A method for preparing high-resistivity chemical fiber titanium dioxide

Abstract

The present invention discloses a method for preparing high-resistivity chemical fiber titanium dioxide, comprising the following steps: subjecting anatase titanium dioxide to a heat treatment at 120-130°C for 10-20 minutes, then cooling to 40-45°C at a rate of 1-3°C / min, maintaining the temperature, adding a regulating modifier in an amount of 10-15% of the total amount of anatase titanium dioxide, stirring for reaction, completing the stirring, washing with water, and drying. The regulating modifier prepared by the present invention can moisten the titanium dioxide, and through interface modification with a silane coupling agent KH560, optimizes the combination of a lanthanum nitrate solution, sodium lignin sulfonate, and a phosphate buffer solution to enhance the activity of the system. Through the coordinated coordination between the raw materials, the activity of the titanium dioxide can be further improved, providing favorable basic conditions for subsequent heat homogenization treatment and ball milling treatment with a silica-polyphonic boron nitride nanosheet modifier.

Description

Technical Field

[0001] The invention relates to the technical field of titanium dioxide preparation, and in particular to a method for preparing high-resistivity chemical fiber titanium dioxide. Background Art

[0002] Titanium dioxide (also known as titanium dioxide) has stable physical and chemical properties, excellent optical and electrical properties, and outstanding pigment properties. Therefore, it is widely used in industries such as coatings, plastics, papermaking, printing inks, chemical fibers, rubber, and cosmetics. The titanium dioxide used in the chemical fiber field is primarily anatase titanium dioxide, and there are relatively few domestic manufacturers of titanium dioxide specifically for chemical fibers. This is mainly due to the high particle size requirements for titanium dioxide used in chemical fibers. During the production process, the particle size of titanium dioxide can be reduced using a series of technologies such as roller mills, colloid mills, ball mills, and sand mills, thereby optimizing the product's application range. Chemical fiber titanium dioxide is titanium dioxide added to chemical fibers and man-made fibers to achieve a matting effect. It makes the fiber surface non-reflective, the fiber opaque, and improves the fiber's dyeing properties and feel. It is an essential additive for matte fibers.

[0003] In order to improve the application effect and resistivity of existing chemical fiber titanium dioxide, it is easy to reduce the water-based dispersibility of the product, making it difficult to coordinate the improvement of dispersibility and resistivity. At the same time, the product has high photocatalytic performance, which degrades polyamide molecules and causes aging of nylon fibers, further limiting the product's utilization efficiency. Based on this, the present invention further improves it. Summary of the Invention

[0004] In view of the defects of the prior art, the purpose of the present invention is to provide a method for preparing high-resistivity chemical fiber titanium dioxide to solve the problems raised in the above background technology.

[0005] The present invention solves the technical problem by adopting the following technical solutions:

[0006] The present invention provides a method for preparing high-resistivity chemical fiber titanium dioxide, comprising the following steps:

[0007] Step 1: heat-treating anatase titanium dioxide at 120-130° C. for 10-20 minutes, then cooling to 40-45° C. at a rate of 1-3° C. / min, keeping the temperature, and setting aside;

[0008] Step 2: The product of step 1 is placed in an ethylene glycol solvent of 3 to 5 times the total amount of the product of step 1 and stirred evenly, and then a regulating modifier of 10 to 15% of the total amount of anatase titanium dioxide is added, and the mixture is stirred for reaction. After stirring is completed, the mixture is washed with water and dried;

[0009] Step 3: Heat homogenization treatment: first, heat to 45-50°C at a rate of 1-2°C / min, keep warm for 5-10 minutes, and spray the impregnation liquid until the surface of the product in step 2 is soaked;

[0010] Step 4: Then continue to heat up to 105-110°C at a rate of 3-5°C / min, keep warm for 5-10 minutes, and then air-cool to room temperature to obtain a hot homogenized material;

[0011] Step 5: Add 20-30% of the total amount of the heat-homogenized material into the heat-homogenized material as a silicon dioxide-polyboron nitride nanosheet modifier, and then send it into a ball mill for ball milling. After the ball milling is completed, wash it with water and dry it to obtain the high resistivity chemical fiber titanium dioxide powder of the present invention.

[0012] Preferably, the stirring reaction in step 2 is carried out at a speed of 750 to 850 r / min, a stirring time of 30 to 40 min, and a stirring temperature of 46 to 48°C.

[0013] Preferably, the preparation method of the regulating modifier is:

[0014] S01: adding the chitosan aqueous solution to an ethanol solvent that is 2 to 5 times the total amount of the chitosan aqueous solution;

[0015] S02: Then add 10-20% of the total amount of chitosan aqueous solution of silane coupling agent KH560 and 2-5% of the total amount of chitosan aqueous solution of lanthanum nitrate solution, and stir evenly;

[0016] S03: Sodium lignin sulfonate in an amount of 1-3% of the total amount of the chitosan aqueous solution is added, and the mixture is stirred thoroughly. Finally, a phosphate buffer solution in an amount of 1-3% of the total amount of the chitosan aqueous solution is added, and the mixture is mixed to obtain a regulating modifier.

[0017] Preferably, the mass fraction of the chitosan aqueous solution is 5-8%; the mass fraction of the lanthanum nitrate solution is 1-3%.

[0018] Preferably, the pH value of the phosphate buffer solution is 5.5-6.5.

[0019] Preferably, the preparation method of the infiltration liquid is:

[0020] The hydroxyapatite is placed in a proton irradiation box for irradiation treatment, the irradiation power is 300-400W, the irradiation time is 20-30 minutes, and after the treatment is completed, the product is stirred in a 3-5 times hydrogen peroxide solution, the stirring speed is 350-450r / min, the stirring temperature is 40-45°C, and the stirring time is 10-20 minutes. After the treatment is completed, the product is washed with water and dried to obtain pre-conditioned hydroxyapatite;

[0021] Then the nano-barium sulfate is added into a 3-5 times hydrochloric acid solution, and then 2-5% of the total amount of the nano-barium sulfate carboxymethyl cellulose and 8-12% of the total amount of the nano-barium sulfate pre-adjusted hydroxyapatite are added, and stirred fully to obtain an infiltration solution.

[0022] Preferably, the mass fraction of the hydrochloric acid solution is 2-6%.

[0023] Preferably, the concentration of the hydrogen peroxide solution is 10-12% wt.

[0024] Preferably, the preparation method of the silicon dioxide polyphonic boron nitride nanosheet modifier is:

[0025] S101: adding 2 to 5 parts of dioctyl phosphate to 5 to 10 parts of ethanol solvent, then adding 1 to 3 parts of sodium lauryl sulfate and 0.45 to 0.65 parts of isopropyl tris(dioctyl pyrophosphate) titanate, stirring evenly, and finally adding 0.15 to 0.25 parts of triethanolamine, stirring thoroughly to obtain a polyhydric solution;

[0026] S102: placing the boron nitride nanosheets in 3 to 5 times the volume of deionized water and stirring evenly to obtain a pre-adjustment, then adding the pre-adjustment to the re-adjustment solution at a weight ratio of 1:5 and continuing to mix thoroughly to obtain a boron nitride nanosheet re-adjustment modification solution;

[0027] S103: heat-treating the nano-silica at 50-60° C. for 5-10 minutes, air-cooling it to room temperature, and then adding it into a 3-5 times volume of boron nitride nanosheet polytuning modification liquid and stirring it thoroughly to obtain a silicon dioxide polytuning boron nitride nanosheet modifier.

[0028] Preferably, the ball milling speed of the ball milling treatment is 1500-1800 r / min, and the ball milling time is 65-75 min.

[0029] Compared with the prior art, the present invention has the following beneficial effects:

[0030] 1. The chemical fiber titanium dioxide of the present invention adopts anatase titanium dioxide, which is heat-treated at 120-130° C., and then cooled at a constant temperature, kept warm, stirred in an ethylene glycol solvent, and then subjected to a stirring reaction treatment by adjusting a modifier; the activity of the product is optimized by heat treatment, and the dispersion of the product is improved by constant temperature cooling and stirring in an ethylene glycol solvent. The adjusting modifier is prepared by combining a chitosan aqueous solution, a silane coupling agent KH560, and a lanthanum nitrate solution, and is optimized by sodium lignin sulfonate and a phosphate buffer solution. The adjusting modifier can moisten the titanium dioxide, and the interface is modified by the silane coupling agent KH560, and the lanthanum nitrate solution, sodium lignin sulfonate and a phosphate buffer solution are optimized to enhance the activity of the system. The coordinated cooperation between the raw materials further improves the activity of the titanium dioxide, providing favorable basic conditions for subsequent heat homogenization treatment and ball milling treatment of the silica polytuned boron nitride nanosheet modifier;

[0031] 2. The temperature is raised to 45-50°C at a rate of 1-2°C / min, kept at this temperature for 5-10 minutes, and then continued to be raised to 105-110°C at a rate of 3-5°C / min, kept at this temperature for 5-10 minutes, and then air-cooled to room temperature. Through the optimization and improvement of thermal homogenization, the performance stability of the product is improved; at the same time, the spraying of the impregnation liquid and the ball milling treatment of the silica polytuned boron nitride nanosheet modifier are combined. Through the coordination and optimization of the two, the dispersibility and resistivity performance of the product are coordinated and improved, and the photocatalytic activity of the product is reduced, thereby improving the performance of the product.

[0032] 3. The impregnation liquid uses hydroxyapatite treated with proton irradiation to improve the irradiation activity, and further optimizes the surface properties of the hydroxyapatite by stirring in a hydrogen peroxide solution. Nano-barium sulfate is dispersed in a hydrochloric acid solution, and coordinated with carboxymethyl cellulose and pre-adjusted hydroxyapatite. The impregnated anatase titanium dioxide is coated with the impregnation liquid to optimize the photocatalytic properties of the product. At the same time, the performance effect is improved by combining with heat homogenization treatment.

[0033] 4. The silica-boron nitride nanosheet modifier is optimized and coordinated by diethyl phosphate, sodium dodecyl sulfate, isopropyl tri(dioctyl pyrophosphate) titanate and triethanolamine. The prepared compounding liquid is coordinated with boron nitride nanosheets and then coordinated with nano-silica. Through ball milling improvement, the resistivity and dispersibility of the improved product are coordinated and optimized, and the photocatalytic activity of the product is suppressed, thereby improving the performance of the product. DETAILED DESCRIPTION

[0034] The following is a clear and complete description of the technical solutions in the embodiments of the present invention in conjunction with specific embodiments. Obviously, the described embodiments 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.

[0035] A method for preparing high-resistivity chemical fiber titanium dioxide in this embodiment includes the following steps:

[0036] Step 1: heat-treating anatase titanium dioxide at 120-130° C. for 10-20 minutes, then cooling to 40-45° C. at a rate of 1-3° C. / min, keeping the temperature, and setting aside;

[0037] Step 2: The product of step 1 is placed in an ethylene glycol solvent of 3 to 5 times the total amount of the product of step 1 and stirred evenly, and then a regulating modifier of 10 to 15% of the total amount of anatase titanium dioxide is added, and the mixture is stirred for reaction. After stirring is completed, the mixture is washed with water and dried;

[0038] Step 3: Heat homogenization treatment: first, heat to 45-50°C at a rate of 1-2°C / min, keep warm for 5-10 minutes, and spray the impregnation liquid until the surface of the product in step 2 is soaked;

[0039] Step 4: Then continue to heat up to 105-110°C at a rate of 3-5°C / min, keep warm for 5-10 minutes, and then air-cool to room temperature to obtain a hot homogenized material;

[0040] Step 5: Add 20-30% of the total amount of the heat-homogenized material into the heat-homogenized material as a silicon dioxide-polyboron nitride nanosheet modifier, and then send it into a ball mill for ball milling. After the ball milling is completed, wash it with water and dry it to obtain the high resistivity chemical fiber titanium dioxide powder of the present invention.

[0041] In step 2 of this embodiment, the stirring reaction is carried out at a speed of 750 to 850 r / min, a stirring time of 30 to 40 min, and a stirring temperature of 46 to 48°C.

[0042] The preparation method of the regulating modifier of this embodiment is:

[0043] S01: adding the chitosan aqueous solution to an ethanol solvent that is 2 to 5 times the total amount of the chitosan aqueous solution;

[0044] S02: Then add 10-20% of the total amount of chitosan aqueous solution of silane coupling agent KH560 and 2-5% of the total amount of chitosan aqueous solution of lanthanum nitrate solution, and stir evenly;

[0045] S03: Sodium lignin sulfonate in an amount of 1-3% of the total amount of the chitosan aqueous solution is added, and the mixture is stirred thoroughly. Finally, a phosphate buffer solution in an amount of 1-3% of the total amount of the chitosan aqueous solution is added, and the mixture is mixed to obtain a regulating modifier.

[0046] The mass fraction of the chitosan aqueous solution in this embodiment is 5-8%; the mass fraction of the lanthanum nitrate solution is 1-3%.

[0047] The pH value of the phosphate buffer solution of this embodiment is 5.5-6.5.

[0048] The preparation method of the infiltration liquid of this embodiment is:

[0049] The hydroxyapatite is placed in a proton irradiation box for irradiation treatment, the irradiation power is 300-400W, the irradiation time is 20-30 minutes, and after the treatment is completed, the product is stirred in a 3-5 times hydrogen peroxide solution, the stirring speed is 350-450r / min, the stirring temperature is 40-45°C, and the stirring time is 10-20 minutes. After the treatment is completed, the product is washed with water and dried to obtain pre-conditioned hydroxyapatite;

[0050] Then the nano-barium sulfate is added into a 3-5 times hydrochloric acid solution, and then 2-5% of the total amount of the nano-barium sulfate carboxymethyl cellulose and 8-12% of the total amount of the nano-barium sulfate pre-adjusted hydroxyapatite are added, and stirred fully to obtain an infiltration solution.

[0051] The mass fraction of the hydrochloric acid solution in this embodiment is 2-6%.

[0052] The concentration of the hydrogen peroxide solution in this embodiment is 10-12% wt.

[0053] The preparation method of the silicon dioxide polyphonic boron nitride nanosheet modifier of this embodiment is:

[0054] S101: adding 2 to 5 parts of dioctyl phosphate to 5 to 10 parts of ethanol solvent, then adding 1 to 3 parts of sodium lauryl sulfate and 0.45 to 0.65 parts of isopropyl tris(dioctyl pyrophosphate) titanate, stirring evenly, and finally adding 0.15 to 0.25 parts of triethanolamine, stirring thoroughly to obtain a polyhydric solution;

[0055] S102: placing the boron nitride nanosheets in 3 to 5 times the volume of deionized water and stirring evenly to obtain a pre-adjustment, then adding the pre-adjustment to the re-adjustment solution at a weight ratio of 1:5 and continuing to mix thoroughly to obtain a boron nitride nanosheet re-adjustment modification solution;

[0056] S103: heat-treating the nano-silica at 50-60° C. for 5-10 minutes, air-cooling it to room temperature, and then adding it into a 3-5 times volume of boron nitride nanosheet polytuning modification liquid and stirring it thoroughly to obtain a silicon dioxide polytuning boron nitride nanosheet modifier.

[0057] The ball milling speed of the ball milling treatment in this embodiment is 1500-1800 r / min, and the ball milling time is 65-75 min.

[0058] Example 1.

[0059] A method for preparing high-resistivity chemical fiber titanium dioxide in this embodiment includes the following steps:

[0060] Step 1: heat-treating anatase titanium dioxide at 120°C for 10 minutes, then cooling to 40°C at a rate of 1°C / min, keeping the temperature, and setting aside;

[0061] Step 2: The product of step 1 is placed in an ethylene glycol solvent at a volume 3 times the total volume of the product of step 1 and stirred evenly, and then a regulating modifier at a volume of 10% of the total volume of anatase titanium dioxide is added, and the mixture is stirred for reaction. After stirring is completed, the mixture is washed with water and dried;

[0062] Step 3: Heat homogenization treatment: first, heat to 45°C at a rate of 1°C / min, keep warm for 5 minutes, and spray the impregnation liquid until the surface of the product in step 2 is soaked;

[0063] Step 4: Then continue to heat up to 105°C at a rate of 3°C / min, keep warm for 5 minutes, and then air-cool to room temperature to obtain a hot homogenized material;

[0064] Step 5: Add 20% of the total amount of the heat-homogenized material into the silicon dioxide-polyboron nitride nanosheet modifier into the heat-homogenized material, and then send it into a ball mill for ball milling. After the ball milling is completed, wash with water and dry; obtain the high resistivity chemical fiber titanium dioxide of the present invention.

[0065] In step 2 of this embodiment, the stirring reaction was carried out at a rotation speed of 750 r / min, a stirring time of 30 min, and a stirring temperature of 46° C.

[0066] The preparation method of the regulating modifier of this embodiment is:

[0067] S01: Add chitosan aqueous solution into ethanol solvent with an amount twice the total amount of chitosan aqueous solution;

[0068] S02: Then add 10% of the total amount of chitosan aqueous solution of silane coupling agent KH560 and 2% of the total amount of chitosan aqueous solution of lanthanum nitrate solution, and stir evenly;

[0069] S03: Sodium lignin sulfonate (1% of the total amount of the chitosan aqueous solution) is added, and the mixture is stirred thoroughly. Finally, a phosphate buffer solution (1% of the total amount of the chitosan aqueous solution) is added, and the mixture is mixed to obtain a regulating modifier.

[0070] The mass fraction of the chitosan aqueous solution in this embodiment is 5%; the mass fraction of the lanthanum nitrate solution is 1%.

[0071] The pH value of the phosphate buffer solution in this example is 5.5.

[0072] The preparation method of the infiltration liquid of this embodiment is:

[0073] The hydroxyapatite was placed in a proton irradiation box for irradiation treatment at an irradiation power of 300 W and an irradiation time of 20 minutes. After the treatment was completed, the product was stirred in a 3-fold hydrogen peroxide solution at a stirring speed of 350 r / min, a stirring temperature of 40° C., and a stirring time of 10 minutes. After the treatment was completed, the product was washed with water and dried to obtain pre-conditioned hydroxyapatite.

[0074] Then the nano-barium sulfate is added into a 3-fold hydrochloric acid solution, and then 2% of the total amount of the nano-barium sulfate carboxymethyl cellulose and 8% of the total amount of the nano-barium sulfate pre-adjusted hydroxyapatite are added, and the mixture is stirred thoroughly to obtain an infiltration solution.

[0075] The mass fraction of the hydrochloric acid solution in this embodiment is 2%.

[0076] The concentration of the hydrogen peroxide solution in this embodiment is 10% wt.

[0077] The preparation method of the silicon dioxide polyphonic boron nitride nanosheet modifier of this embodiment is:

[0078] S101: Add 2 parts of dioctyl phosphate to 5 parts of ethanol solvent, then add 1 part of sodium lauryl sulfate and 0.45 parts of isopropyl tris(dioctyl pyrophosphate) titanate, stir evenly, and finally add 0.15 parts of triethanolamine and stir thoroughly to obtain a polyhydric solution;

[0079] S102: placing the boron nitride nanosheets in 3 times the volume of deionized water and stirring evenly to obtain a pre-adjustment, then adding the pre-adjustment to the re-adjustment solution at a weight ratio of 1:5 and continuing to mix thoroughly to obtain a boron nitride nanosheet re-adjustment modification solution;

[0080] S103: heat-treating the nano-silica at 50° C. for 5 minutes, air-cooling the nano-silica to room temperature, and then adding the nano-silica to a 3-fold volume of a boron nitride nanosheet polytuning modification solution and stirring the solution thoroughly to obtain a silicon dioxide polytuning boron nitride nanosheet modifier.

[0081] The ball milling speed of the ball milling treatment in this embodiment is 1500 r / min, and the ball milling time is 65 min.

[0082] Example 2.

[0083] A method for preparing high-resistivity chemical fiber titanium dioxide in this embodiment includes the following steps:

[0084] Step 1: heat-treating anatase titanium dioxide at 130°C for 20 minutes, then cooling to 45°C at a rate of 3°C / min, keeping the temperature, and setting aside;

[0085] Step 2: The product of step 1 is placed in an ethylene glycol solvent of 5 times the total amount of the product of step 1 and stirred evenly, and then a regulating modifier of 15% of the total amount of anatase titanium dioxide is added, and the mixture is stirred for reaction. After stirring is completed, the mixture is washed with water and dried;

[0086] Step 3: Heat homogenization treatment: first, heat to 50°C at a rate of 2°C / min, keep warm for 10 minutes, and spray the impregnation liquid until the surface of the product in step 2 is soaked;

[0087] Step 4: Then continue to heat up to 110°C at a rate of 5°C / min, keep warm for 10 minutes, and then air-cool to room temperature to obtain a hot homogenized material;

[0088] Step 5: Add 30% of the total amount of the heat-homogenized material into the silicon dioxide-polyboron nitride nanosheet modifier into the heat-homogenized material, and then send it into a ball mill for ball milling. After the ball milling is completed, wash with water and dry; obtain the high resistivity chemical fiber titanium dioxide of the present invention.

[0089] In step 2 of this embodiment, the stirring reaction was carried out at a rotation speed of 850 r / min, a stirring time of 40 min, and a stirring temperature of 48°C.

[0090] The preparation method of the regulating modifier of this embodiment is:

[0091] S01: Add chitosan aqueous solution into ethanol solvent which is 5 times the total amount of chitosan aqueous solution;

[0092] S02: Then add silane coupling agent KH560 (20% of the total amount of chitosan aqueous solution) and lanthanum nitrate solution (5% of the total amount of chitosan aqueous solution) and stir evenly;

[0093] S03: Sodium lignin sulfonate (3% of the total amount of the chitosan aqueous solution) is added and stirred thoroughly. Finally, a phosphate buffer solution (3% of the total amount of the chitosan aqueous solution) is added and mixed to obtain a regulating modifier.

[0094] The mass fraction of the chitosan aqueous solution in this embodiment is 8%; the mass fraction of the lanthanum nitrate solution is 3%.

[0095] The pH value of the phosphate buffer solution in this example is 6.5.

[0096] The preparation method of the infiltration liquid of this embodiment is:

[0097] The hydroxyapatite was placed in a proton irradiation box for irradiation treatment at an irradiation power of 400 W and an irradiation time of 30 minutes. After the treatment was completed, the product was stirred in a 5-fold hydrogen peroxide solution at a stirring speed of 450 r / min, a stirring temperature of 45° C., and a stirring time of 20 minutes. After the treatment was completed, the product was washed with water and dried to obtain pre-conditioned hydroxyapatite.

[0098] Then the nano-barium sulfate is added into a 5-fold hydrochloric acid solution, and then 5% of the total amount of the nano-barium sulfate carboxymethyl cellulose and 12% of the total amount of the nano-barium sulfate pre-adjusted hydroxyapatite are added, and the mixture is stirred thoroughly to obtain an infiltration solution.

[0099] The mass fraction of the hydrochloric acid solution in this embodiment is 6%.

[0100] The concentration of the hydrogen peroxide solution in this embodiment is 12% wt.

[0101] The preparation method of the silicon dioxide polyphonic boron nitride nanosheet modifier of this embodiment is:

[0102] S101: 5 parts of dioctyl phosphate are added to 10 parts of ethanol solvent, followed by 3 parts of sodium lauryl sulfate and 0.65 parts of isopropyl tris(dioctyl pyrophosphate) titanate, and the mixture is stirred evenly. Finally, 0.25 parts of triethanolamine are added and stirred thoroughly to obtain a polyhydric solution;

[0103] S102: placing the boron nitride nanosheets in 5 times the volume of deionized water and stirring evenly to obtain a pre-adjustment, then adding the pre-adjustment to the re-adjustment solution at a weight ratio of 1:5 and continuing to mix thoroughly to obtain a boron nitride nanosheet re-adjustment modification solution;

[0104] S103: heat-treating the nano-silica at 60° C. for 10 minutes, then air-cooling to room temperature, and then adding the nano-silica into a 5-fold polytuning modification solution of boron nitride nanosheets and stirring thoroughly to obtain a silicon dioxide polytuning boron nitride nanosheet modifier.

[0105] The ball milling speed of the ball milling treatment in this embodiment is 1800 r / min, and the ball milling time is 75 min.

[0106] Example 3.

[0107] A method for preparing high-resistivity chemical fiber titanium dioxide in this embodiment includes the following steps:

[0108] Step 1: heat-treating anatase titanium dioxide at 125°C for 15 minutes, then cooling to 42°C at a rate of 2°C / min, keeping the temperature, and setting aside;

[0109] Step 2: The product of step 1 is placed in ethylene glycol solvent at a volume of 4 times the total volume of the product of step 1 and stirred evenly, and then a regulating modifier at a volume of 12.5% of the total volume of anatase titanium dioxide is added, and the mixture is stirred for reaction. After stirring is completed, the mixture is washed with water and dried;

[0110] Step 3: Heat homogenization treatment: first, heat to 47°C at a rate of 1.5°C / min, keep warm for 7.5 minutes, and spray the impregnation liquid until the surface of the product in step 2 is soaked;

[0111] Step 4: Then continue to heat up to 107°C at a rate of 4°C / min, keep warm for 7.5 minutes, and then air-cool to room temperature to obtain a hot homogenized material;

[0112] Step 5: Add 25% of the total amount of the heat-homogenized material to the silicon dioxide-polyboron nitride nanosheet modifier into the heat-homogenized material, and then send it into a ball mill for ball milling. After the ball milling is completed, wash and dry; obtain the high resistivity chemical fiber titanium dioxide of the present invention.

[0113] In step 2 of this embodiment, the stirring reaction was carried out at a speed of 800 r / min, a stirring time of 35 min, and a stirring temperature of 47°C.

[0114] The preparation method of the regulating modifier of this embodiment is:

[0115] S01: Add the chitosan aqueous solution into an ethanol solvent that is 3.5 times the total amount of the chitosan aqueous solution;

[0116] S02: Then add 15% of the total amount of chitosan aqueous solution of silane coupling agent KH560 and 3.5% of the total amount of chitosan aqueous solution of lanthanum nitrate solution, and stir evenly;

[0117] S03: Sodium lignin sulfonate (2% of the total amount of the chitosan aqueous solution) is added, and the mixture is stirred thoroughly. Finally, a phosphate buffer solution (2% of the total amount of the chitosan aqueous solution) is added, and the mixture is mixed to obtain a regulating modifier.

[0118] The mass fraction of the chitosan aqueous solution in this embodiment is 6.5%; the mass fraction of the lanthanum nitrate solution is 2%.

[0119] The pH value of the phosphate buffer solution in this example is 6.0.

[0120] The preparation method of the infiltration liquid of this embodiment is:

[0121] The hydroxyapatite was placed in a proton irradiation box for irradiation treatment at an irradiation power of 350 W and an irradiation time of 25 minutes. After the treatment was completed, the product was stirred in a 4-fold hydrogen peroxide solution at a stirring speed of 400 r / min, a stirring temperature of 42° C., and a stirring time of 15 minutes. After the treatment was completed, the product was washed with water and dried to obtain pre-conditioned hydroxyapatite.

[0122] Then the nano-barium sulfate is added to a 4-fold hydrochloric acid solution, and then carboxymethyl cellulose (3.5% of the total amount of the nano-barium sulfate) and pre-adjusted hydroxyapatite (10% of the total amount of the nano-barium sulfate) are added, and the mixture is stirred thoroughly to obtain an infiltration solution.

[0123] The mass fraction of the hydrochloric acid solution in this embodiment is 4%.

[0124] The concentration of the hydrogen peroxide solution in this embodiment is 11% wt.

[0125] The preparation method of the silicon dioxide polyphonic boron nitride nanosheet modifier of this embodiment is:

[0126] S101: 3.5 parts of dioctyl phosphate are added to 7.5 parts of ethanol solvent, followed by 2 parts of sodium lauryl sulfate and 0.50 parts of isopropyl tris(dioctyl pyrophosphate) titanate, and the mixture is stirred evenly. Finally, 0.20 parts of triethanolamine are added and stirred thoroughly to obtain a polyhydric solution;

[0127] S102: placing the boron nitride nanosheets in 4 times the volume of deionized water and stirring evenly to obtain a pre-adjustment, then adding the pre-adjustment to the re-adjustment solution at a weight ratio of 1:5 and continuing to mix thoroughly to obtain a boron nitride nanosheet re-adjustment modification solution;

[0128] S103: The nano-silica is first heat-treated at 55° C. for 7.5 minutes, then air-cooled to room temperature, and then added into a 4-fold boron nitride nanosheet polytuning modification liquid and stirred thoroughly to obtain a silica polytuning boron nitride nanosheet modifier.

[0129] The ball milling speed of the ball milling treatment in this embodiment is 1650 r / min, and the ball milling time is 70 min.

[0130] Comparative Example 1.

[0131] The difference from Example 3 is that no conditioning modifier treatment was used.

[0132] Comparative Example 2.

[0133] The difference from Example 3 is that the preparation method of the regulating modifier is different, specifically:

[0134] 15% of the total amount of the ethanol solvent was added to the silane coupling agent KH560, and the mixture was stirred evenly. 2% of the total amount of the ethanol solvent was added to the phosphate buffer solution, and the mixture was mixed evenly to obtain a regulating modifier.

[0135] Comparative Example 3.

[0136] The difference from Example 3 is that the preparation steps of the heat homogenization treatment are different:

[0137] Heat homogenization treatment: first raise the temperature to 47°C at a rate of 1.5°C / min, keep warm for 7.5 minutes, spray the infiltration liquid until the surface of the product in step 2 is infiltrated, and the heat homogenized material can be obtained.

[0138] Comparative Example 4.

[0139] The difference from Example 3 is that no immersion liquid treatment is used.

[0140] Comparative Example 5.

[0141] The difference from Example 3 is that no pre-conditioned hydroxyapatite is added in the preparation of the infiltration solution.

[0142] Comparative Example 6.

[0143] The difference from Example 3 is the preparation method of the infiltration liquid:

[0144] The hydroxyapatite is placed in a proton irradiation box for irradiation treatment, with an irradiation power of 350W and an irradiation time of 25 minutes. After the treatment is completed, pre-conditioned hydroxyapatite is obtained;

[0145] Then, the nano-barium sulfate is added into 4 times of deionized water, and then 10% of the total amount of the nano-barium sulfate pre-adjusted hydroxyapatite is added and stirred thoroughly to obtain an infiltration solution.

[0146] Comparative Example 7.

[0147] The difference from Example 3 is that the silicon dioxide polytuned boron nitride nanosheet modifier was not used for ball milling. The hot homogenized material was directly fed into the ball mill for ball milling. After the ball milling was completed, it was washed with water and dried.

[0148] The water dispersibility, resistivity, and dye degradation performance of Examples 1-3 and Comparative Examples 1-7 were tested as follows: The dye degradation rate was determined by measuring the absorbance of the dye solution at its maximum absorption wavelength using an ultraviolet spectrophotometer, converting the absorbance to dye concentration using a standard curve, and calculating the dye degradation rate R (%) using the following formula: Wherein C initial and C final refer to the initial dye concentration in the solution and the dye concentration after degradation, respectively: C initial - C final / C initial × 100;

[0149] The performance test of the products of Examples 1-3 and Comparative Examples 1-7 of the present invention was carried out.

[0150] Water dispersibility (%) Resistivity (Ω.cm) Dye degradation rate (%) Example 1 97 3850 6.2 Example 2 98 3855 6.1 Example 3 98 3860 5.8 Comparative Example 1 91 3245 12.4 Comparative Example 2 93 3350 11.1 Comparative Example 3 94 3435 10.7 Comparative Example 4 92 3025 19.2 Comparative Example 5 94 3275 17.3 Comparative Example 6 96 3410 15.1 Comparative Example 7 86 2875 28.1

[0151] As can be seen from Examples 1-3 and Comparative Examples 1-7, the water dispersibility, resistivity, and dye degradation rate of Example 3 of the present invention can be improved in a coordinated manner. By adjusting the specific preparation steps of the modifier treatment and heat homogenization treatment, combined with the infiltration liquid treatment, and the ball milling treatment using the silica-polyphonic boron nitride nanosheet modifier, coordinated synergy and synergy can be achieved, and the performance of the product is significantly improved.

[0152] The performance of the products tends to deteriorate when the preparation methods of the regulating modifier, the preparation steps of the heat homogenization treatment and the preparation methods of the impregnation liquid are different. Only the regulating modifier, heat homogenization treatment and impregnation liquid prepared by the method of the present invention have the most significant product performance effect. The effects of other methods are not as significant as those of the present invention. In addition, the inventors of the present invention also found that the performance of the product changed significantly when the ball milling treatment of the silica polytuned boron nitride nanosheet modifier was not adopted. Based on this, the present invention further explored and processed it.

[0153] The preparation method of the silicon dioxide polyphonic boron nitride nanosheet modifier is as follows:

[0154] S101: 3.5 parts of dioctyl phosphate are added to 7.5 parts of ethanol solvent, followed by 2 parts of sodium lauryl sulfate and 0.50 parts of isopropyl tris(dioctyl pyrophosphate) titanate, and the mixture is stirred evenly. Finally, 0.20 parts of triethanolamine are added and stirred thoroughly to obtain a polyhydric solution;

[0155] S102: placing the boron nitride nanosheets in 4 times the volume of deionized water and stirring evenly to obtain a pre-adjustment, then adding the pre-adjustment to the re-adjustment solution at a weight ratio of 1:5 and continuing to mix thoroughly to obtain a boron nitride nanosheet re-adjustment modification solution;

[0156] S103: The nano-silica is first heat-treated at 55° C. for 7.5 minutes, then air-cooled to room temperature, and then added into a 4-fold boron nitride nanosheet polytuning modification liquid and stirred thoroughly to obtain a silica polytuning boron nitride nanosheet modifier.

[0157] The present invention further explores the silicon dioxide polytuned boron nitride nanosheet modifier and explores its impact on product performance.

[0158] Experimental Example 1.

[0159] The difference from Example 3 is that in the preparation of the silicon dioxide polytuned boron nitride nanosheet modifier, no isopropyl tris(dioctyl pyrophosphate) titanate was added to the polytuning solution.

[0160] Experimental Example 2.

[0161] The difference from Example 3 is that in the preparation of the silicon dioxide polytuned boron nitride nanosheet modifier, no triethanolamine was added to the polytuning solution.

[0162] Experimental Example 3.

[0163] The difference from Example 3 is that nano-silica is not added in the preparation of the silica polytuned boron nitride nanosheet modifier.

[0164] Experimental Example 4.

[0165] The difference from Example 3 is that in the preparation of the silica polytuned boron nitride nanosheet modifier, graphene is used instead of boron nitride nanosheets.

[0166] The performance tests of product experimental examples 1-4 are as follows:

[0167] Water dispersibility (%) Resistivity (Ω.cm) Dye degradation rate (%) Example 1 94 3280 11.8 Example 2 93 3175 13.5 Example 3 89 2960 24.1 Example 4 92 3055 19.2

[0168] It can be seen from Experimental Examples 1-4 that in the preparation of the silica polytuned boron nitride nanosheet modifier, when nano-silica was not added, the performance of the product deteriorated significantly. At the same time, when the boron nitride nanosheets were replaced by graphene, the performance of the product also showed a significant trend of deterioration. No isopropyl tri(dioctyl pyrophosphate) titanate and no triethanolamine were added to the polytuning liquid, and the performance of the product showed a trend of deterioration. Only the silica polytuned boron nitride nanosheet modifier prepared by using the raw materials and process of the present invention has the most significant product performance. At the same time, the selection of boron nitride nanosheets is proprietary, and the use of other raw materials instead cannot achieve the effect of the present invention.

[0169] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the invention can be embodied in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as illustrative and non-restrictive, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations that come within the meaning and range of equivalents of the claims be embraced therein.

[0170] In addition, it should be understood that although this specification is described in terms of implementation methods, not every implementation method contains only one independent technical solution. This narrative method of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment can also be appropriately combined to form other implementation methods that can be understood by those skilled in the art.

Claims

1. A method for preparing high resistivity chemical fiber titanium dioxide, characterized in that: The following steps are involved: Step 1: heat-treating anatase titanium dioxide at 120-130°C for 10-20 minutes, then cooling to 40-45°C at a rate of 1-3°C / min, keeping the temperature, and setting aside; Step 2: The product of step 1 is placed in an ethylene glycol solvent of 3 to 5 times the total amount of the product of step 1 and stirred evenly, and then a regulating modifier of 10 to 15% of the total amount of anatase titanium dioxide is added, and the mixture is stirred for reaction. After stirring is completed, the mixture is washed with water and dried; Step 3: Heat homogenization treatment: first increase the temperature to 45-50°C at a rate of 1-2°C / min, keep warm for 5-10 minutes, and spray the impregnation liquid until the surface of the product in step 2 is soaked; Step 4: Then continue to heat up to 105-110°C at a rate of 3-5°C / min, keep warm for 5-10 minutes, and then air-cool to room temperature to obtain a heat-homogenized material; Step 5: adding 20-30% of the total amount of the heat-homogenized material to the heat-homogenized material and a silicon dioxide-polyboron nitride nanosheet modifier, and then feeding the heat-homogenized material into a ball mill for ball milling. After the ball milling is completed, washing and drying are performed to obtain a high-resistivity chemical fiber titanium dioxide powder; The preparation method of the regulating modifier is: S01: adding chitosan aqueous solution to ethanol solvent with a volume of 2 to 5 times the total volume of chitosan aqueous solution; S02: Then add 10-20% of the total amount of chitosan aqueous solution of silane coupling agent KH560 and 2-5% of the total amount of chitosan aqueous solution of lanthanum nitrate solution, and stir evenly; S03: adding sodium lignin sulfonate at 1-3% of the total amount of the chitosan aqueous solution, stirring thoroughly, and finally adding phosphate buffer solution at 1-3% of the total amount of the chitosan aqueous solution, mixing well, to obtain a regulating modifier; The preparation method of the infiltration liquid is: The hydroxyapatite is placed in a proton irradiation box for irradiation treatment, the irradiation power is 300-400W, the irradiation time is 20-30 minutes, and after the treatment is completed, the product is stirred in a 3-5 times hydrogen peroxide solution, the stirring speed is 350-450r / min, the stirring temperature is 40-45°C, and the stirring time is 10-20 minutes. After the treatment is completed, the product is washed with water and dried to obtain pre-conditioned hydroxyapatite; Then, the nano-barium sulfate is added to a 3-5 times hydrochloric acid solution, and then 2-5% of the total amount of the nano-barium sulfate and 8-12% of the total amount of the nano-barium sulfate are added with pre-adjusted hydroxyapatite, and the mixture is stirred thoroughly to obtain an infiltration solution; The preparation method of the silicon dioxide polyphonic boron nitride nanosheet modifier is as follows: S101: Add 2-5 parts of dioctyl phosphate to 5-10 parts of ethanol solvent, then add 1-3 parts of sodium lauryl sulfate and 0.45-0.65 parts of isopropyl tris(dioctyl pyrophosphate) titanate, stir evenly, and finally add 0.15-0.25 parts of triethanolamine, stir thoroughly to obtain a polyhydric solution; S102: placing the boron nitride nanosheets in 3-5 times the volume of deionized water and stirring evenly to obtain a pre-adjustment, then adding the pre-adjustment to the re-adjustment solution at a weight ratio of 1:5 and continuing to mix thoroughly to obtain a boron nitride nanosheet re-adjustment modification solution; S103: The nano-silica is first heat-treated at 50-60° C. for 5-10 minutes, then air-cooled to room temperature, and then added into 3-5 times the volume of the boron nitride nanosheet polytuning modification liquid and stirred thoroughly to obtain a silica polytuning boron nitride nanosheet modifier.

2. The method for preparing a high resistivity chemical fiber titanium dioxide according to claim 1, characterized in that: In the step 2, the stirring reaction is carried out at a speed of 750-850 r / min, a stirring time of 30-40 min, and a stirring temperature of 46-48° C.

3. The method for preparing a high resistivity chemical fiber titanium dioxide according to claim 1, characterized in that: The mass fraction of the chitosan aqueous solution is 5-8%; the mass fraction of the lanthanum nitrate solution is 1-3%.

4. The method for preparing a high resistivity chemical fiber titanium dioxide according to claim 1, characterized in that: The pH value of the phosphate buffer solution is 5.5-6.

5.

5. The method for preparing a high resistivity chemical fiber titanium dioxide according to claim 1, characterized in that: The mass fraction of the hydrochloric acid solution is 2-6%.

6. The method for preparing a high resistivity chemical fiber titanium dioxide according to claim 1, characterized in that: The concentration of the hydrogen peroxide solution is 10-12%wt.

7. The method for preparing a high resistivity chemical fiber titanium dioxide according to claim 1, characterized in that: The ball milling speed of the ball milling treatment is 1500-1800 r / min, and the ball milling time is 65-75 min.