CN-121379205-B - Conductive titanium dioxide and preparation method and application thereof

Abstract

The invention relates to the technical field of pigment and filler preparation, and discloses conductive titanium dioxide and a preparation method and application thereof. The preparation method of the conductive titanium dioxide comprises the following steps of taking tantalum ethoxide, titanium tetraisopropoxide, isopropanol and aqueous solution of glycolic acid as raw materials for reaction to prepare doped modified titanium dioxide, coating the doped modified titanium dioxide through an organic monomer to obtain the organic modified titanium dioxide, and coating the organic modified titanium dioxide through a metal oxide to obtain the conductive titanium dioxide. The conductive titanium dioxide disclosed by the invention not only has excellent conductivity and weather resistance, but also has the advantages of small particle size and easiness in dispersion, has good formula applicability, and can be used in conductive paint.

Inventors

• HUANG JIANWEN
• HE GUANGYING
• QU HAIYI
• LUO JIANFANG
• Die Weibin
• WANG HUAJUN
• HE MINGCHUAN
• LIU FUXIANG
• Su Jianze
• CHEN XIANGTAO
• ZHAO PING
• LIN XIAOLONG
• LIN HAOYUAN
• HUANG LILI

Assignees

• 广东惠云钛业股份有限公司

Dates

Publication Date

20260512

Application Date

20251114

Claims (6)

1. 1. The preparation method of the conductive titanium dioxide is characterized by comprising the following steps: step one, taking tantalum ethoxide, titanium tetraisopropoxide, isopropanol and aqueous solution of glycollic acid as raw materials, and reacting to prepare doped modified titanium dioxide; Coating the doped modified titanium dioxide through an organic monomer to obtain organic modified titanium dioxide; wherein the organic monomer is prepared by the following method: S1, adding acetoacetate ethyl methacrylate into ethanol, stirring, adding 3-mercapto-2-methyl-valeraldehyde and azodiisobutyronitrile, heating to 60-70 ℃, stirring, reacting for 3-5 hours, and purifying to obtain an intermediate product A, wherein the mass ratio of acetoacetate ethyl methacrylate, ethanol, 3-mercapto-2-methyl-valeraldehyde and azodiisobutyronitrile is (2.5-4.5): (80-100): (1.3-2.6): (0.03-0.05); Mixing the intermediate product A, 1-amino-3-butene-2-ol and ethanol according to the mass ratio of (2.4-3.6): 1.3-2.5): 80-100, stirring, heating to 66-74 ℃, stirring and reacting for 2-4h, and purifying to obtain an intermediate product B; S2, mixing 2, 5-dicarboxylic acid-3, 4-ethylenedioxythiophene and thionyl chloride in a mass ratio of (2.3-3.5) (5.9-11.8), stirring for 3-4h, then reacting for 20-30min at 76-84 ℃, and purifying to obtain a thienyl compound; Mixing the intermediate product B and the ethanol in the mass ratio of (4.2-6.2) to (60-80), dripping the thienyl compound dispersion in an ice-water bath, reacting for 2 hours at 0 ℃ and then reacting for 3.5-4.5 hours at 23-28 ℃ and purifying to obtain an organic monomer; Coating the organic modified titanium dioxide through metal oxide to obtain conductive titanium dioxide, wherein the specific method comprises the following steps of: Adding tin chloride pentahydrate into ethanol to prepare a solution A, adding zinc chloride and citric acid into water to prepare a solution B, adding the solution A into the solution B, stirring, adding organic modified titanium dioxide, adding 4mol/L sodium hydroxide aqueous solution, performing ultrasonic treatment for 1-2h, filtering, washing, drying, calcining the dried product in an argon atmosphere at 590-610 ℃ for 100-150min to obtain conductive titanium dioxide, wherein the mass ratio of the tin chloride pentahydrate, the zinc chloride, the citric acid, the organic modified titanium dioxide and the 4mol/L sodium hydroxide aqueous solution is (1.4-2.8): (0.55-1.1): (0.84-1.68): (12-20): (55-110).
2. 2. The method for preparing conductive titanium dioxide according to claim 1, wherein in the first step, the volume ratio of the tantalum ethoxide to the titanium tetraisopropoxide to the aqueous solution of isopropanol to the aqueous solution of glycolic acid is (0.22-0.3) 5:5:50, and the average particle size of the doped modified titanium dioxide is 170nm.
3. 3. The method for preparing conductive titanium pigment according to claim 1, wherein in the first step, the reaction condition is that stirring is carried out for 1.5-2.5 hours at a speed of 500r/min at 78-82 ℃, and then hydrothermal reaction is carried out for 5-7 hours at a temperature of 195-205 ℃ and a pressure of 1.6 MPa.
4. 4. The method for preparing conductive titanium dioxide according to claim 1, wherein in the second step, the method for preparing organic modified titanium dioxide specifically comprises: Adding doped modified titanium dioxide into dimethylformamide, carrying out ultrasonic treatment, adding an organic monomer, stirring for 40-60min at 23-28 ℃ in a nitrogen atmosphere, then heating to 75-85 ℃, adding ammonium persulfate, stirring and reacting for 5-7h, and purifying to obtain the organic modified titanium dioxide, wherein the mass ratio of the doped modified titanium dioxide, the dimethylformamide, the organic monomer and the ammonium persulfate is (5-9): 200-300): 6.6-17.2): 0.1-0.2.
5. 5. A conductive titanium pigment prepared by the method for preparing a conductive titanium pigment according to any one of claims 1 to 4.
6. 6. The use of the conductive titanium dioxide according to claim 5 in conductive paint.

Description

Conductive titanium dioxide and preparation method and application thereof Technical Field The invention relates to the technical field of pigment and filler preparation, in particular to conductive titanium dioxide and a preparation method and application thereof. Background Titanium dioxide has the characteristics of higher whiteness, hiding power, opacity, brightness and the like, is one of the inorganic white pigments with the best application effect currently acknowledged, has the reputation of 'king of inorganic white pigment', and can be used in various fields of plastics, paint, water-based paint, rubber, printing ink, masterbatch, decorative paper and the like. At present, the preparation process of the conductive coating is mature, is widely applied to static elimination, and has the advantages of simple operation, less construction process flow, low cost and the like. The main function of titanium dioxide in general conductive paint is to improve the mechanical strength, optical property and rheological property of paint, but the titanium dioxide is worse to improve the conductivity of paint, so the research of conductive titanium dioxide is proposed. For example, chinese patent CN111040474B discloses a conductive titanium dioxide and a preparation method thereof, which solves the problem of poor conductivity of titanium dioxide, but titanium dioxide has photochemical activity and poor weather resistance, and gradually loses luster and hiding ability under illumination and climate change. Therefore, it is also important to improve the weather resistance of titanium dioxide. Disclosure of Invention In order to solve the technical problems, the invention provides a preparation method of conductive titanium dioxide, which comprises the following steps: step one, taking tantalum ethoxide, titanium tetraisopropoxide, isopropanol and aqueous solution of glycollic acid as raw materials, and reacting to prepare doped modified titanium dioxide; Coating the doped modified titanium dioxide through an organic monomer to obtain organic modified titanium dioxide; And thirdly, coating the organically modified titanium dioxide through metal oxide to obtain the conductive titanium dioxide. Preferably, in the first step, the volume ratio of the tantalum ethoxide to the titanium tetraisopropoxide to the aqueous solution of isopropanol to the aqueous solution of glycollic acid is (0.22-0.3): 5:5:50, and the average particle size of the doped modified titanium dioxide is 170nm. Preferably, in the first step, the reaction condition is that stirring is carried out for 1.5-2.5 hours at the speed of 500r/min at the temperature of 78-82 ℃, and then hydrothermal reaction is carried out for 5-7 hours at the temperature of 195-205 ℃ and the pressure of 1.6 MPa; In the process, the rutile type modified titanium dioxide containing the metal tantalum is obtained by using the traditional hydrothermal method, using tantalum ethoxide and titanium tetraisopropoxide as a tantalum source and a titanium source, using isopropanol as a solvent and using glycollic acid as an auxiliary agent, the rutile type titanium dioxide has better stability and better weather resistance compared with anatase type titanium dioxide, and the doping of tantalum improves the conductivity of the rutile type titanium dioxide. Preferably, in the second step, the preparation method of the organically modified titanium dioxide specifically includes: Adding doped modified titanium dioxide into dimethylformamide, carrying out ultrasonic treatment, adding an organic monomer, stirring for 40-60min at 23-28 ℃ in a nitrogen atmosphere, then heating to 75-85 ℃, adding ammonium persulfate, stirring and reacting for 5-7h, and purifying to obtain the organic modified titanium dioxide, wherein the mass ratio of the doped modified titanium dioxide, the dimethylformamide, the organic monomer and the ammonium persulfate is (5-9): 200-300): 6.6-17.2: (0.1-0.2); in the process, the beta-ketoester group in the organic monomer can coordinate with metal ions in the doped modified titanium dioxide, and then under the initiation of ammonium persulfate, carbon-carbon double bonds and thiophene parts can be self-polymerized, so that a compact and firm conductive organic layer is formed on the surface of the doped modified titanium dioxide, on one hand, the conductivity of the doped modified titanium dioxide is improved, on the other hand, the doped modified titanium dioxide is coated, the agglomeration of the doped modified titanium dioxide is prevented, the particle size is reduced, the photoactivity of the doped modified titanium dioxide is reduced, and the conductivity, the dispersibility and the weather resistance of the doped modified titanium dioxide are improved. Preferably, the organic monomer in the second step is prepared by the following steps: step S1, mixing an intermediate product A, 1-amino-3-butene-2-ol and ethanol in a mass ratio of (2.4-3.6): (1.3-2.5): (80-100), s