CN108299811B - Preparation method of calcium carbonate rod-shaped nanoparticle composite material - Google Patents
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Abstract
A preparation method of a calcium carbonate rod-shaped nanoparticle composite material comprises the following steps: dispersing calcium oxide particles in deionized water, adding a composite surfactant, uniformly stirring, treating feed liquid under microwave, introducing the feed liquid into a liquid inlet end of an atomizing nozzle, introducing carbon dioxide gas into a gas inlet end of the atomizing nozzle, spraying the feed liquid under an ultrasonic condition, carrying out centrifugal separation on the feed liquid by the number of revolutions, taking clear liquid, carrying out high-speed centrifugation, washing with deionized water, drying, and carrying out melt coextrusion on the obtained calcium carbonate rod-shaped nanoparticles and polycaprolactone to obtain the calcium carbonate rod-shaped nanoparticle composite material.
Description
Technical Field
The invention belongs to the field of calcium carbonate material preparation, and particularly relates to a method for preparing a calcium carbonate rod-shaped nanoparticle composite material.
Background
The calcium carbonate is widely used in the industries of rubber, plastics, coating, papermaking, printing ink, sizing agent DIAN, sealant and the like, and can also be applied to the industries of toothpaste, food, medicine, word materials, building materials, chemical fibers and the like. The crystal form of calcium carbonate includes three types of calcite, aragonite and vaterite, wherein the calcite structure is the most stable, and the aragonite and the vaterite are both unstable.
Calcium carbonate is an important plastic filler, the affinity of the calcium carbonate with a matrix polymer and the properties of the mechanical properties of filling modified materials are influenced by the particle size, the particle uniformity, the specific surface area and the surface state of the calcium carbonate, and how to obtain nano calcium carbonate which is easy to disperse, uniform in particle size and high in surface activity is still a goal pursued in the industry.
Disclosure of Invention
The technical scheme of the invention is to overcome the defects of the prior art and provide a method for preparing a calcium carbonate rodlike nano particle composite material.
The invention provides a preparation method of a calcium carbonate rodlike nano particle composite material, which comprises the following steps:
1) dispersing calcium oxide particles with the particle size of 1-1.5 mu m in deionized water, adding a composite surfactant, and uniformly stirring;
2) treating the feed liquid obtained in the step 1) for 40-50min under microwave;
3) introducing the feed liquid obtained in the step 2) into a liquid inlet end of an atomizing nozzle, introducing carbon dioxide gas into a gas inlet end of the atomizing nozzle, and spraying the feed liquid under an ultrasonic condition;
4) collecting the sprayed feed liquid, controlling the revolution of centrifugal separation, taking clear liquid, centrifuging at a high speed, washing for 2-3 times by deionized water, and drying to obtain calcium carbonate rod-like nanoparticles;
5) and melting and co-extruding the obtained calcium carbonate rod-shaped nano particles and polycaprolactone at the temperature of 140-160 ℃, wherein the weight of the nano particles accounts for 1-5 wt% of the weight of the polycaprolactone, and the calcium carbonate rod-shaped nano particle composite material is obtained.
Wherein the composite surfactant is prepared from dodecyl dimethyl benzyl ammonium chloride and dodecyl polyoxyethylene aminoacetic acid.
Wherein, the power of the microwave is 500-600W.
Wherein the mol ratio of the calcium oxide to the dodecyl dimethyl benzyl ammonium chloride and the dodecyl polyoxyethylene glycine is 1: 0.3-0.5: 0.2-0.5.
Wherein, in the step 1), the mass ratio of the calcium oxide to the deionized water is 1: 250-400.
Wherein, in the step 3), the feeding ratio of the feed liquid to the carbon dioxide is 1 g: 200-400 mL.
Wherein, in the step 4), the centrifugal rotation number is controlled to be 3000-5000 rpm.
Wherein, in the step 3), the ultrasonic power is 150-200W.
Wherein, in the step 4), the high-speed centrifugation rotation number is 6000-8000 rpm.
The invention adopts microwave condition to control the hydration of calcium oxide particles, so that calcium hydroxide is continuously formed on the surface layer of calcium oxide and is dissolved in aqueous solution, the composite surfactant reacts with calcium ions, and the calcium ions are induced to form rod-shaped nano particles in carbonization reaction. By regulating and controlling the microwave power and time, the hydration speed of calcium oxide particles in the solution can be regulated, and further the concentration of calcium ions in the solution can be regulated. Calcium hydroxide in the solution reacts with carbon dioxide under the condition of ultrasonic spraying, feed liquid is impacted and wrapped by a large amount of carbon dioxide gas under the condition of turbulent flow and is dispersed into tiny liquid drops by the carbon dioxide under the action of ultrasonic, and the ultrasonic promotes the gas-liquid phase material to react at the moment of contact, and is favorable for avoiding the agglomeration of particles in the reaction process. The composite surfactant is combined on the surface of the particles, so that the particles are stabilized, agglomeration is avoided, and simultaneously, the calcium carbonate is induced to form a rod shape.
The invention has the beneficial effects that: the method adopts the carbon dioxide as the gas for feed liquid atomization, and compared with the method of contacting with the carbon dioxide after atomization, the particle size of the obtained product is more uniform. The microwave activation is combined with the instantaneous reaction under ultrasonic spraying, so that the active points on the surface of the particles are more, the reaction is fast, the surface of the particles is uneven, and the specific surface area of the particles with the same size and appearance is obviously increased. The obtained calcium carbonate has a rod shape with a length of about 300-600nm, and the particles can be uniformly dispersed in the polycaprolactone. The addition amount of the particles is controlled, so that the aggregation of inorganic nanoparticles formed in an organic phase when the particles are excessive can be avoided, and the crystallization temperature of the polycaprolactone is increased from 35.2 ℃ to 38.4 ℃, thereby obviously improving the thermodynamic stability of the polycaprolactone.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
1) Dispersing calcium oxide particles with the particle size of 1 mu m in deionized water, adding a composite surfactant, and uniformly stirring; the mass ratio of the calcium oxide to the deionized water is 1: 250, and the molar ratio of the calcium oxide to the dodecyl dimethyl benzyl ammonium chloride and the dodecyl polyoxyethylene glycine is 1: 0.3: 0.2;
2) treating the feed liquid obtained in the step 1) for 40min under microwave with the microwave power of 500W;
3) introducing the feed liquid obtained in the step 2) into a liquid inlet end of an atomizing nozzle, introducing carbon dioxide gas into a gas inlet end of the atomizing nozzle, and spraying the feed liquid under an ultrasonic condition; the feeding ratio of the feed liquid to the carbon dioxide is 1 g: 200 mL;
4) collecting the sprayed feed liquid, controlling the revolution of centrifugal separation, taking clear liquid, centrifuging at high speed, washing for 2-3 times by deionized water, and drying to obtain calcium carbonate rodlike nanoparticles with the length of about 510nm and uniform particles;
5) and melting and co-extruding the obtained calcium carbonate rod-shaped nano particles and polycaprolactone at the temperature of 140-160 ℃, wherein the weight of the nano particles accounts for 1-5 wt% of the weight of the polycaprolactone, and the calcium carbonate rod-shaped nano particle composite material is obtained.
Example 2
1) Dispersing calcium oxide particles with the particle size of 1.5 mu m in deionized water, adding a composite surfactant, and uniformly stirring; the mass ratio of the calcium oxide to the deionized water is 1: 400, and the molar ratio of the calcium oxide to the dodecyl dimethyl benzyl ammonium chloride and the dodecyl polyoxyethylene glycine is 1: 0.5;
2) treating the feed liquid obtained in the step 1) for 50min under microwave with the microwave power of 600W;
3) introducing the feed liquid obtained in the step 2) into a liquid inlet end of an atomizing nozzle, introducing carbon dioxide gas into a gas inlet end of the atomizing nozzle, and spraying the feed liquid under an ultrasonic condition; the feeding ratio of the feed liquid to the carbon dioxide is 1 g: 400 mL;
4) collecting the sprayed feed liquid, controlling the revolution of centrifugal separation, taking clear liquid, centrifuging at high speed, washing for 2-3 times by deionized water, and drying to obtain calcium carbonate rodlike nanoparticles with the length of about 450nm and uniform particles;
5) and melting and co-extruding the obtained calcium carbonate rod-shaped nano particles and polycaprolactone at the temperature of 140-160 ℃, wherein the weight of the nano particles accounts for 1-5 wt% of the weight of the polycaprolactone, and the calcium carbonate rod-shaped nano particle composite material is obtained.
Example 3
1) Dispersing calcium oxide particles with the particle size of 2 mu m in deionized water, adding a composite surfactant, and uniformly stirring; the mass ratio of the calcium oxide to the deionized water is 1: 250, and the molar ratio of the calcium oxide to the dodecyl dimethyl benzyl ammonium chloride and the dodecyl polyoxyethylene glycine is 1: 0.3: 0.2;
2) treating the feed liquid obtained in the step 1) for 40min under microwave with the microwave power of 500W;
3) introducing the feed liquid obtained in the step 2) into a liquid inlet end of an atomizing nozzle, introducing carbon dioxide gas into a gas inlet end of the atomizing nozzle, and spraying the feed liquid under an ultrasonic condition; the feeding ratio of the feed liquid to the carbon dioxide is 1 g: 200 mL;
4) collecting the sprayed feed liquid, controlling the revolution of centrifugal separation, taking clear liquid, centrifuging at a high speed, washing for 2-3 times by deionized water, and drying to obtain calcium oxide/calcium carbonate core-shell nanoparticles;
5) and carrying out melt co-extrusion on the obtained nanoparticles and polycaprolactone at the temperature of 140-160 ℃, wherein the particles account for 1-5 wt% of the weight of the polycaprolactone, and thus obtaining the calcium carbonate nanoparticle composite material.
Example 4
1) Dispersing calcium oxide particles with the particle size of 1 mu m in deionized water, adding a composite surfactant, and uniformly stirring; the mass ratio of the calcium oxide to the deionized water is 1: 150, and the molar ratio of the calcium oxide to the dodecyl dimethyl benzyl ammonium chloride and the dodecyl polyoxyethylene glycine is 1: 0.3: 0.2;
2) treating the feed liquid obtained in the step 1) for 40min under microwave with the microwave power of 500W;
3) introducing the feed liquid obtained in the step 2) into a liquid inlet end of an atomizing nozzle, introducing carbon dioxide gas into a gas inlet end of the atomizing nozzle, and spraying the feed liquid under an ultrasonic condition; the feeding ratio of the feed liquid to the carbon dioxide is 1 g: 200 mL;
4) collecting the sprayed feed liquid, controlling the revolution of centrifugal separation, taking clear liquid, centrifuging at high speed, washing for 2-3 times with deionized water, and drying;
5) and melting and co-extruding the obtained particles and polycaprolactone at the temperature of 140-160 ℃, wherein the particles account for 1-5 wt% of the weight of the polycaprolactone, and the calcium carbonate particle composite material is obtained.
Example 5
1) Dispersing calcium oxide particles with the particle size of 1 mu m in deionized water, adding a composite surfactant, and uniformly stirring; the mass ratio of the calcium oxide to the deionized water is 1: 500, and the molar ratio of the calcium oxide to the dodecyl dimethyl benzyl ammonium chloride and the dodecyl polyoxyethylene glycine is 1: 0.3: 0.2;
2) treating the feed liquid obtained in the step 1) for 40min under microwave with the microwave power of 500W;
3) introducing the feed liquid obtained in the step 2) into a liquid inlet end of an atomizing nozzle, introducing carbon dioxide gas into a gas inlet end of the atomizing nozzle, and spraying the feed liquid under an ultrasonic condition; the feeding ratio of the feed liquid to the carbon dioxide is 1 g: 200 mL;
4) collecting the sprayed feed liquid, controlling the revolution of centrifugal separation, taking clear liquid, centrifuging at high speed, washing for 2-3 times with deionized water, and drying;
5) and melting and co-extruding the obtained particles and polycaprolactone at the temperature of 140-160 ℃, wherein the particles account for 1-5 wt% of the weight of the polycaprolactone, and the calcium carbonate particle composite material is obtained.
Example 6
1) Dispersing calcium oxide particles with the particle size of 1 mu m in deionized water, adding a composite surfactant, and uniformly stirring; the mass ratio of the calcium oxide to the deionized water is 1: 250, and the molar ratio of the calcium oxide to the dodecyl dimethyl benzyl ammonium chloride and the dodecyl polyoxyethylene glycine is 1: 0.3: 0.2;
2) treating the feed liquid obtained in the step 1) for 40min under microwave, wherein the microwave power is 400W;
3) introducing the feed liquid obtained in the step 2) into a liquid inlet end of an atomizing nozzle, introducing carbon dioxide gas into a gas inlet end of the atomizing nozzle, and spraying the feed liquid under an ultrasonic condition; the feeding ratio of the feed liquid to the carbon dioxide is 1 g: 200 mL;
4) collecting the sprayed feed liquid, controlling the revolution of centrifugal separation, taking clear liquid, centrifuging at high speed, washing for 2-3 times with deionized water, and drying;
5) and melting and co-extruding the obtained particles and polycaprolactone at the temperature of 140-160 ℃, wherein the particles account for 1-5 wt% of the weight of the polycaprolactone, and the calcium carbonate particle composite material is obtained.
Example 7
1) Dispersing calcium oxide particles with the particle size of 1 mu m in deionized water, adding a composite surfactant, and uniformly stirring; the mass ratio of the calcium oxide to the deionized water is 1: 250, and the molar ratio of the calcium oxide to the dodecyl dimethyl benzyl ammonium chloride and the dodecyl polyoxyethylene glycine is 1: 0.3: 0.2;
2) treating the feed liquid obtained in the step 1) for 40min under microwave, wherein the microwave power is 700W;
3) introducing the feed liquid obtained in the step 2) into a liquid inlet end of an atomizing nozzle, introducing carbon dioxide gas into a gas inlet end of the atomizing nozzle, and spraying the feed liquid under an ultrasonic condition; the feeding ratio of the feed liquid to the carbon dioxide is 1 g: 200 mL;
4) collecting the sprayed feed liquid, controlling the revolution of centrifugal separation, taking clear liquid, centrifuging at high speed, washing for 2-3 times with deionized water, and drying;
5) and melting and co-extruding the obtained particles and polycaprolactone at the temperature of 140-160 ℃, wherein the particles account for 1-5 wt% of the weight of the polycaprolactone, and the calcium carbonate particle composite material is obtained.
Example 8
1) Dispersing calcium oxide particles with the particle size of 1 mu m in deionized water, adding a composite surfactant, and uniformly stirring; the mass ratio of the calcium oxide to the deionized water is 1: 250, and the molar ratio of the calcium oxide to the dodecyl dimethyl benzyl ammonium chloride and the dodecyl polyoxyethylene glycine is 1: 0.3: 0.2;
2) treating the feed liquid obtained in the step 1) for 30min under microwave with the microwave power of 500W;
3) introducing the feed liquid obtained in the step 2) into a liquid inlet end of an atomizing nozzle, introducing carbon dioxide gas into a gas inlet end of the atomizing nozzle, and spraying the feed liquid under an ultrasonic condition; the feeding ratio of the feed liquid to the carbon dioxide is 1 g: 200 mL;
4) collecting the sprayed feed liquid, controlling the revolution of centrifugal separation, taking clear liquid, centrifuging at high speed, washing for 2-3 times with deionized water, and drying;
5) and melting and co-extruding the obtained particles and polycaprolactone at the temperature of 140-160 ℃, wherein the particles account for 1-5 wt% of the weight of the polycaprolactone, and the calcium carbonate particle composite material is obtained.
Example 9
1) Dispersing calcium oxide particles with the particle size of 1 mu m in deionized water, adding a composite surfactant, and uniformly stirring; the mass ratio of the calcium oxide to the deionized water is 1: 250, and the molar ratio of the calcium oxide to the dodecyl dimethyl benzyl ammonium chloride and the dodecyl polyoxyethylene glycine is 1: 0.3: 0.2;
2) treating the feed liquid obtained in the step 1) for 40min under microwave with the microwave power of 500W;
3) introducing the feed liquid obtained in the step 2) into a liquid inlet end of an atomizing nozzle, introducing carbon dioxide gas into a gas inlet end of the atomizing nozzle, and spraying the feed liquid under an ultrasonic condition; the feeding ratio of the feed liquid to the carbon dioxide is 1 g: 100 mL;
4) collecting the sprayed feed liquid, controlling the revolution of centrifugal separation, taking clear liquid, centrifuging at high speed, washing for 2-3 times with deionized water, and drying;
5) and melting and co-extruding the obtained particles and polycaprolactone at the temperature of 140-160 ℃, wherein the particles account for 1-5 wt% of the weight of the polycaprolactone, and the calcium carbonate particle composite material is obtained.
Example 10
1) Dispersing calcium oxide particles with the particle size of 1 mu m in deionized water, adding a composite surfactant, and uniformly stirring; the mass ratio of the calcium oxide to the deionized water is 1: 250, and the molar ratio of the calcium oxide to the dodecyl dimethyl benzyl ammonium chloride and the dodecyl polyoxyethylene glycine is 1: 0.3: 0.2;
2) treating the feed liquid obtained in the step 1) for 40min under microwave with the microwave power of 500W;
3) introducing the feed liquid obtained in the step 2) into a liquid inlet end of an atomizing nozzle, introducing carbon dioxide gas into a gas inlet end of the atomizing nozzle, and spraying the feed liquid under an ultrasonic condition; the feeding ratio of the feed liquid to the carbon dioxide is 1 g: 500 mL;
4) collecting the sprayed feed liquid, controlling the revolution of centrifugal separation, taking clear liquid, centrifuging at high speed, washing for 2-3 times with deionized water, and drying;
5) and melting and co-extruding the obtained particles and polycaprolactone at the temperature of 140-160 ℃, wherein the particles account for 1-5 wt% of the weight of the polycaprolactone, and the calcium carbonate particle composite material is obtained.
Example 11
1) Dispersing calcium oxide particles with the particle size of 1 mu m in deionized water, adding a composite surfactant, and uniformly stirring; the mass ratio of the calcium oxide to the deionized water is 1: 250, and the molar ratio of the calcium oxide to the dodecyl dimethyl benzyl ammonium chloride and the dodecyl polyoxyethylene glycine is 1: 0.1: 0.2;
2) treating the feed liquid obtained in the step 1) for 40min under microwave with the microwave power of 500W;
3) introducing the feed liquid obtained in the step 2) into a liquid inlet end of an atomizing nozzle, introducing carbon dioxide gas into a gas inlet end of the atomizing nozzle, and spraying the feed liquid under an ultrasonic condition; the feeding ratio of the feed liquid to the carbon dioxide is 1 g: 200 mL;
4) collecting the sprayed feed liquid, controlling the revolution of centrifugal separation, taking clear liquid, centrifuging at high speed, washing for 2-3 times with deionized water, and drying;
5) and melting and co-extruding the obtained particles and polycaprolactone at the temperature of 140-160 ℃, wherein the particles account for 1-5 wt% of the weight of the polycaprolactone, and the calcium carbonate particle composite material is obtained.
Example 12
1) Dispersing calcium oxide particles with the particle size of 1 mu m in deionized water, adding a composite surfactant, and uniformly stirring; the mass ratio of the calcium oxide to the deionized water is 1: 250, and the molar ratio of the calcium oxide to the dodecyl dimethyl benzyl ammonium chloride and the dodecyl polyoxyethylene glycine is 1: 0.7: 0.2;
2) treating the feed liquid obtained in the step 1) for 40min under microwave with the microwave power of 500W;
3) introducing the feed liquid obtained in the step 2) into a liquid inlet end of an atomizing nozzle, introducing carbon dioxide gas into a gas inlet end of the atomizing nozzle, and spraying the feed liquid under an ultrasonic condition; the feeding ratio of the feed liquid to the carbon dioxide is 1 g: 200 mL;
4) collecting the sprayed feed liquid, controlling the revolution of centrifugal separation, taking clear liquid, centrifuging at high speed, washing for 2-3 times with deionized water, and drying;
5) and melting and co-extruding the obtained particles and polycaprolactone at the temperature of 140-160 ℃, wherein the particles account for 1-5 wt% of the weight of the polycaprolactone, and the calcium carbonate particle composite material is obtained.
Example 13
1) Dispersing calcium oxide particles with the particle size of 1 mu m in deionized water, adding a composite surfactant, and uniformly stirring; the mass ratio of the calcium oxide to the deionized water is 1: 250, and the molar ratio of the calcium oxide to the dodecyl dimethyl benzyl ammonium chloride and the dodecyl polyoxyethylene glycine is 1: 0.3: 0.1;
2) treating the feed liquid obtained in the step 1) for 40min under microwave with the microwave power of 500W;
3) introducing the feed liquid obtained in the step 2) into a liquid inlet end of an atomizing nozzle, introducing carbon dioxide gas into a gas inlet end of the atomizing nozzle, and spraying the feed liquid under an ultrasonic condition; the feeding ratio of the feed liquid to the carbon dioxide is 1 g: 200 mL;
4) collecting the sprayed feed liquid, controlling the revolution of centrifugal separation, taking clear liquid, centrifuging at high speed, washing for 2-3 times with deionized water, and drying;
5) and melting and co-extruding the obtained particles and polycaprolactone at the temperature of 140-160 ℃, wherein the particles account for 1-5 wt% of the weight of the polycaprolactone, and the calcium carbonate particle composite material is obtained.
Example 14
1) Dispersing calcium oxide particles with the particle size of 1 mu m in deionized water, adding a composite surfactant, and uniformly stirring; the mass ratio of the calcium oxide to the deionized water is 1: 250, and the molar ratio of the calcium oxide to the dodecyl dimethyl benzyl ammonium chloride and the dodecyl polyoxyethylene glycine is 1: 0.3: 0.7;
2) treating the feed liquid obtained in the step 1) for 40min under microwave with the microwave power of 500W;
3) introducing the feed liquid obtained in the step 2) into a liquid inlet end of an atomizing nozzle, introducing carbon dioxide gas into a gas inlet end of the atomizing nozzle, and spraying the feed liquid under an ultrasonic condition; the feeding ratio of the feed liquid to the carbon dioxide is 1 g: 200 mL;
4) collecting the sprayed feed liquid, controlling the revolution of centrifugal separation, taking clear liquid, centrifuging at high speed, washing for 2-3 times with deionized water, and drying;
5) and melting and co-extruding the obtained particles and polycaprolactone at the temperature of 140-160 ℃, wherein the particles account for 1-5 wt% of the weight of the polycaprolactone, and the calcium carbonate particle composite material is obtained.
The morphology of the calcium carbonate particles obtained in examples 1 to 14 is shown in Table 1.
TABLE 1
Example 15
The process and parameters of example 1 were used, and only the carrier gas for ultrasonic atomization in example 1 was replaced with nitrogen gas, and the atomized liquid was brought into countercurrent contact with carbon dioxide gas. The calcium carbonate particles obtained were non-uniformly sized particles.
The calcium carbonate particles obtained in examples 3 to 15 were not uniformly dispersed in polycaprolactone due to non-uniformity of the particles, and were not effective in increasing the crystallization temperature and thermodynamic stability of polycaprolactone.
Claims (5)
1. The preparation method of the calcium carbonate rod-shaped nano particle composite material is characterized by comprising the following steps of:
1) dispersing calcium oxide particles with the particle size of 1-1.5 mu m in deionized water, adding a composite surfactant, and uniformly stirring;
2) treating the feed liquid obtained in the step 1) for 40-50min under microwave;
3) introducing the feed liquid obtained in the step 2) into a liquid inlet end of an atomizing nozzle, introducing carbon dioxide gas into a gas inlet end of the atomizing nozzle, and spraying the feed liquid under an ultrasonic condition;
4) collecting the sprayed feed liquid, controlling the revolution of centrifugal separation, taking clear liquid, centrifuging at a high speed, washing for 2-3 times by deionized water, and drying to obtain calcium carbonate rod-like nanoparticles;
5) melting and co-extruding the obtained calcium carbonate rod-shaped nano particles and polycaprolactone at the temperature of 140-160 ℃, wherein the weight of the nano particles accounts for 1-5 wt% of the weight of the polycaprolactone, so as to obtain a calcium carbonate rod-shaped nano particle composite material;
the composite surfactant consists of dodecyl dimethyl benzyl ammonium chloride and dodecyl polyoxyethylene aminoacetic acid;
the power of the microwave is 500-600W;
the mol ratio of the calcium oxide to the dodecyl dimethyl benzyl ammonium chloride and the dodecyl polyoxyethylene amino acetic acid is 1: 0.3-0.5: 0.2-0.5;
in the step 3), the feeding ratio of the feed liquid to the carbon dioxide is 1 g: 200 and 400 mL.
2. The method of claim 1, wherein: in the step 1), the mass ratio of the calcium oxide to the deionized water is 1: 250-400.
3. The method of claim 1, wherein: in the step 4), the centrifugal rotation number is controlled to be 3000-.
4. The method of claim 1, wherein: in the step 3), the ultrasonic power is 150-.
5. The method of claim 1, wherein: in the step 4), the high-speed centrifugation rotation number is 6000-.
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