CN115818707A - Micron-sized spherical rutile titanium dioxide and preparation method and application thereof - Google Patents
Micron-sized spherical rutile titanium dioxide and preparation method and application thereof Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 33
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 31
- 230000007062 hydrolysis Effects 0.000 claims abstract description 29
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 238000001354 calcination Methods 0.000 claims abstract description 17
- 239000010936 titanium Substances 0.000 claims abstract description 15
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 14
- 239000000945 filler Substances 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 9
- 239000002270 dispersing agent Substances 0.000 claims abstract description 9
- 230000001376 precipitating effect Effects 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 21
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- 238000003756 stirring Methods 0.000 claims description 16
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical group [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 239000012798 spherical particle Substances 0.000 claims description 7
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 2
- 229910001415 sodium ion Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 21
- 235000010215 titanium dioxide Nutrition 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000013078 crystal Substances 0.000 description 9
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- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000004891 communication Methods 0.000 description 4
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- 239000000126 substance Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
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- 238000001556 precipitation Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011163 secondary particle Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 2
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- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
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- 230000009466 transformation Effects 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses rutile titanium dioxide and a preparation method and application thereof, belonging to the technical field of new materials, and comprising the following preparation steps: the method comprises the following steps: the organic liquid solvent is used as a dispersing agent, simultaneously bottom water is added, the organic liquid solvent and the bottom water are mutually soluble, tetraalkyl titanate is used as a titanium source, weak base is used as a precipitating agent, weak acid is used as a hydrolysis control agent, the mass percentage of the tetraalkyl titanate, the hydrolysis control agent, the organic liquid solvent and the bottom water is 40-60; step two: and (2) taking the calcination temperature multiplied by the time as a new variable called curing time, calcining the titanium dioxide prepared in the step one at the curing time of 60-600 ℃ per hour, then calcining at the curing time of 600-2500 ℃ per hour, and finally calcining at the curing time of 2500-7200 ℃ per hour to obtain the application of the micron-sized rutile type titanium dioxide as the filler in the copper-clad plate.
Description
Technical Field
The invention belongs to the technical field of new material manufacturing, and particularly relates to micron-sized spherical rutile titanium dioxide and a preparation method and application thereof.
Background
In recent years, with the rapid development of the semiconductor industry, especially the electronic communication entering the high-frequency era, the appearance of the internet of things and the block chain, the requirement of the automobile unmanned on low-delay communication, the use frequency of the aerospace communication and radar positioning system is higher and higher, and the requirement on high dielectric constant (Dk) materials is increasing. The application of the high dielectric constant material provides possibility for solving the problem of the thickness limit of the gate oxide layer caused by miniaturization, light weight and integration of the current semiconductor device. At present, a large amount of high-frequency high-speed Printed Circuit Boards (PCBs) are needed for 5G communication antenna systems and Advanced Driving Assistance Systems (ADAS) of automotive electronics, and therefore a large amount of high-frequency Copper Clad Laminates (CCLs) are needed as basic materials.
Due to the special molecular structure, polytetrafluoroethylene (PTFE) has strong corrosion resistance and low water absorption, and can maintain stable dielectric property in a large temperature range. It also has a number of disadvantages, such as: the mechanical property is poor, and the rebound resilience, the strength and the hardness are weak; the thermal expansion coefficient is large, and the copper foil can fall off due to mismatching with the copper foil; poor heat conduction performance and easy heat accumulation; dk is only 2.1, and some ultrahigh frequency fields cannot be used independently, so that the processability is difficult, and the like. Therefore, the addition of fillers is a common modification.
Silica fume can meet some of the above requirements, but because it has a smaller Dk of only 3.9, it is difficult to adjust the dielectric constant of the whole sheet, so some other metal oxides enter our field of view. Titanium dioxide (chemical formula TiO) 2 Also known as titanium dioxide) as one of the important fillers, the physical, chemical, electrical, optical and other properties of the CCL have great influence on the performance and quality of the CCL. TiO 2 2 Is an important inorganicChemical products have important application in the industries of paint, printing ink, papermaking, plastic rubber, chemical fiber, ceramics and the like.
Chinese patent CN 114988468A discloses a method for preparing rutile TiO by using metatitanic acid as raw material and titanium carbide as auxiliary agent through microwave segmented calcination method 2 The material can obtain TiO with higher purity and uniform shape at lower reaction temperature 2 Particles; wherein the rutile phase accounts for>95 percent to obtain rutile type TiO 2 The particle size distribution of (A) is 100-400nm, and the decolorization power (TCS) is 1500-1800. At present, nano-sized titanium dioxide is usually researched in a laboratory stage in China, but the nano-sized titanium dioxide is applied to the field of copper-clad plates, and because the nano-sized material has large specific surface area and high surface energy, the nano-sized material is easy to agglomerate, so that the nano-sized titanium dioxide is difficult to uniformly disperse in a resin composition, and the dielectric constant is unstable. When a resin composition is prepared by mixing this with a PTFE emulsion, the viscosity of the resin composition increases, and the resin composition is difficult to use as a raw material of CCL, and a smaller filler particle size tends to mean that water absorption is easier. On the other hand, the particle shape of the filler also has a great influence on the performance of the filler, which can be well reflected in the field of silica fine powder fillers.
Chinese patent CN 113402774A discloses a method for preparing micron-sized titanium dioxide powder by using nano-sized titanium dioxide grains as raw materials and calcining at high temperature. The titanium dioxide powder with the grain diameter ranging from 1 mu m to 30 mu m is obtained. In the patent, the influence of the components and the content of impurity elements on the dielectric property of the titanium dioxide material is mentioned, in the calcining process, the radius of some impurity ions is larger, and the impurity ions enter titanium dioxide crystal lattices to cause crystal lattice distortion, so that the polarization strength of positive and negative ions is increased, the dielectric constant of a titanium dioxide powder product is increased, and meanwhile, the internal porosity of the powder material can be reduced by high-temperature calcining, so that the dielectric loss is also smaller. The titanium dioxide morphology in the above application includes spherical, angular and irregular shapes, which results in poor flowability, large sliding friction coefficient, and low expansibility.
Chinese patent CN 112678867A discloses a method for preparing titanium dioxide by reacting tetrabutyl titanate as a titanium source with ammonia water in a hexadecane solvent; however, the device is not limited to the specific type of the deviceThen, under a certain temperature rise program, the obtained titanium dioxide is heated to a temperature higher than 800 ℃ and calcined for 3-8 h to obtain rutile type titanium dioxide. The rutile TiO is finally prepared by optimizing factors such as roasting temperature, roasting time, titanium source, solvent, mass ratio of a reaction system, mass concentration of ammonia water, feeding sequence, stirring speed, system pH value and the like 2 The spheroidization rate is more than or equal to 95 percent, and the granularity D50 is 2-8 mu m. The production process needs ammonia water harmful to the environment, and the preparation process is complex.
Disclosure of Invention
The invention aims to solve the technical problem of synthesizing micron-sized spherical rutile titanium dioxide powder with high dielectric constant and low dielectric loss in one step, and the micron-sized spherical rutile titanium dioxide powder is used as a filler in the field of high-frequency copper-clad plate substrates.
A preparation method of rutile titanium dioxide is characterized in that: the method comprises the following steps: the method comprises the following steps: the organic liquid solvent is used as a dispersing agent, simultaneously bottom water is added, the organic liquid solvent and the bottom water are mutually soluble, tetraalkyl titanate is used as a titanium source, weak base is used as a precipitating agent, weak acid is used as a hydrolysis control agent, the mass percentage of the tetraalkyl titanate, the hydrolysis control agent, the organic liquid solvent and the bottom water is 40-60; step two: calcining the titanium dioxide prepared in the step one at the curing time of 60-600 ℃ per hour, calcining at the curing time of 600-2500 ℃ per hour, and finally calcining at the curing time of 2500-7200 ℃ per hour to obtain the micron-grade rutile titanium dioxide, wherein the particle size D50 of the rutile titanium dioxide is 8-30 microns, the water content is lower than 0.2%, and TiO in the rutile titanium dioxide is 2 The content of the titanium dioxide is more than or equal to 99wt%, the sphericity is more than 0.90, the sodium ion content of the rutile titanium dioxide is less than 10ppm, the chloride ion content is less than 20ppm, and the hydrogen ion content in the water extraction liquid is 1.00 to 10 -4 ～1.00*10 -6 mol/L. The prepared micron-sized rutile titanium dioxide is used as a filler in the application of a copper-clad plate.
Preferably: the tetraalkyl titanate is tetrabutyl titanate.
Preferably: the organic liquid solvent is liquid alcohol with 2-6 carbon atoms.
Preferably: the precipitant includes, but is not limited to, urea, dimethylamine, pyridine or ammonia, and the weak acid includes, but is not limited to, formic acid, carbonic acid, acetic acid, phosphoric acid.
Preferably: the stirring speed of the first step is 100-600 rpm.
The key technical steps of the invention are as follows:
(1) Adding alcohol as solvent and adding bottom water in certain proportion. On one hand, the alcohol can better dissolve the tetra-alkyl titanate and water, so that the tetra-alkyl titanate can be more easily contacted with hydroxide radicals required by hydrolysis; on the other hand, the polarity of the solvent can ensure the dispersibility of spherical particles and larger spherical particle size, so that liquid alcohol with 2-6 carbon atoms is selected as the solvent and plays a role of a dispersing agent. Tetrabutyl titanate is selected from commonly used titanium sources such as tetrabutyl titanate, titanium isopropoxide, titanyl sulfate, metatitanic acid and the like, and mainly in consideration of solubility, material stability and environmental protection of post-treatment, compared with titanium isopropoxide, tetrabutyl titanate is more stable and hydrolysis is easier to control, tetrabutyl titanate is free of sulfate radical, hydrolysis only generates butanol with a higher boiling point, and requirements on equipment and tail gas are not so high. Deionized water was used as bottom water in order not to introduce ions.
(2) Adding alkalescent substance as hydroxyl releasing agent, which is heated to decompose uniformly and slowly to release hydroxyl, and allowing the hydroxyl and titanium source to have precipitation reaction to obtain amorphous Ti (OH) 4 A white precipitate. To control the rate of hydrolysis, we add a certain amount of weak acid as hydroxyl inhibitor, also called hydrolysis controller, for OH control - Concentration, by hydrolysis of tetraalkyl titanates and weak acid with OH - The competitive reaction of acid-base neutralization can further control the hydrolysis process, so that crystal nuclei are generated in the reaction system as little as possible, and the growth of crystal grains is realized. Adding a dispersant, bottom water, a hydrolysis control agent and a titanium source, and stirringAnd carrying out processes of reaction, centrifugation, washing, drying, roasting and the like to finally obtain the titanium hydroxide particles.
(3) Urea, dimethylamine, pyridine or ammonia water is selected as a precipitator, formic acid, carbonic acid, acetic acid and phosphoric acid are selected as hydrolysis control agents to control the concentration and the generation rate of hydroxyl in a system, and organic titanium sources such as tetrabutyl titanate, titanium isopropoxide and the like are selected as titanium sources.
(4) Stirring speed and bath temperature. The stirring speed has great influence on the grain diameter of the hydrolysate, and researches show that the stirring speed can be ignored on the reaction kinetics of the precipitation process, has no influence on the sizes of crystal grains and primary aggregated particles and only influences the size of the finally recovered secondary particles. The larger the stirring speed, the more easily the small crystal grains collide and agglomerate, resulting in obtaining agglomerated secondary particles having a larger particle diameter. Preferably, we choose the speed of rotation between 0 and 700rpm. The hydrolysis reaction of the titanium liquid is endothermic reaction, so the hydrolysis reaction rate can be accelerated by increasing the reaction temperature, and the control requirement of the hydrolysis temperature is usually controlled near the boiling point to keep slight boiling. The boiling points of the titanium liquid are different for titanium liquids with different compositions. Because the adopted solvent is ethanol, the water bath temperature is 50-90 ℃.
(5) The proportioning of the whole reaction system is optimized, which is also the technical key point of the invention. The amount of dispersant, the amount of bottom water and the concentration of hydrolysis control agent were all studied one by one. Too low dispersant dosage can result in too fast hydrolysis rate, difficult control of particle size distribution, wider particle size distribution, low particle dispersibility, and too large dispersant dosage can result in smaller crystal grains, and cannot meet the requirements of electronic grade powder materials on filler size. The quantity of the bottom water not only influences the quality of the seed crystal at the initial stage of hydrolysis, but also influences the number of crystal nuclei in the whole precipitation process. Too high a quantity of bottom water tends to generate more nuclei, resulting in a reduction in particle size. Meanwhile, the bottom water amount plays an important role in the sphericity of the particles, the particles are small spherical particles at the beginning in the growth process, the growth rate is high, the growth rate is reduced along with the growth of the spherical particles, the sphericity cannot be maintained, and in the selected dispersing agent, the maximum reaction amount is reached and the solvent dosage capable of maintaining the spherical particles is: the bottom water amount ratio is 200-1000. High inhibitor concentrations in hydrolysis control agents consume too much OH - Influence the hydrolysis of the titanium source, and finally, the solvent dosage selected by a series of experiments is as follows: bottom water amount: the dosage of the inhibitor = 200-1000.
(6) The heat treatment conditions are critical to the phase transformation, and the rutile phase is known to be a thermally stable phase, and the anatase phase will transform to the rutile phase at high temperatures, so we chose a higher calcination temperature above 800 degrees. At such a higher heat treatment temperature, the anatase phase can be completely converted into the rutile phase after the holding time of more than 6 hours, namely the curing time of more than 4800 ℃ h. In addition, it should be noted that the temperature rise rate of the heat treatment is lower, so as to ensure that the morphology of the particles does not change greatly after the heat treatment. The titanium hydroxide generated by hydrolysis emits gas in the process of converting into anatase-phase titanium dioxide, bound water and absorbed water are lost, if the temperature rising rate is too fast, pores are easily generated and spherical particles are easy to crack, so that the preferred heat treatment rate is lower than 3 ℃/min. In the practical implementation process, in order to facilitate control, the concept of maintenance time is adopted for operation.
Compared with the prior art, the invention has the beneficial effects that: the invention provides rutile type titanium dioxide, wherein the proportion of rutile phase in the rutile type titanium dioxide>99.9 percent, the granularity D50 is 3-30 mu m, the relative dielectric constant is 100-120, the dielectric loss is 0.0005-0.002, and the rutile type titanium dioxide contains TiO 2 The content of (A) is more than or equal to 99.9wt%. The conductivity is less than or equal to 50 mu s/cm. Compared with two titanium dioxides mentioned in the background art, the material has the characteristics of high sphericity, high rutile phase ratio and the like, so that the material has the advantages of good fluidity, good dielectric property and the like.
Detailed Description
Example 1
Adding 300ml of ethanol and 20ml of deionized water into a three-neck flask provided with a mechanical stirrer, stirring at the rotating speed of 500rpm for 10min to fully mix the materials to obtain a solution A, and heating in a water bath at 50 ℃; premixing 30ml of tetrabutyl titanate and 3g of a hydrolysis control agent in a beaker to obtain a solution B, adding the solution B into the solution A, continuously stirring for 9 hours to obtain a reaction solution, centrifuging, drying and carrying out heat treatment at a final temperature of 1000 ℃ for 4 hours to obtain spherical titanium dioxide with the granularity D50 of 29 microns, wherein the rutile phase accounts for more than 99%.
Example 2
Adding 300ml of ethanol and 20ml of deionized water into a three-neck flask provided with a mechanical stirrer, stirring at the rotating speed of 500rpm for 10min to fully mix the materials to obtain a solution A, and heating in a water bath at 50 ℃; premixing 30ml of tetrabutyl titanate and 3g of a hydrolysis control agent in a beaker to obtain a solution B, adding the solution B into the solution A, stirring for 9 hours at 300rpm, centrifuging and drying the obtained reaction solution, and carrying out heat treatment at the final temperature of 1000 ℃ for 4 hours to obtain spherical titanium dioxide with the particle size D50 of 20 micrometers, wherein the rutile phase accounts for more than 99%.
Example 3
Adding 300ml of ethanol and 20ml of deionized water into a three-neck flask provided with a mechanical stirrer, stirring at the rotating speed of 500rpm for 10min to fully mix the materials to obtain a solution A, and simultaneously heating in a water bath at 70 ℃; premixing 30ml of tetrabutyl titanate and 3g of a hydrolysis control agent in a beaker to obtain a solution B, adding the solution B into the solution A to react for 9 hours at 100rpm, centrifuging and drying the obtained reaction solution, and carrying out heat treatment at the final temperature of 1000 ℃ for 4 hours to obtain spherical titanium dioxide with the particle size D50 of 12 micrometers, wherein the rutile phase ratio is more than 99%.
Example 4
Adding 300ml of ethanol and 20ml of deionized water into a three-neck flask provided with a mechanical stirrer, stirring at the rotating speed of 500rpm for 10min to fully mix the materials to obtain a solution A, and simultaneously heating in a water bath at 70 ℃; premixing 30ml of tetrabutyl titanate and 9g of a hydrolysis control agent (the inhibitor accounts for a small percentage) in a beaker to obtain a solution B, adding the solution B into the solution A to react for 9 hours at 100rpm, centrifuging and drying the obtained reaction solution, and carrying out heat treatment at the final temperature of 1000 ℃ for 4 hours to obtain the agglomerated angle type titanium dioxide with the granularity D50 of 21 microns, wherein the rutile phase accounts for more than 99%.
Example 5
Adding 300ml of ethanol and 20ml of deionized water into a three-neck flask provided with a mechanical stirrer, stirring at the rotating speed of 500rpm for 10min to fully mix the materials to obtain a solution A, and heating in a water bath at 50 ℃; premixing 30ml of tetrabutyl titanate and 3g of a hydrolysis control agent in a beaker to obtain a solution B, adding the solution B into the solution A to react for 9 hours at 100rpm, centrifuging and drying the obtained reaction solution, and carrying out heat treatment at the final temperature of 700 ℃ for 4 hours to obtain spherical titanium dioxide with the particle size D50 of 12 microns, wherein the rutile phase accounts for 78%.
Example 6
Adding 300ml of ethanol and 20ml of deionized water into a three-neck flask provided with a mechanical stirrer, stirring at the rotating speed of 500rpm for 10min to fully mix the materials to obtain a solution A, and heating in a water bath at 50 ℃; premixing 30ml of tetrabutyl titanate and 3g of a hydrolysis control agent in a beaker to obtain a solution B, adding the solution B into the solution A to react for 9 hours at 100rpm, centrifuging and drying the obtained reaction solution, and carrying out heat treatment at the final temperature of 900 ℃ for 4 hours to obtain spherical titanium dioxide with the particle size D50 of 14 microns, wherein the rutile phase accounts for 89 percent.
Example 7
Adding 100ml of ethanol and 20ml of deionized water into a three-neck flask provided with a mechanical stirrer, stirring at the rotating speed of 500rpm for 10min to fully mix the materials to obtain a solution A, and heating in a water bath at 50 ℃; premixing 30ml of tetrabutyl titanate and 3g of a hydrolysis control agent in a beaker to obtain a solution B, adding the solution B into the solution A to react for 9 hours at 100rpm, centrifuging and drying the obtained reaction solution, and carrying out heat treatment at the final temperature of 1000 ℃ for 4 hours to obtain the agglomerated angle type titanium dioxide with the granularity D50 of 30 micrometers, wherein the rutile phase accounts for 99 percent.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (10)
1. A preparation method of rutile titanium dioxide is characterized in that: the method comprises the following steps:
the method comprises the following steps: the organic liquid solvent is used as a dispersing agent, simultaneously bottom water is added, the organic liquid solvent and the bottom water are mutually soluble, tetraalkyl titanate is used as a titanium source, weak base is used as a precipitating agent, weak acid is used as a hydrolysis control agent, the mass percentage of the tetraalkyl titanate, the hydrolysis control agent, the organic liquid solvent and the bottom water is 40-60;
step two: and (3) taking the calcination temperature multiplied by the time as a new variable called curing time, calcining the titanium dioxide prepared in the step one at the curing time of 60-600 ℃ per hour, then calcining at the curing time of 600-2500 ℃ per hour, and finally calcining at the curing time of 2500-7200 ℃ per hour to obtain the micron-sized rutile titanium dioxide.
2. The process for producing rutile titanium dioxide according to claim 1, wherein: the tetraalkyl titanate is tetrabutyl titanate.
3. A process for producing rutile titanium dioxide according to claim 1, wherein the organic liquid solvent is a liquid alcohol having 2 to 6 carbon atoms.
4. A process for preparing rutile titanium dioxide as claimed in claim 1, wherein the precipitant includes but is not limited to urea, dimethylamine, pyridine or ammonia, and the weak acid includes but is not limited to formic acid, carbonic acid, acetic acid, phosphoric acid.
5. The process for producing rutile titanium dioxide according to claim 1, wherein: the stirring speed of the step one is 100-600 rpm.
6. The method for producing rutile titanium dioxide according to claim 1, wherein: the dosage of the organic liquid solvent is as follows: bottom water amount: the dosage of the inhibitor = 200-1000.
7. The method for producing rutile titanium dioxide according to claim 1, wherein: the heating rate of the heat treatment with the calcination temperature above 800 ℃ is lower than 3 ℃/min.
8. Use of micron-sized rutile titanium dioxide prepared by the process of any of claims 1 to 7 as a filler in copper-clad laminates.
9. A rutile titanium dioxide, characterized by: the particle size D50 of the rutile type titanium dioxide is 10-30 microns, the water content is lower than 0.2 percent, and TiO in the rutile type titanium dioxide 2 The content of the spherical particles is more than or equal to 98wt percent, and the sphericity is more than 0.90 percent.
10. A rutile titanium dioxide as claimed in claim 8, wherein: the rutile titanium dioxide has a sodium ion content of less than 10ppm, a chloride ion content of less than 20ppm, and a hydrogen ion content of 1.00 x 10 in the water extract -4 ～1.00*10 -6 mol/L。
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| US20040161380A1 (en) * | 2003-02-19 | 2004-08-19 | Degussa Ag | Titanium dioxide particles, their preparation and use |
| CN103833074A (en) * | 2014-03-19 | 2014-06-04 | 吉林大学 | Method for preparing titanium dioxide nanoparticles |
| CN112678867A (en) * | 2020-12-25 | 2021-04-20 | 苏州锦艺新材料科技有限公司 | Rutile type titanium dioxide and preparation method and application thereof |
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| US20040161380A1 (en) * | 2003-02-19 | 2004-08-19 | Degussa Ag | Titanium dioxide particles, their preparation and use |
| CN103833074A (en) * | 2014-03-19 | 2014-06-04 | 吉林大学 | Method for preparing titanium dioxide nanoparticles |
| CN112678867A (en) * | 2020-12-25 | 2021-04-20 | 苏州锦艺新材料科技有限公司 | Rutile type titanium dioxide and preparation method and application thereof |
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