CN112678867B - Rutile type titanium dioxide and preparation method and application thereof - Google Patents
Rutile type titanium dioxide and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to rutile titanium dioxide and a preparation method and application thereof, wherein the spheroidization rate of the rutile titanium dioxide is more than or equal to 95%, the granularity D50 is 2-8 microns, the relative dielectric constant is 100-120, the dielectric loss is 0.0005-0.002, and TiO in the rutile titanium dioxide2The content of (A) is more than or equal to 98 wt%. The rutile type titanium dioxide in the invention has high spheroidization rate, high dielectric constant and low dielectric loss.
Description
Technical Field
The invention belongs to the field of copper-clad plates, and particularly relates to rutile titanium dioxide and a preparation method and application thereof.
Background
The copper-clad plate can be used as a substrate material in the manufacturing process of a printed circuit board, is widely applied to industries such as computers, communication, consumer electronics, industry/medical treatment, military, semiconductors, automobiles and the like, and almost relates to all electronic information products.
With the rapid development of the fields of satellite, 5G communication, navigation and the like, the application requirements of various electronic products are higher and higher, and in order to meet the requirements of miniaturization, light weight, high speed, high frequency, precision and the like, the filler for the copper-clad plate with high dielectric constant and low dielectric loss and the copper-clad plate prepared by the filler are required to be developed. Most of high dielectric constant materials on the market at present have low filling amount, and the copper-clad plate filled with the high dielectric constant materials has low dielectric constant or high dielectric loss, so that the requirements of customers cannot be met.
Disclosure of Invention
The invention aims to provide rutile titanium dioxide with high dielectric constant and low dielectric loss, and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
one aspect of the present invention provides a rutile formTitanium dioxide, wherein the spheroidization rate of the rutile titanium dioxide is more than or equal to 95%, the granularity D50 is 2-8 microns, the relative dielectric constant is 100-120, the dielectric loss is 0.0005-0.002, and TiO in the rutile titanium dioxide2The content of (A) is more than or equal to 98 wt%.
Preferably, the rutile titanium dioxide has a conductivity of 100us/cm or less.
Preferably, the pH of the rutile titanium dioxide is 6-8.
In a second aspect, the present invention provides a process for the preparation of rutile titanium dioxide by reacting a tetraalkyl titanate with aqueous ammonia in the presence of an organic non-polar liquid solvent to form titanium dioxide; and calcining the titanium dioxide at 100-200 ℃ for 1-3 h, calcining at 500-800 ℃ for 1-3 h, and calcining at a temperature higher than 800 ℃ to obtain the rutile titanium dioxide.
Preferably, the temperature higher than 800 ℃ means that the temperature is 900-1400 ℃.
Further preferably, the calcination is carried out for 3-8 h at the temperature of 900-1400 ℃. The higher the calcination temperature is, the higher the preparation cost of the rutile titanium dioxide is, the preparation cost of the rutile titanium dioxide is increased, and therefore, the preparation method is preferably 900-1400 ℃.
Preferably, the tetraalkyl titanate is tetrabutyl titanate. The price of tetrabutyl titanate is relatively low, the preparation cost of titanium dioxide can be reduced by using tetrabutyl titanate to prepare rutile type titanium dioxide, the impurity content is low, and the method is economical and practical.
The organic nonpolar liquid solvent is liquid alkane with 5-16 carbon atoms, and the chemical formula of the liquid alkane is CxH2x+2Wherein x =5~ 16.
Further preferably, the organic non-polar liquid solvent is hexadecane. The hexadecane is adopted as the organic nonpolar liquid solvent, and the hexadecane has good emulsifying property, is easier to form emulsion with ammonia water, can form uniform emulsified microspheres with the ammonia water, and is more beneficial to the formation of spherical rutile type titanium dioxide.
Preferably, the mass percentage of the tetraalkyl titanate, the organic nonpolar liquid solvent and the ammonia water is 3-15: 20-100: 1, preferably 5-10: 40-80: 1, and more preferably 5-8: 50-65: 1. Too little tetraalkyl titanate, too little ammonia water, or too much organic nonpolar liquid solvent can result in too small a particle size of the produced rutile titanium dioxide, and when the particle size of the rutile titanium dioxide is too small, it is mixed with the PTFE emulsion to produce a resin composition, which results in too large a viscosity of the resin composition and the resin composition cannot be used.
Preferably, the mass concentration of the ammonia water is 3-8 mol/L.
Preferably, the ammonia water and the organic nonpolar liquid solvent are stirred to form an emulsion, the emulsion and the tetraalkyl titanate form titanium dioxide, the stirring speed is 1500-4000 rpm, and the stirring time is not less than 15 min.
Further preferably, the stirring time is 20-40 min. The upper limit of the time for forming the emulsion by stirring is not limited to 40min, and can be 60min, 80min and 100min, but the cost is increased due to the overlong stirring time, so 20-40 min is preferred in the invention.
Preferably, the emulsion and the tetraalkyl titanate form titanium dioxide under the condition of stirring, the stirring speed is 2000-4000 rpm, and the stirring time is not less than 2 h.
Further preferably, the stirring time is 2-10 h. The upper limit of the stirring time in the present invention is not limited to 10 hours, and may be 12 hours, 13 hours, or 14 hours, but an excessively long stirring time increases the cost, and therefore, the present invention is preferably 2 to 10 hours.
Preferably, the temperature of the emulsion and the tetraalkyl titanate reaction is controlled to be 100-300 ℃.
Preferably, the pH of the reaction system is controlled to be 8-9.
The third aspect of the invention provides an application of the rutile type titanium dioxide or the rutile type titanium dioxide prepared by the preparation method as the filler in a copper-clad plate.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages: the rutile type titanium dioxide in the invention has high spheroidization rate, high dielectric constant and low dielectric loss.
Drawings
FIG. 1 is an XRD pattern of rutile titanium dioxide prepared in example 1 of the present invention;
FIG. 2 is a graph of the particle size of rutile titanium dioxide produced in example 1 of the present invention;
FIG. 3 is a scanning electron micrograph of rutile titanium dioxide prepared in example 1 of the present invention;
FIG. 4 is a graph of the particle size of rutile titanium dioxide produced in comparative example 1 of the present invention;
FIG. 5 is a scanning electron micrograph of rutile titanium dioxide prepared in comparative example 1 of the present invention;
FIG. 6 is a scanning electron micrograph of rutile titanium dioxide prepared in comparative example 2 of the present invention;
FIG. 7 is a scanning electron micrograph of rutile titanium dioxide prepared in comparative example 3 of the present invention;
FIG. 8 is a scanning electron micrograph of rutile titanium dioxide prepared in comparative example 4 of the present invention;
FIG. 9 is a scanning electron micrograph of rutile titanium dioxide prepared in comparative example 5 of the present invention;
FIG. 10 is a scanning electron micrograph of rutile titanium dioxide prepared in comparative example 6 of the present invention;
FIG. 11 is a scanning electron micrograph of rutile titanium dioxide prepared in comparative example 7 of the present invention;
FIG. 12 is a scanning electron micrograph of rutile titanium dioxide prepared in comparative example 8 of the present invention;
FIG. 13 is an XRD pattern of rutile titanium dioxide prepared in comparative example 9 of the present invention;
FIG. 14 is a graph of the particle size of rutile titanium dioxide produced in comparative example 9 of the present invention;
FIG. 15 is a scanning electron micrograph of rutile titanium dioxide prepared in comparative example 9 of the present invention;
FIG. 16 is an XRD pattern of rutile titanium dioxide produced in comparative example 10 of the present invention;
FIG. 17 is a scanning electron micrograph of rutile titanium dioxide prepared in comparative example 10 of the present invention;
FIG. 18 is a graph of the particle size of rutile titanium dioxide produced in comparative example 10 of the present invention;
FIG. 19 is a scanning electron micrograph of rutile titanium dioxide prepared in comparative example 11 in accordance with the present invention;
FIG. 20 is a scanning electron micrograph of rutile titanium dioxide prepared in comparative example 12 of the present invention;
FIG. 21 is a scanning electron micrograph of rutile titanium dioxide prepared in comparative example 13 of the present invention;
FIG. 22 is a scanning electron micrograph of rutile titanium dioxide prepared in comparative example 14 of the present invention;
FIG. 23 is a scanning electron micrograph of rutile titanium dioxide prepared according to comparative example 15 of the present invention;
FIG. 24 is a scanning electron micrograph of rutile titanium dioxide prepared in comparative example 16 in accordance with the present invention;
FIG. 25 is an XRD pattern of rutile titanium dioxide produced in comparative example 17 of the present invention;
FIG. 26 is a graph of the particle size of rutile titanium dioxide produced in comparative example 17 of the present invention;
FIG. 27 is a scanning electron micrograph of rutile titanium dioxide prepared according to comparative example 17 of the present invention;
FIG. 28 is an XRD pattern of rutile titanium dioxide produced in comparative example 18 of the present invention;
FIG. 29 is a graph of the particle size of rutile titanium dioxide produced in comparative example 18 of the present invention;
FIG. 30 is a scanning electron micrograph of rutile titanium dioxide prepared according to comparative example 18 of the present invention;
FIG. 31 is a scanning electron micrograph of rutile titanium dioxide prepared according to comparative example 19 of the present invention;
FIG. 32 is a graph of the particle size of rutile titanium dioxide produced in comparative example 19 of the present invention;
FIG. 33 is a scanning electron micrograph of rutile titanium dioxide prepared in comparative example 20 of the present invention;
FIG. 34 is a graph of the particle size of rutile titanium dioxide produced in comparative example 20 of the present invention;
FIG. 35 is a scanning electron micrograph of rutile titanium dioxide prepared in comparative example 21 of the present invention;
FIG. 36 is a scanning electron micrograph of rutile titanium dioxide prepared according to comparative example 22 of the present invention;
FIG. 37 is a graph showing the particle size of rutile titanium dioxide produced in comparative example 22 of the present invention;
FIG. 38 is a scanning electron micrograph of rutile titanium dioxide prepared according to comparative example 23 of the present invention;
FIG. 39 is a particle size diagram of rutile titanium dioxide produced in comparative example 23 of the present invention;
FIG. 40 is a scanning electron micrograph of rutile titanium dioxide prepared according to comparative example 24 of the present invention;
FIG. 41 is a scanning electron micrograph of rutile titanium dioxide prepared according to comparative example 25 of the present invention;
FIG. 42 is an XRD pattern of rutile titanium dioxide produced in comparative example 26 of the present invention;
FIG. 43 is a scanning electron micrograph of rutile titanium dioxide prepared according to comparative example 26 of the present invention;
FIG. 44 is a graph of the particle size of rutile titanium dioxide produced in comparative example 26 of the present invention;
FIG. 45 is an XRD pattern of rutile titanium dioxide produced in comparative example 27 of the present invention;
FIG. 46 is a scanning electron micrograph of rutile titanium dioxide prepared according to comparative example 27 of the present invention;
FIG. 47 is a particle size diagram of rutile titanium dioxide produced by comparative example 27 of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples. However, the present invention is not limited to the following examples. The implementation conditions adopted in the embodiments can be further adjusted according to different requirements of specific use, and the implementation conditions not mentioned are conventional conditions in the industry. The technical features of the embodiments of the present invention may be combined with each other as long as they do not conflict with each other.
The following titanium dioxide performance test and copper clad laminate performance test mainly adopt the following measurement methods:
1. the dielectric property test of the powder shows that the powder is sintered into ceramic, and then a network analyzer is used for testing the dielectric property (dielectric constant and dielectric loss) index of the ceramic under 10G.
2. The dielectric property test of the copper-clad plate is to test the dielectric property indexes (dielectric constant and dielectric loss) of the copper-clad plate by a network analyzer under 10G.
3. And (3) viscosity testing: the powder and the resin composition were mixed uniformly, and the viscosity data was measured with a rotational viscometer.
4. The detection method of the sphericity ratio comprises the following steps: respectively selecting 3 areas by using a scanning electron microscope, counting the number n of non-spherical particles in the powder and the number m of spherical powder in the powder under 10000 times, and selecting the powder according to the requirements: the major diameter is more than or equal to 2.0 um;
spheroidization rate = [ (m)/(m + n) ] + 100%.
5. The method for measuring the rutile content comprises the following steps: an X-ray diffraction method for measuring the ratio of anatase type to rutile type in the nanometer titanium dioxide by GB/T37054 and 2018 nanotechnology. 6. The titanium dioxide chemical composition determination method comprises the following steps: testing was performed using XRF.
7. And (3) measuring the pH value: the pH of 10g dispersed in 100g of pure water was measured using a pH meter.
8. And (3) particle size determination: measured using a malvern type 2000 particle sizer.
9. Measuring ignition loss; calcination was carried out at 1000 ℃ using a muffle furnace until constant weight measurement was achieved.
The rutile titanium dioxide prepared in the following examples and comparative examples has a small amount of SiO present therein2、Fe2O3、Al2O3、Na2O、K2And O, mainly caused by the introduction of impurities in the reaction and calcination processes, and the copper-clad plate cannot be manufactured for testing when the material has poor sphericity.
Example 1
The rutile titanium dioxide is prepared by the following steps:
(1) adding hexadecane (2000 parts) into a reaction kettle, then adding an ammonia water solution (35 parts), wherein the concentration of ammonia water is 5mol/L, emulsifying and stirring at a high speed of 3000rpm for 30 minutes;
(2) adding 300 parts of tetrabutyl titanate into the reaction kettle emulsified in the step (1) for homogenizing and high-speed stirring, and supplementing ammonia water into the reaction kettle to control the pH value to be 8.5, the temperature to be 240 ℃, the stirring speed to be 3000rpm and the reaction time to be 6h to prepare the spherical titanium dioxide.
(3) And (3) calcining the spherical titanium dioxide prepared in the step (2) at a high temperature, wherein the temperature rise curve is as follows: calcining at 150 deg.C for 2 hr, 600 deg.C for 1.5 hr, and 1200 deg.C for 5 hr.
As can be seen from FIGS. 1 to 3, the chemical composition of titanium dioxide prepared in the preparation method of example 1 is TiO2: 99.50%、SiO2:0.03%、Fe2O3:0.01%、Al2O3:0.03%、Na2O:0.002%、K20.001% of O, 6 us/cm of conductivity, 7.2 of pH, 112 of dielectric constant, 0.0008 of dielectric loss, 99.5% of rutile crystal titanium dioxide and H20.05% of O, loss on ignition: 0.05% and a particle size of D50:3.452 μm.
Example 2
Using the spherical rutile titanium dioxide and PTFE emulsion prepared in example 1, the ratio of 6: 1, drying, pressing into bonding sheets of 500 x 500mm x 5mm by using a die, then using 5 bonding sheets and pasting copper foils on two sides, and pressing at 50kg of pressure and 385 ℃ to synthesize the copper-clad plate.
The resin composition has a viscosity of 600cps, a dielectric constant of 13, and a dielectric loss of 0.0012.
Comparative example 1
The difference from example 1 is that the speed of emulsification high-speed stirring was 1300 rpm.
As can be seen from FIGS. 4 and 5, the titanium dioxide prepared in comparative example 1 has a particle size D50: 10.533. mu.m, and the titanium dioxide has non-uniform spherical shape and nonuniform size, and too low a stirring speed results in a large size of the resulting spheres.
Comparative example 2
The difference from example 1 is that the speed of emulsification high-speed stirring was 4500 rpm.
As can be seen from FIG. 6, there are many non-spherical structures in the material, and too much stirring speed results in too few spherical structures in the material.
Comparative example 3
The difference from example 1 is that the pH value was controlled to 7.5 during the homogenization high-speed stirring.
As can be seen from fig. 7, the material contains more non-spherical structures and the pH is too low, which may result in insufficient reaction.
Comparative example 4
The difference from example 1 is that the pH was controlled to 10 during the homogenization and high-speed stirring.
As can be seen from FIG. 8, the material contains a large amount of non-spherical structures, the pH value is too high, the reaction is too fast, and a lot of non-spherical structures are generated
Comparative example 5
The difference from example 1 is that the temperature was controlled to 80 ℃ during homogenization and high-speed stirring.
As can be seen from FIG. 9, there are a large number of non-spherical structures in the material and the temperature is too low, which may result in incomplete reaction.
Comparative example 6
The difference from example 1 is that the temperature was controlled to 350 ℃ during homogenization and high-speed stirring.
As can be seen from FIG. 10, the material has a non-spherical aggregate structure, and too high temperature causes too violent reaction and spherical structure is not easy to generate.
Comparative example 7
The difference from example 1 is that the homogenizing high-speed stirring speed was 4500 rpm.
As can be seen from fig. 11, the material contains a large amount of non-spherical structures, and the stirring speed is such that the material does not form spherical structures well.
Comparative example 8
The difference from example 1 is that the reaction time was controlled to 1 hour during the homogenization and high-speed stirring.
As can be seen from fig. 12, the material contains a large amount of non-spherical structures, and the reaction time is too short to facilitate the formation of spherical structures, resulting in few spherical structures.
Comparative example 9
The difference from example 1 is that the reaction time was controlled to be 11 hours during the high-speed stirring of the emulsion.
As can be seen from FIGS. 13 to 15, the chemical composition of titanium dioxide produced in the production manner of comparative example 9 was TiO2: 99.51%、SiO2:0.020%、Fe2O3:0.009%、Al2O3:0.02%、Na2O:0.0024%、K20.0012 percent of O, the conductivity of 9 us/cm, the pH value of 7.5, the dielectric constant of 113, the dielectric loss of 0.0009, the content of rutile crystal type titanium dioxide of 99.56 percent, the particle size of D50 of 3.012 microns, H20.08 percent of O and 0.02 percent of loss on ignition.
The required rutile form of titanium dioxide can be obtained by increasing the reaction time, but the cost increases with an increase in the reaction time.
Comparative example 10
The difference from example 1 is that the calcination step of step (3) was not performed.
As shown in FIGS. 16 to 18, the chemical composition of the titanium dioxide prepared in the preparation method of comparative example 10 was TiO2: 96.50%、SiO2:0.030%、Fe2O3:0.008%、Al2O3:0.03%、Na2O:0.0030%、K2O:0.0025%、H22.05% of O, loss on ignition: 1.82 percent, the conductivity is 15 us/cm, the pH value is 7.5, the dielectric constant is 95, the dielectric loss is 0.008, the rutile crystal form content is 99.56 percent, and the particle size is D50:3.050 microns.
The spherical titanium dioxide obtained after the reaction is not calcined, and has high moisture content, high ignition loss, low dielectric constant and high dielectric loss.
Comparative example 11
The difference from example 1 is that the temperature rise curve in step (3) is different, and the temperature rise curve is: calcining at 80 deg.C for 2 hr, 600 deg.C for 1.5 hr, and 1200 deg.C for 5 hr.
As can be seen from fig. 19, the material contained a large amount of non-spherical structures, and the initial calcination temperature was too low, and drainage was insufficient, resulting in a material with few spherical structures.
Comparative example 12
The difference from example 1 is that the temperature rise curve in step (3) is different, and the temperature rise curve is: calcining at 250 deg.C for 2 hr, at 600 deg.C for 1.5 hr, and at 1200 deg.C for 5 hr.
As can be seen in FIG. 20, the material contained a large amount of non-spherical structures, and the initial calcination temperature was too high and drainage was too rapid, resulting in a material with few spherical structures.
Comparative example 13
The difference from example 1 is that the temperature rise curve in step (3) is different, and the temperature rise curve is: calcining at 150 deg.C for 0.5 hr, at 600 deg.C for 1.5 hr, and at 1200 deg.C for 5 hr.
As can be seen from FIG. 21, the material contained a large amount of non-spherical structures, and the calcination time at 150 ℃ was too short, the water contained in the material could not be completely discharged, and the subsequent temperature increase resulted in the breakage of the spherical material.
Comparative example 14
The difference from example 1 is that the temperature rise curve in step (3) is different, and the temperature rise curve is: calcining at 150 deg.C for 2 hr, 400 deg.C for 1.5 hr, and 1200 deg.C for 5 hr.
As can be seen from FIG. 22, the material contains a large amount of non-spherical structures, and the organic substances cannot be completely calcined at the temperature of 400 ℃, so that the organic substances are largely decomposed due to high temperature at the later stage, and the spherical structures in the material are few.
Comparative example 15
The difference from example 1 is that the temperature rise curve in step (3) is different, and the temperature rise curve is: calcining at 150 deg.C for 2 hr, 900 deg.C for 1.5 hr, and 1200 deg.C for 5 hr.
As can be seen from fig. 23, there are a large number of non-spherical structures in the material, mainly due to the rapid decomposition of the organic substances after the 900 ℃ calcination and the too high calcination temperature.
Comparative example 16
The difference from example 1 is that the temperature rise curve in step (3) is different, and the temperature rise curve is: calcining at 150 deg.C for 2 hr, at 600 deg.C for 0.5 hr, and at 1200 deg.C for 5 hr.
As can be seen from FIG. 24, the material contains a large amount of non-spherical structures, and the calcination time at 600 ℃ is too short, which results in insufficient organic emission and thus few spherical structures.
Comparative example 17
The difference from example 1 is that the temperature rise curve in step (3) is different, and the temperature rise curve is: calcining at 150 deg.C for 2 hr, 600 deg.C for 1.5 hr, and 800 deg.C for 5 hr.
As can be seen from FIGS. 25 to 27, the chemical composition of the titanium dioxide prepared in the manner of comparative example 17 was TiO2: 98.03%、SiO2:0.018%、Fe2O3:0.008%、Al2O3:0.16%、Na2O:0.0022%、K20.0015% of O, conductivity of 13 us/cm, pH of 7.2, H20.06% of O, loss on ignition: 0.81 percent, the dielectric constant is 102, the dielectric loss is 0.003, the content of rutile type titanium dioxide is 99.45 percent, and the particle size is D50:3.068 microns.
Because the high-temperature calcination temperature is only 800 ℃, organic substances cannot be completely discharged, the ignition loss is high, the dielectric constant is low, and the dielectric loss is high.
Comparative example 18
The difference from example 1 is that the temperature rise curve in step (3) is different, and the temperature rise curve is: calcining at 150 deg.C for 2 hr, 600 deg.C for 1.5 hr, and 1500 deg.C for 5 hr.
As can be seen from FIGS. 28 to 30, the chemical composition of the titanium dioxide prepared in the manner of comparative example 18 was TiO2: 99.52%、SiO2:0.02%、Fe2O3:0.008%、Al2O3:0.05%、Na2O:0.004%、K20.001% of O, an electric conductivity of 5 us/cm, a pH of 7.0, a dielectric constant of 115, a dielectric loss of 0.0009 and rutileThe content of the crystal form titanium dioxide is 99.54 percent, H20.03 percent of O, loss on ignition: 0.04% and a particle size of D50:3.094 μm.
Higher high temperature calcination temperatures result in higher yields of the desired material, but the cost increases with higher calcination temperatures.
Comparative example 19
The difference from example 1 is that tetrabutyl titanate (30 parts) was charged into the reaction vessel.
As can be seen in fig. 31 and 32, the resulting material was a uniform spherical structure but with a small particle size of D50:0.837 microns. The granularity is small due to too little tetrabutyl titanate, the viscosity of the mixture of the tetrabutyl titanate and PTFE is 6520cps, the viscosity is too high, the materials are difficult to disperse, and the copper-clad plate cannot be manufactured.
Comparative example 20
The difference from example 1 is that tetrabutyl titanate (600 parts) was charged into the reaction vessel.
As can be seen from fig. 33 and 34, too much tetrabutyl titanate results in a large particle size of the resulting material with a large amount of non-spherical structures in the material.
Comparative example 21
The difference from example 1 is that hexadecane (300 parts) was charged into the reaction vessel.
As can be seen in fig. 35, too little hexadecane resulted in a material with a large number of non-spherical structures.
Comparative example 22
The difference from example 1 is that hexadecane (4000 parts) was added to the reaction vessel.
As can be seen from FIGS. 36 and 37, too much cetane makes the particle size of the prepared material too small, the viscosity of the mixture with PTFE is 6520cps, the viscosity is too high, the material is difficult to disperse, and the copper-clad plate can not be prepared.
Comparative example 23
Except for adding ammonia (3 parts) to the reaction vessel in the same manner as in example 1.
As can be seen from FIGS. 38 and 39, the amount of ammonia water is too small, and although the prepared material is spherical, the particle size is too small, the viscosity of the mixture with PTFE is 6520cps, the viscosity is too large, the material is difficult to disperse, and the copper-clad plate cannot be prepared.
Comparative example 24
Except for adding ammonia (150 parts) to the reaction vessel in the same manner as in example 1.
As can be seen from FIG. 40, too much ammonia caused too fast reaction, and the resulting material was substantially non-spherical in structure.
Comparative example 25
The difference from example 1 is that the homogenization high-speed stirring time is 10 minutes.
As can be seen from FIG. 41, the stirring time is too short to easily form a spherical structure.
Comparative example 26
The difference from example 1 is that the high speed stirring time was homogenized for 60 minutes.
As can be seen from FIGS. 42 to 44, the chemical composition of the titanium dioxide prepared in the manner of comparative example 26 was TiO2: 99.55%、SiO2:0.02%、Fe2O3:0.02%、Al2O3:0.01%、Na2O:0.003%、K20.002% of O, 7.2 us/cm of conductivity, 7.3 of pH, 113 of dielectric constant, 0.0007 of dielectric loss, 99.6% of rutile crystal form titanium dioxide and H20.06% of O, loss on ignition: 0.04% and a particle size of D50:2.409 μm.
While extended stirring times can produce acceptable spherical rutile titanium dioxide, extended stirring times result in corresponding increased production costs.
Comparative example 27
The difference from example 2 is that an angular non-spherical rutile titanium dioxide and PTFE emulsion was used, as in 6: 1 mass ratio, and pressing into 500 × 500mm × 5mm bonding sheets using a die.
As can be seen from FIGS. 45 to 47, the chemical composition of the angular non-spherical rutile titanium dioxide is TiO2: 99.51%、SiO2:0.03%、Fe2O3:0.007%、Al2O3:0.04%、Na2O:0.006%、K20.003% of O, the conductivity of 8 us/cm, the pH of 7.3, the dielectric constant of 108, the dielectric loss of 0.0012 and the content of rutile crystal type titanium dioxide of 99.52%，H20.04% of O, loss on ignition: 0.05% and the particle size is D50:2.470 microns.
The viscosity of the resin composition is 8000cps, the viscosity is too high, the materials are difficult to disperse, and the copper-clad plate can not be manufactured.
Comparative example 28
The difference from example 2 is that commercially available amorphous rutile titanium dioxide is used, in a ratio of 2: 1 mass ratio, pressing into bonding sheets of 500 x 500mm x 5mm by using a mold, then using 5 bonding sheets and pasting copper foils on two sides, and pressing at the pressure of 50kg and the temperature of 385 ℃ to synthesize the copper-clad plate.
The viscosity of the resin composition is 900cps, the dielectric constant of the copper-clad plate is 6, the dielectric loss is 0.0024, compared with spherical rutile titanium dioxide, the filling amount of the commercially available amorphous rutile titanium dioxide is low, the dielectric constant of the copper-clad plate is not improved sufficiently, meanwhile, the rutile titanium dioxide is less, and the dielectric loss reduction effect of the material is general.
The present invention has been described in detail in order to enable those skilled in the art to understand the invention and to practice it, and it is not intended to limit the scope of the invention, and all equivalent changes and modifications made according to the spirit of the present invention should be covered by the present invention.
Claims (5)
1. A rutile titanium dioxide, characterized by: the spheroidization rate of the rutile titanium dioxide is more than or equal to 95%, the granularity D50 is 2-8 microns, the relative dielectric constant is 100-120, the dielectric loss is 0.0005-0.002, and TiO in the rutile titanium dioxide2The content of (A) is more than or equal to 98 wt%.
2. The rutile titanium dioxide of claim 1, wherein: the conductivity of the rutile titanium dioxide is less than or equal to 100 mu S/cm, and the pH value is 6-8.
3. A preparation method of rutile titanium dioxide is characterized in that: reacting tetraalkyl titanate with ammonia water in the presence of an organic nonpolar liquid solvent to form titanium dioxide, calcining the titanium dioxide at 100-200 ℃ for 1-3 h, calcining at 500-800 ℃ for 1-3 h, and calcining at 900-1400 ℃ for 3-8 h to obtain rutile titanium dioxide;
wherein the organic nonpolar liquid solvent is hexadecane, and the mass ratio of the tetraalkyl titanate to the organic nonpolar liquid solvent to the ammonia water is 3-15: 20-100: 1;
stirring the ammonia water and the organic nonpolar liquid solvent to form an emulsion, and then forming titanium dioxide by the emulsion and the tetraalkyl titanate, wherein the stirring speed is 1500-4000 rpm, and the stirring time is not less than 15 min;
the emulsion and the tetraalkyl titanate form titanium dioxide under the condition of stirring, the stirring speed is controlled to be 2000-4000 rpm, the stirring time is not less than 2 hours, the reaction temperature of the emulsion and the tetraalkyl titanate is controlled to be 100-300 ℃, and the pH of a reaction system is controlled to be 8-9.
4. The process for producing rutile titanium dioxide according to claim 3, wherein: the tetraalkyl titanate is tetrabutyl titanate.
5. Use of the rutile titanium dioxide according to any of claims 1 to 2 or of the rutile titanium dioxide obtained by the process according to claims 3 or 4 as a filler in copper-clad laminates.
Priority Applications (1)
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| CN113402774B (en) * | 2021-06-16 | 2022-09-02 | 山东国瓷功能材料股份有限公司 | Titanium dioxide filler with high dielectric property and application thereof in preparation of PTFE (polytetrafluoroethylene) high-frequency substrate |
| CN114409965B (en) * | 2022-01-19 | 2024-02-09 | 山东国瓷功能材料股份有限公司 | Functionalized titanium dioxide filler, preparation method thereof and PTFE (polytetrafluoroethylene) high-frequency copper-clad laminate |
| CN115818707A (en) * | 2022-12-02 | 2023-03-21 | 联瑞新材(连云港)有限公司 | Micron-sized spherical rutile titanium dioxide and preparation method and application thereof |
| CN115849438A (en) * | 2022-12-16 | 2023-03-28 | 联瑞新材(连云港)有限公司 | Micron-sized spherical rutile titanium dioxide and microfluidic preparation method thereof |
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