Organic-inorganic composite functional pigment preparation method

Abstract

An organic-inorganic composite functional pigment preparation method, comprising the following steps: step 1, dissolving 10 parts of raw material A in 300 parts of water according to a mass ratio, and adding 2 parts of raw material B and 0.2 parts of polyethylene glycol; step 2, adding 5 parts of butyl titanate and 1 part of an organic acid, and heating at 75°C for reaction for 2 hours; step 3, adding 4 parts of ethylene glycol and 0.2 parts of hydrochloric acid, and carrying out stirring for 1 hour; step 4, carrying out aging under a sealed condition at 50°C for 24 hours, carrying out water washing and centrifugal separation, and carrying out oxygen-free calcination for 4 hours to obtain a pre-product; step 5, dispersing 10 parts of the product into 400 parts of N,N'-dimethylacetamide, adding 0.2 parts of 4-dimethylaminopyridine, adding 5 parts of a styrene-maleic anhydride copolymer, and heating at 45°C for reaction for 12 hours; and step 6, after washing with ethanol, separation, and drying, mixing a dispersing agent, a pigment, a coupling agent, and a solvent, and grinding a mixture to form a composite functional pigment. In step 1, A is a mixture formed by sodium tungstate and sodium metavanadate at a mass ratio of 2:8, and the raw material B is two or three selected from aluminum nitrate, zinc nitrate, cobalt nitrate, barium nitrate, manganese nitrate, and indium nitrate. The preparation method is simple and convenient, has low energy consumption and wide applicability, and has good economic efficiency and high efficiency in batch production.

Description

A method for preparing organic-inorganic composite functional pigment Technical Field

[0001] The present invention relates to the technical field of functional pigments, and more specifically to a method for preparing an organic-inorganic composite functional pigment. Background Art

[0002] Pigments imbue the world with a rich tapestry of color. They are widely used across industries. Traditional pigments, based on inorganic materials, offer stable color, but often lack vividness. Organic pigments, while offering a wide variety of color options, often suffer from poor weather resistance, discoloration, and fading in actual use. Organic-inorganic composite pigments offer complementary advantages to a certain extent. Furthermore, by providing pigments with heat insulation and UV protection, they enhance the overall value of the material while enriching the visual experience, thereby fulfilling the societal need for energy conservation and environmental protection.

[0003] Nowadays, pigments no longer simply provide color; they encompass a wider range of functionalities. Chinese patent CN106398321A discloses a method for preparing a green organic / inorganic composite infrared reflective pigment. This method involves hydrolyzing tetrabutyl titanate as a precursor and coating it with phthalocyanine green pigment particles. This method yields a series of green infrared reflective pigments in varying shades, with a total solar reflectivity of approximately 60%. Chinese patent CN110028811A discloses a high-near-infrared reflectivity blue pigment and its preparation method. This pigment utilizes rutile titanium dioxide as a core and utilizes a combustion reaction to form a cobalt blue pigment shell on its surface. The resulting blue pigment has a controllable color depth and can achieve an infrared reflectivity of approximately 70%. These advances have enhanced the functionality of organic / inorganic composite pigments, allowing for further expansion of their composite functions and enhancing energy conservation and emission reduction benefits. Furthermore, through technological improvements, the richness of their colors can be further expanded to meet the demands of practical applications.

[0004] Summary of the Invention

[0005] The purpose of the present invention is to provide a method for preparing an organic-inorganic composite functional pigment, which solves the problem that the functional pigments prepared by the above application have a single color and the composite structure is not stable enough.

[0006] To achieve the above object, the present invention provides the following technical solution: a method for preparing an organic-inorganic composite functional pigment, wherein the method for preparing the composite functional pigment capable of achieving heat insulation and UV protection functions comprises the following steps:

[0007] Step 1: Dissolve 10 parts of raw material A in 300 parts of water, add 1 to 3 parts of raw material B, and then add 0.2 parts of polyethylene glycol;

[0008] Step 2: Add 5 parts of butyl titanate and 1 part of organic acid, and heat to 70-80°C for 2 hours;

[0009] Step 3: Add 3 to 5 parts of ethylene glycol, stir for 1 hour, add 0.2 parts of hydrochloric acid, and stir for 1 hour;

[0010] Step 4: Aging at 50°C for 24 hours, washing with water and centrifuging, and calcining in the absence of oxygen for 3 to 5 hours to obtain a pre-product at a calcination temperature of 150 to 220°C;

[0011] Step 5: 10 parts of the product are dispersed in 300-500 parts of N,N′-dimethylacetamide, 0.1-0.3 parts of 4-dimethylaminopyridine and 5 parts of styrene-maleic anhydride copolymer are added, and the mixture is heated at 40-50°C for 12 hours.

[0012] Step 6: After washing with ethanol and separating and drying, mix it with 0.2 parts of dispersant, 0.5-2 parts of pigment, 0.1 parts of coupling agent, and 50 parts of solvent, heat and stir at 50-70℃ for 2-5 hours, and grind to form a composite functional pigment.

[0013] As a preferred embodiment of the present invention, the raw material A in step 1 is a mixture of sodium tungstate and sodium metavanadate, with a mass ratio of 2:8.

[0014] As a preferred embodiment of the present invention, the raw material B in step 1 is selected from two or three of aluminum nitrate, zinc nitrate, cobalt nitrate, barium nitrate, manganese nitrate and indium nitrate.

[0015] As a preferred embodiment of the present invention, the organic acid in step 4 is a mixture of citric acid and glacial acetic acid in a mass ratio of 4:1.

[0016] As a preferred embodiment of the present invention, the dispersant in step 6 is selected from polyvinyl pyrrolidone and high molecular weight polyether, the coupling agent is a silane coupling agent, and the solvent is selected from acetone, ethylene glycol methyl ether acetate, and butyl acetate.

[0017] As a preferred embodiment of the present invention, the number average molecular weight of the polyethylene glycol in step 1 is 800 to 2000 g / mol.

[0018] As a preferred embodiment of the present invention, the number average molecular weight of the styrene-maleic anhydride copolymer in step 5 is 2000 to 5000 g / mol.

[0019] As a preferred embodiment of the present invention, in step 6, the red pigment is selected from Pigment Red 254; the yellow pigment is selected from Pigment Yellow 138; the green pigment is selected from Pigment Green 7; the blue pigment is selected from Pigment Blue 15:4; and the purple pigment is selected from Pigment Violet 23.

[0020] As a preferred embodiment of the present invention, the composite functional pigment is prepared by the preparation method according to any one of claims 1 to 8.

[0021] Compared with the prior art, the present invention has the following beneficial effects:

[0022] The present invention obtains primary functional particles by catalytic hydrolysis reaction and doping with multiple metal ions, by aging and calcining, and further coating the surface with styrene-maleic anhydride copolymer, and achieving physical and chemical dual compounding with the pigment through π-π conjugation and coupling to obtain the final product. The organic-inorganic composite functional pigment deeply combines the inorganic particles with the organic pigment, which not only achieves rich colors but also has outstanding functionality and weather resistance. The preparation method uses a relatively simple method to obtain a composite pigment with outstanding performance, which can be widely used in various color-required application fields such as plastic films, plastic products, and coatings. The organic pigment and the inorganic particles have good compositeness, outstanding weather resistance and rich colors; the prepared composite functional pigment has outstanding ultraviolet protection and infrared protection dual properties; the prepared composite functional pigment can achieve high transparency and high clarity while enriching the color; the preparation method is simple, low-energy consumption, meets the requirements of industrial production, has wide applicability, and has good economy and efficiency in mass production. DETAILED DESCRIPTION

[0023] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0024] Example 1

[0025] The present invention provides a method for preparing an organic-inorganic composite functional pigment, comprising the following steps:

[0026] Step 1: Dissolve 2g sodium tungstate and 8g sodium metavanadate in 300ml water, add 0.5g barium nitrate, 1g aluminum nitrate, and 0.8g zinc nitrate, and then stir and add 0.2g polyethylene glycol (Mn=1000g / mol);

[0027] Step 2: Add 5 g of butyl titanate, 0.8 g of citric acid, and 0.2 g of glacial acetic acid, and heat at 70°C for 2 h;

[0028] Step 3: Add 3 g of ethylene glycol, stir for 1 h, add 0.2 g of hydrochloric acid, and stir for 1 h;

[0029] Step 4: Aging at 50°C for 24 hours, washing three times, centrifuging, and calcining at 220°C in the absence of oxygen for 5 hours to obtain the pre-product;

[0030] Step 5: Disperse 10 g of the pre-product in 400 ml of N,N′-dimethylacetamide, add 0.1 g of 4-dimethylaminopyridine, add 5 g of styrene-maleic anhydride copolymer (Mn=2000 g / mol), and heat to 40°C for 12 h.

[0031] Step 6: After repeated washing with ethanol three times, centrifugation and vacuum drying, the product was mixed with 0.2 g of oleic acid polyoxyethylene ether 105, 0.7 g of pigment red 254, and 0.1 g of silane coupling agent KH550 in a solvent of 20 g of acetone and 30 g of ethylene glycol methyl ether acetate, heated and stirred at 50°C for 3 hours, and ground to form a red composite functional pigment.

[0032] Example 2

[0033] A method for preparing an organic-inorganic composite functional pigment comprises the following steps:

[0034] Step 1: Dissolve 2g sodium tungstate and 8g sodium metavanadate in 300ml water, add 0.8g aluminum nitrate, 0.3g cobalt nitrate, and 0.5g zinc nitrate, and then add 0.2g polyethylene glycol (Mn=800g / mol) while stirring;

[0035] Step 2: Add 5 g of butyl titanate, 0.8 g of citric acid, and 0.2 g of glacial acetic acid, and heat at 70°C for 2 h;

[0036] Step 3: Add 3 g of ethylene glycol, stir for 1 h, add 0.2 g of hydrochloric acid, and stir for 1 h;

[0037] Step 4: Aging at 50°C for 24 hours, washing three times, centrifuging, and calcining at 200°C in the absence of oxygen for 5 hours to obtain the pre-product;

[0038] Step 5: 10 g of the pre-product was dispersed in 400 ml of N,N′-dimethylacetamide, 0.1 g of 4-dimethylaminopyridine and 5 g of styrene-maleic anhydride copolymer (Mn=3000 g / mol) were added, and the mixture was heated at 40° C. for 12 h.

[0039] Step 6: After repeated washing with ethanol three times, centrifugation and vacuum drying, the product was mixed with 0.2g polyvinyl pyrrolidone, 0.7g pigment blue 15:4, and 0.1g silane coupling agent KH550 in a solvent of 20g acetone and 30g ethylene glycol methyl ether acetate, heated and stirred at 50°C for 5h, and ground to form a blue composite functional pigment.

[0040] Example 3

[0041] A method for preparing an organic-inorganic composite functional pigment comprises the following steps:

[0042] Step 1: Dissolve 2g sodium tungstate and 8g sodium metavanadate in 300ml water, add 0.8g aluminum nitrate, 0.2g indium nitrate, and 0.7g zinc nitrate, and then add 0.2g polyethylene glycol (Mn=800g / mol) while stirring;

[0043] Step 2: Add 5 g of butyl titanate, 0.8 g of citric acid, and 0.2 g of glacial acetic acid, and heat at 70°C for 2 h;

[0044] Step 3: Add 3 g of ethylene glycol, stir for 1 h, add 0.2 g of hydrochloric acid, and stir for 1 h;

[0045] Step 4: Aging at 50°C for 24 hours, washing three times, centrifuging, and calcining at 180°C in the absence of oxygen for 5 hours to obtain the pre-product;

[0046] Step 5: 10 g of the pre-product was dispersed in 400 ml of N,N′-dimethylacetamide, 0.1 g of 4-dimethylaminopyridine and 5 g of styrene-maleic anhydride copolymer (Mn=3000 g / mol) were added, and the mixture was heated at 40°C for 12 h.

[0047] Step 6: After repeated washing with ethanol three times, centrifugation and vacuum drying, the product was mixed with 0.2g polyvinyl pyrrolidone, 0.8g pigment yellow 138, and 0.1g silane coupling agent KH560 in a solvent of 20g acetone, 20g ethylene glycol methyl ether acetate, and 10g butyl acetate, heated and stirred at 70°C for 3h, and ground to form a yellow composite functional pigment.

[0048] Example 4

[0049] A method for preparing an organic-inorganic composite functional pigment comprises the following steps:

[0050] Step 1: Dissolve 2g sodium tungstate and 8g sodium metavanadate in 300ml water, add 0.8g aluminum nitrate, 0.3g manganese nitrate, and 0.5g zinc nitrate, and then stir and add 0.2g polyethylene glycol (Mn=1000g / mol);

[0051] Step 2: Add 5 g of butyl titanate, 0.8 g of citric acid, and 0.2 g of glacial acetic acid, and heat at 70°C for 2 h;

[0052] Step 3: Add 4 g of ethylene glycol, stir for 1 h, add 0.2 g of hydrochloric acid, and stir for 1 h;

[0053] Step 4: Aging at 50°C for 24 hours, washing three times, centrifuging, and calcining at 220°C in the absence of oxygen for 5 hours to obtain the pre-product;

[0054] Step 5: Disperse 10 g of the pre-product in 400 ml of N,N′-dimethylacetamide, add 0.1 g of 4-dimethylaminopyridine, add 5 g of styrene-maleic anhydride copolymer (Mn=3000 g / mol), and heat at 45°C for 12 h.

[0055] Step 6: After repeated washing with ethanol three times, centrifugation and vacuum drying, the product was mixed with 0.2g of Digo 655, 0.7g of Pigment Violet 23, and 0.1g of silane coupling agent KH560 in a solvent of 20g of acetone, 25g of ethylene glycol methyl ether acetate, and 5g of butyl acetate, heated and stirred at 60°C for 5h, and ground to form a purple composite functional pigment.

[0056] Example 5

[0057] A method for preparing an organic-inorganic composite functional pigment comprises the following steps:

[0058] Step 1: Dissolve 2g sodium tungstate and 8g sodium metavanadate in 300ml water, add 0.8g aluminum nitrate, 0.3g barium nitrate, and 0.5g zinc nitrate, and then add 0.2g polyethylene glycol (Mn=800g / mol) while stirring;

[0059] Step 2: Add 5 g of butyl titanate, 0.8 g of citric acid, and 0.2 g of glacial acetic acid, and heat at 70°C for 2 h;

[0060] Step 3: Add 5 g of ethylene glycol, stir for 1 h, add 0.2 g of hydrochloric acid, and stir for 1 h;

[0061] Step 4: Aging at 50°C for 24 hours, washing three times, centrifuging, and calcining at 200°C in the absence of oxygen for 4 hours to obtain the pre-product;

[0062] Step 5: Disperse 10 g of the pre-product in 400 ml of N,N′-dimethylacetamide, add 0.1 g of 4-dimethylaminopyridine, add 5 g of styrene-maleic anhydride copolymer (Mn=2000 g / mol), and heat to 45°C for 12 h.

[0063] Step 6: After repeated washing with ethanol three times, centrifugation and vacuum drying, the product was mixed with 0.2g of Digo 655, 0.9g of Pigment Green 7, and 0.1g of silane coupling agent KH550 in a solvent of 20g of acetone, 25g of ethylene glycol methyl ether acetate, and 5g of butyl acetate, heated and stirred at 60°C for 3h, and ground to form a green composite functional pigment.

[0064] Test example

[0065] The composite functional pigments obtained in each example were mixed with acrylic resin (40% solids content) in a 4:1 ratio. The mixture was then coated onto a PET film, maintaining a coating thickness of approximately 10 μm. Another PET film was then overlaid on top to form a three-layer composite film. After drying in a 100°C oven for 2 minutes and allowing the film to cool naturally, the visible light transmittance, infrared rejection, and UV rejection were measured using a spectrophotometer and a Linshang solar film tester LS101. The haze value of the sample was measured using a WGT-S haze meter. Weather resistance was tested for 5000 hours using the ASTM-D4329-13 accelerated weathering test method. The test results are shown in Table 1.

[0066] Table 1. Performance parameters of film samples in various examples

[0067] Table 1 demonstrates that the film samples prepared in each example exhibit outstanding UV and IR blocking properties, while maintaining good transparency and clarity (haze). Furthermore, they exhibit outstanding weather resistance, with no fading observed after 5000 hours of QUV testing. This demonstrates that the organic-inorganic composite functional pigments prepared using the preparation method of the present invention possess UV and IR protection, high transparency, high clarity, and excellent weather resistance, and are suitable for use in related fields such as functional window films, printing and dyeing, coatings, fibers, and plastic products, demonstrating significant application value in these markets.

[0068] Finally, it should be noted that the above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art will be able to modify the technical solutions described in the aforementioned embodiments or substitute equivalents for some of the technical features. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention shall be included within the scope of protection of the present invention.

Claims

1. A method for preparing an organic-inorganic composite functional pigment, characterized in that: The preparation method of the composite functional pigment capable of realizing heat insulation and UV protection function comprises the following steps: Step 1: According to the mass ratio, 10 parts of raw material A are dissolved in 300 parts of water, 1 to 3 parts of raw material B are added, and then 0.2 parts of polyethylene glycol are added; Step 2: Add 5 parts of butyl titanate and 1 part of organic acid, and heat at 70-80°C for 2 hours; Step 3: Add 3-5 parts of ethylene glycol, stir for 1 hour, add 0.2 parts of hydrochloric acid, stir for 1 hour; Step 4: ageing at 50°C for 24h, washing with water and centrifuging, calcining in the absence of oxygen for 3-5h to obtain a pre-product, the calcination temperature being 150-220°C; Step 5: 10 parts of the product are dispersed in 300-500 parts of N,N′-dimethylacetamide, 0.1-0.3 parts of 4-dimethylaminopyridine and 5 parts of styrene-maleic anhydride copolymer are added, and the mixture is heated at 40-50° C. to react for 12 hours; Step 6: After washing with ethanol and separating and drying, mix it with 0.2 parts of dispersant, 0.5-2 parts of pigment, 0.1 parts of coupling agent, and 50 parts of solvent, heat and stir at 50-70°C for 2-5 hours, and grind to form a composite functional pigment.

2. The method for preparing an organic-inorganic composite functional pigment according to claim 1, characterized in that: In the step 1, the raw material A is a mixture of sodium tungstate and sodium metavanadate, and the mass ratio thereof is 2:

8.

3. The method for preparing an organic-inorganic composite functional pigment according to claim 1, characterized in that: In the step 1, the raw material B is selected from two or three of aluminum nitrate, zinc nitrate, cobalt nitrate, barium nitrate, manganese nitrate and indium nitrate.

4. The method for preparing an organic-inorganic composite functional pigment according to claim 1, characterized in that: The organic acid in step 4 is a mixture of citric acid and glacial acetic acid in a mass ratio of 4:

1.

5. The method for preparing an organic-inorganic composite functional pigment according to claim 1, characterized in that: The dispersant in step 6 is selected from polyvinyl pyrrolidone and high molecular weight polyether, the coupling agent is a silane coupling agent, and the solvent is selected from acetone, ethylene glycol methyl ether acetate, and butyl acetate.

6. The method for preparing an organic-inorganic composite functional pigment according to claim 1, characterized in that: The number average molecular weight of the polyethylene glycol in step 1 is 800 to 2000 g / mol.

7. The method for preparing an organic-inorganic composite functional pigment according to claim 1, characterized in that: The number average molecular weight of the styrene-maleic anhydride copolymer in step 5 is 2000-5000 g / mol.

8. The method for preparing an organic-inorganic composite functional pigment according to claim 1, characterized in that: In step 6, the red pigment is selected from Pigment Red 254; the yellow pigment is selected from Pigment Yellow 138; the green pigment is selected from Pigment Green 7; the blue pigment is selected from Pigment Blue 15:4; and the violet pigment is selected from Pigment Violet 23.

9. An organic-inorganic composite functional pigment, characterized in that: The composite functional pigment is prepared by the preparation method described in any one of claims 1 to 8.

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