinding ball of 0.06-0.1 mm, the stirring rotor speed is controlled at 15-18 m / sec, and the grinding temperature is controlled at 30-40°C;

[0054] The preparation method of the dispersant is as follows: first, acrylic acid, butyl acrylate, vinyl acetate, zinc acetate, ethylene glycol and water are mixed and stirred in a mass ratio of 10:12:15:0.5:30:32.5 in a water bath heating condition of 65-70°C, then 5 ml of dimethylformamide and 3.5 ml of ammonium persulfate aqueous solution are dripped into the mixed solution and stirred continuously, then 4 ml of hydrogen peroxide is added and stirred for reaction, finally, after natural cooling, the pH value of the solution is adjusted to between 7.5 and 7.8 using sodium carbonate, and the solution is dripped into an 80% acetone solution to obtain a precipitate, and the precipitate is filtered out, washed, dried and ground into powder to obtain the dispersant.

[0055] Step 3: Dissolution and adsorption treatment: pre-treat the silicon-based aerogel, then mix it with the nano-scale mixed powder and add it into deionized water for stirring and adsorption, and finally evaporate, dry and crush to obtain a semi-finished pigment;

[0056] The pretreatment specifically includes crushing the silicon-based aerogel, grinding it in a grinding machine, and passing it through a 200-mesh sieve to obtain a powdered aerogel.

[0057] Step 4, finished product mixing treatment: the crushed semi-finished pigment is mixed with the remaining dispersant and poured into the nano-grinder for grinding again to obtain a nano-grade quinophthalone pigment. The nano-grinding uses a grinding ball of 0.1-0.3 mm, the stirring rotor speed is controlled at 13-15 m / sec, and the grinding temperature is controlled at 30-40 ° C.

[0058] In order to further understand the performance of the quinophthalone pigment prepared by the present invention, the pigments prepared in Example 1 and Example 2 were tested for performance together with conventional quinophthalone pigments and high tinting strength pigments on the market. The tinting strength and stability tests were performed under the same environment.

[0059] In the tinting strength test, the four groups of pigments were dyed on the fabric and left to stand for 20-30 minutes, then the excess pigment was washed off with water, and the color depth was observed. At the same time, the four groups of dyed fabrics were subjected to a one-month stability test. During the test, the fabrics were washed once a day and dried. This was repeated for one month. During this period, the dyeing conditions were recorded at 10, 20 and 30 days respectively. The experimental results are shown in the following table.

[0060] Tinting strength and stability test table

[0061]

[0062] It can be seen from the data in the above table that the tinting power of the quinophthalone pigment prepared in the present application is comparable to that of some high tinting power pigments on the market, but has better stability after long-term use, and its stability is better than that of high tinting power pigments on the market; and compared with traditional quinophthalone pigments, the tinting ability is significantly improved, but the difference in stability is small, which shows that the tinting power of the quinophthalone pigment of the present application is better than that of traditional quinophthalone pigments. In summary, the quinophthalone pigment prepared in the present application effectively improves the stability of the pigment while improving the tinting power.

[0063] The above shows and describes the basic principles, main features and advantages of the present invention. It should be understood by those skilled in the art that the present invention is not limited to the above embodiments. The above embodiments and descriptions are only for explaining the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention may have various changes and improvements, which fall within the scope of the present invention. The scope of protection of the present invention is defined by the attached claims and their equivalents.

Claims

1. A quinophthalone pigment, characterized in that: The quinophthalone pigment comprises modified quinophthalone, a functional additive, a gel filler and a dispersant mixed in a mass ratio of 70-75:3-5:15-20:6-8; wherein the functional additive is a mixture of ferrocene-polyethylene glycol-thiol and a metal antibacterial agent in a mass ratio of 1-2:0.4-1; the modified quinophthalone is prepared by mixing and modifying quinophthalone with titanium dioxide and a silane coupling agent, and the mass ratio of quinophthalone, titanium dioxide and silane coupling agent is 1.5-2:3-5; The dispersant is prepared by first mixing acrylic acid, butyl acrylate, vinyl acetate, zinc acetate, ethylene glycol and water in a mass ratio of 10:12:15:0.5:30:32.5 under a water bath heating condition of 65-70°C, then dropping dimethylformamide and an aqueous solution of ammonium persulfate into the mixed solution and continuously stirring, then adding hydrogen peroxide and stirring for reaction, finally adjusting the pH value of the solution to between 7.5 and 7.8 with sodium carbonate after natural cooling, dropping the solution into an acetone solution to obtain a precipitate, filtering out the precipitate, washing, drying, and then grinding the precipitate to obtain the dispersant.

2. A quinophthalone pigment according to claim 1, characterized in that: The metal antibacterial agent is one of silver ions, copper ions, zinc ions, iron ions and titanium ions, and the gel filler is silicon-based aerogel.

3. A method for synthesizing a quinophthalone pigment, characterized in that: The following steps are involved: Step 1: firstly mix quinaldine and pyromellitic anhydride to obtain an intermediate, then mix the intermediate with a bisamide bridge to obtain a quinophthalone pigment connected by a bisamide bridge, and modify it with titanium dioxide and a silane coupling agent to obtain a modified quinophthalone; Specifically: S1, mixing quinaldine and pyromellitic anhydride and adding them to an inert solvent, then adding a catalyst to carry out a condensation reaction for 4 hours to obtain an intermediate; S2, purifying the intermediate, and then mixing it with a diamide bridge reagent to obtain a diamide bridge-connected quinophthalone pigment; S3, filtering, washing, and drying the quinophthalone pigment connected with the diamide bridge to obtain quinophthalone pigment powder; S4, mixing quinophthalone pigment powder and titanium dioxide and homogenizing, adding a silane coupling agent, heating, mixing and stirring, and then drying and grinding to obtain modified quinophthalone; Step 2: adding the modified quinophthalone, the functional additive and half of the dispersant into deionized water for mixing and stirring, then evaporating and drying the mixed solution to obtain a mixed solid, and finally adding the mixed solid into a nano-grinder for nano-grinding to obtain a nano-grade mixed powder; The preparation method of the dispersant used therein is to first mix acrylic acid, butyl acrylate, vinyl acetate, zinc acetate, ethylene glycol and water in a mass ratio of 10:12:15:0.5:30:32.5 in a water bath heating condition of 65-70°C, then drop dimethylformamide and ammonium persulfate aqueous solution into the mixed solution and continue stirring, then add hydrogen peroxide and stir to react, finally adjust the pH value of the solution to between 7.5 and 7.8 with sodium carbonate after natural cooling, and drop the solution into an acetone solution to obtain a precipitate, filter out the precipitate, wash, dry and grind to obtain a dispersant; Step 3: pre-treat the gel filler, then mix it with the nano-scale mixed powder, add it into deionized water for stirring and adsorption, and finally evaporate, dry and crush to obtain a semi-finished pigment; Step 4: Mix the crushed semi-finished pigment with the remaining dispersant and pour it into the nano grinder for grinding again to obtain the nano-grade quinophthalone pigment.

4. The method for synthesizing a quinophthalone pigment according to claim 3, wherein: In the S1, the inert solvent is xylene and the catalyst is zinc chloride.

5. The method for synthesizing a quinophthalone pigment according to claim 3, wherein: The mixed reaction in S2 is carried out at 80° C. for 2 hours. After the reaction in S3, the mixture is washed with ethanol and then dried. In S4, a silane coupling agent is added, and the mixture is heated to 80-90° C. and mixed and stirred for 70-80 minutes.

6. The method for synthesizing a quinophthalone pigment according to claim 3, wherein: The gel filler pretreatment in step 3 specifically comprises crushing the aerogel, grinding it in a grinder and passing it through a 200-mesh sieve to obtain a powdered aerogel.

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