Modification method of spherical silicon dioxide and ball milling equipment

Abstract

The invention discloses a spherical silicon dioxide modification method and ball milling equipment, and belongs to the technical field of new material production, the spherical silicon dioxide modification method is characterized by comprising the following steps: step a, adding grinding beads into a grinding cavity; b, a solvent is added into the grinding cavity; c, adding silicon dioxide powder into the grinding cavity; step d, adding a modifier into the grinding cavity or compounding a plurality of modifiers for use; e, the reaction temperature of the grinding machine is 0-60 DEG C; f, filtering the ground pulp by a filter screen; and g, recycling the solvent of the filtered pulp by a rotary evaporator. The modified spherical silicon dioxide is lower in production cost and better in hydrophobicity, and is mainly applied to advanced packaging technologies such as DAF and CUF.

Description

Technical Field

[0001] The invention relates to the technical field of new material production, in particular to a modification method of spherical silicon dioxide and a ball milling device. Background Art

[0002] With the rapid development of electronic packaging technology, the market's requirements for packaging materials are constantly increasing, and silica as a packaging filler directly affects the packaging effect. In recent years, more and more research has focused on the modification of nano-silica to improve the hydrophobicity and dispersibility of the material, but the modification steps are complicated, the process is cumbersome, and the conditions are harsh, which is not conducive to the needs of industrialization.

[0003] The invention patent with patent publication number CN111422877A discloses a method for preparing nano-silicon dioxide and a surface modification method. Silicon dioxide is prepared using tetraethyl orthosilicate as a raw material, and then methacryloxypropyltrimethoxysilane (MPS) is added to the dispersion to react at a high temperature to obtain modified nano-silicon dioxide. However, the modification time is long, the steps are complicated, and the subsequent powder still needs to be ground and separated before use.

[0004] The invention patent with the patent publication number CN104860320B discloses a method for preparing modified nano-silica, which uses chitosan to reduce the agglomeration of silica during the nucleation process; secondly, disodium ethylenediaminetetraacetic acid is used to modify a small amount of amino groups on the surface of silica; finally, tin dichloride is used to increase the reactivity of silanol and silanol amino groups, accelerate the reaction process, and thus increase the grafting rate. However, the modification cost is high and the modification process is complicated.

[0005] The invention patent with the patent publication number JP2000256008A discloses a method for preparing hydrophobic silica, which uses mechanical pulverization to hydrophobize fumed silica, or re-hydrophobizes it while pulverizing it, to obtain highly hydrophobic silica. However, this method requires secondary modification of the powder, which is cumbersome and costly.

[0006] The purpose of the present invention is to provide a method for preparing modified silicon dioxide with controllable cost, high reaction efficiency, simple steps and environmental protection. A ball mill is used as a reaction device to modify the powder while dispersing it, and the solvent is recycled and reused by reacting the modifier with the hydroxyl group on the surface of the powder, thereby reducing the production cost. Summary of the invention

[0007] In order to solve the technical problems mentioned in the background technology, the present invention performs mechanochemical modification on the liquid-phase synthesized silicon dioxide, and fully disperses the powder during the modification. The technical solution adopted is as follows:

[0008] Step a: mixing the ground spherical silica and the solvent, an organic reagent having a boiling point lower than 150° C., and a compound solution by mechanical stirring;

[0009] Step b: Add slurry to the grinding chamber and start the equipment. After the equipment runs stably, set the reaction temperature of the grinder to 0-60°C. Control the grinding temperature so that the temperature change in the grinding chamber is less than 3°C / min. Start grinding after the temperature stabilizes. Use a peristaltic pump, diaphragm pump or other equipment that can transfer slurry to add the ultrasonically stirred and dispersed slurry to the grinding chamber.

[0010] Step c: Add silazane or other modifiers and compound modifiers to the grinding chamber for use. The modifiers are quantitatively added to the grinding chamber in batches. The modifiers are quantitatively added to the grinding chamber in batches using a peristaltic pump or other equipment. The modifiers are added in 1-4 times, and the effect is better when added in 2-3 times. In addition, the compound modifier can be added in sequence, such as using silazane alone for modification for the first time. After grinding, fluorinated silicone oil is added to the grinding chamber for modification.

[0011] The amount of modifier added is calculated based on the number of surface hydroxyl groups according to the formula in patent CN111094184A. Silazane is a fixed modifier in the modifier, and other modifiers include silane coupling agent, silazane coupling agent, silicone oil, fluorinated silicone oil, halogenated alkane compounds with large steric hindrance such as benzene and naphthalene, etc.

[0012] Step d: Take a small amount of slurry every 5 minutes for particle size monitoring. When the equipment setting time is reached and no micron-sized particles are found in the test, the grinding is completed. There are many methods for particle size monitoring, including fineness plate, nanoparticle size analyzer, particle counter and other equipment for monitoring.

[0013] Step e: The slurry after grinding is filtered using a filter element, and the filtered slurry is separated into solid and liquid. The separation methods include centrifugation, filter filtration, rotary evaporation, etc., and the effect is better when rotary evaporation is used.

[0014] Preferably: in order to achieve a better modification effect, after the silicon dioxide and the solvent are evenly mixed in step a, the stirring speed is set to 200 rpm-1500 rpm, and all stirring is performed under ultrasonic conditions.

[0015] Preferably: in order to achieve better modification effect, the particle size of the silicon dioxide in step a is 0.01-1 μm, preferably 0.01-0.5 μm, and more preferably 0.01-0.15 μm.

[0016] Preferably, the boiling point of the organic reagent in step a is lower than 105°C, and lower alcohols, ethyl acetate or other organic reagents with a boiling point lower than 105°C can be selected as needed.

[0017] Preferably: in order to achieve better modification effect, the ultrasonic frequency is 25KHZ-130KHZ, and the grinding speed is 3-18m / s.

[0018] A novel ball milling device comprises a supporting body, a frame, a control cabinet, a driving motor and a grinding chamber. The control cabinet is provided with a controller, the supporting body is installed with a frame, a driving motor is arranged in the frame, the driving motor is used to provide power to the device, a pulley a is arranged on the output shaft of the driving motor, the pulley a is fixedly connected with the pulley b, a supporting frame is arranged on the frame, and a grinding chamber is arranged on the supporting frame.

[0019] The main improvements of the above equipment are as follows: the grinding chamber includes a cover plate, which is provided with a feed port and a detection port, the cover plate is sealed and connected to the shell, a stirring and mixing device is provided in the shell, and the stirring and mixing device is used to improve the mixing effect, the stirring and mixing device includes a cylindrical stirring assembly, the upper part of the cylindrical stirring assembly is fixedly connected to the rotating shaft a, a cylindrical through hole is provided in the rotating shaft a, a plurality of sealed bearings are provided in the cylindrical through hole, the sealed bearing is movably connected to the rotating shaft b, a screw is provided at the lower part of the rotating shaft b, the lower part of the screw is fixedly connected to the stirring blade, the upper part of the rotating shaft a is connected to the pulley c, the upper part of the rotating shaft b is connected to the pulley d, the pulley a is connected to the pulley c by a belt, and the pulley b is connected to the pulley d by a belt, a cylindrical cavity is provided in the middle of the cylindrical stirring assembly, a screw is provided in the cylindrical cavity, a plurality of diversion channels are provided on the cylindrical stirring assembly, the diversion channels are connected to the cylindrical cavity, a plurality of stirring rods are provided outside the cylindrical stirring assembly, and a discharge port is provided at the lower part of the shell.

[0020] The working principle of the above device is as follows:

[0021] The slurry is added into the grinding chamber, and the driving motor drives pulley a to rotate, which drives pulley c to rotate, which drives rotating shaft a to rotate, which drives pulley b to rotate, which drives pulley d to rotate, which drives rotating shaft b to rotate, which drives the screw to rotate and transport the slurry upward, and the slurry is diverted and output from the diversion channel, thereby achieving a fully mixed diversion effect.

[0022] Preferably, in order to achieve a better diversion and mixing effect, a diversion cap is provided outside the diversion channel, and the slurry is dispersed by contacting the diversion cap to achieve better diversion and mixing.

[0023] Preferably: in order to better control the temperature of the device, an inner cavity is provided in the shell, and the inner cavity is respectively connected with the water inlet and the water outlet.

[0024] Preferably: in order to achieve a better modification effect, in step a, 20%-40% by volume of grinding beads are added to the grinding chamber, and the particle size of the grinding beads is 0.1 mm-0.6 mm.

[0025] Preferably: in order to achieve better modification effect, the amount of siloxane added in step b is 40%-60% of the volume of the grinding chamber. Preferably: in order to achieve better modification effect, the amount of silicon dioxide powder added in step c is 15%-50% of the weight of siloxane.

[0026] Preferably: in order to achieve a better modification effect, the amount of the modifier added in step d is 0.5-6 times the number of hydroxyl groups on the surface of the silicon dioxide.

[0027] Preferably: in order to achieve better modification effect, the grinding time in step e is 15 min-4 h.

[0028] Preferably: in order to achieve a better modification effect, the specification of the filter in step f is 1-5 μm, the filtered slurry is used to recover the solvent through a rotary evaporator, and the liquid after rotary evaporation is measured by GC (Gas chromatograph) to measure the content of silazane. The content of silazane in the solution is 0.05%-1.5%. The solvent is recycled according to the test results, and the solvent recovery rate can reach more than 90%.

[0029] Preferably: in order to achieve a better modification effect, the temperature of the rotary evaporation in step g is 50-120°C, and the vacuum degree is 95-98 kPa. The powder aggregates due to the rotary evaporation drying, and the powder is not easy to spray. The hydroxyl content of the surface of the highly surface-treated silicon dioxide is greatly reduced, and the number of hydroxyl groups is less than 0.8 / nm. 2 , the powder shrinks after drying and its cohesion becomes weaker, making it easy to disperse in the resin.

[0030] The powder modified by the present invention has a good hydrophobic effect. The hydrophobicity is tested by a methanol titration method, and the hydrophobicity range is between 55 and 70. Since the surface of the modified powder has fewer hydroxyl groups, the dielectric constant is lower than 3.2.

[0031] The modification method of the present invention utilizes the hydroxyl groups on the surface of silicon dioxide to react with the modifier, thereby making the powder have a better hydrophobic effect. Compared with the existing scheme, it has the following beneficial effects:

[0032] 1. This method uses a customized ball mill as the modification equipment, and the dispersion effect is better than that of the traditional ball mill. By using a professional ball mill, the powder can be fully separated and reacted with the modifier, thereby increasing the reaction rate, and the powder does not need to be dispersed again later.

[0033] 2. This method utilizes the reaction between the modifier and the hydroxyl group on the surface of the powder to generate the solvent required for the raw material mixing, and the solvent can be recovered and reused through a rotary evaporator. The liquid after solid-liquid separation is recovered and collected and reused.

[0034] The collected solvent is tested by Gas chromatograph to detect the content of the modifier in the solution. If the content of the modifier is insufficient, it is added. If it is sufficient, there is no need to add it again.

[0035] 3. The temperature requirement during the reaction of this method is obtained through the heat generated by high-speed grinding, without the need for an additional heat source, thus reducing costs.

[0036] 4. This method reduces and simplifies the process flow and improves production efficiency;

[0037] 5. This method has a high degree of automated production, stable product performance and good repeatability.

[0038] 6. After wet grinding, silica powder has good hydrophobicity and is easily dispersed in the resin. It can be used in advanced packaging technologies such as DAF and CUF. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 This is an internal structure diagram of a novel ball milling device of the present invention;

[0040] Figure 2 for Figure 1 A local enlarged view of point A;

[0041] Figure 3 A stirring and mixing device structure of a new type of ball mill equipment of the present invention Figure 1 ;

[0042] Figure 4 A stirring and mixing device structure of a new type of ball mill equipment of the present invention Figure 2 ; Figure 5 for Figure 4 A partial enlarged view of point B.

[0043] In the figure: 1 supporting body; 2 control cabinet; 3 controller; 4 driving motor; 5 pulley a; 6 pulley b; 7 housing; 7-1 feed inlet; 7-2 water inlet; 7-3 water outlet; 7-4 discharge outlet; 7-5 inner cavity; 7-6 detection port; 8 rotating shaft b; 8-1 screw; 8-2 stirring blade; 9 cylindrical through hole; 10 cylindrical stirring assembly; 10-1 stirring rod; 10-2 diversion channel; 10-3 diversion cap; 11 supporting frame; 12 frame; 13 cover plate. DETAILED DESCRIPTION

[0044] The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

[0045] Example 1

[0046] This experimental example provides a method for preparing hydrophobic silica, comprising the following steps:

[0047] Step 1: Add 0.45 L of 0.1 mm grinding beads into the grinding chamber of the special ball mill of the present invention, and then add 0.4 L of HMDSO into the grinding chamber. Add 61 g of 10 nm silica particles into the grinding chamber, and then start stirring for 30 min.

[0048] Step 2: Add 0.6 g of modifier HMDS to the uniformly mixed system in the grinding chamber, set the sand mill temperature to 40° C., the grinding speed to 3 m / s, and keep stirring for 30 min.

[0049] Step 3: Transfer the stirred system to a rotary evaporator, set the temperature to 90°C and the vacuum degree to 95 kPa, recover the solvent, and obtain the modified powder.

[0050] Example 2

[0051] This experimental example provides a method for preparing hydrophobic silica, comprising the following steps:

[0052] Step 1: Add 0.45 L of 0.1 mm grinding beads into the grinding chamber of a common ball mill, and then add 0.4 L of trimethoxysilane into the grinding chamber. Add 61 g of 10 nm silica particles into the grinding chamber, and then start stirring for 30 minutes.

[0053] Step 2: Add 0.6 g of modifier HMDS to the uniformly mixed system in the grinding chamber, set the sand mill temperature to 40° C., the grinding speed to 3 m / s, and keep stirring for 30 min.

[0054] Step 3: Transfer the stirred system to a rotary evaporator, set the temperature to 60°C and the vacuum degree to 95 kPa, recover the solvent, and obtain the modified powder.

[0055] Example 3

[0056] Step 1: Add 0.45 L of 0.1 mm grinding beads into the grinding chamber of the special ball mill of the present invention, and then add 0.4 L of trimethoxysilane into the grinding chamber. Add 61 g of 50 nm silica particles into the grinding chamber, and then start stirring for 40 minutes.

[0057] Step 2: Add 1.2 g of dodecyltrimethylsilane, a modifier, to the uniformly mixed system in the grinding chamber, set the sand mill temperature to 40° C., the grinding speed to 3 m / s, and keep stirring for 30 min.

[0058] Step 3: Transfer the stirred system to a rotary evaporator, set the temperature to 60°C and the vacuum degree to 95 kPa, recover the solvent, and obtain the modified powder.

[0059] Example 4

[0060] Step 1: Add 0.45 L of 0.1 mm grinding beads into the grinding chamber of a common ball mill, and then add 0.4 L of HMDSO into the grinding chamber. Add 61 g of 50 nm silica particles into the grinding chamber, and then start stirring for 40 min.

[0061] Step 2: Add 1.2 g of HMDS and a 1:1 composite modifier of dodecyltrimethylsilane to the uniformly mixed system in the grinding chamber, set the sand mill temperature to 40° C., the grinding speed to 6 m / s, and keep stirring for 30 min.

[0062] Step 3: Transfer the stirred system to a rotary evaporator, set the temperature to 90°C and the vacuum degree to 95 kPa, recover the solvent, and obtain the modified powder.

[0063] Example 5

[0064] Step 1: Add 0.45 L of 0.1 mm grinding beads into the grinding chamber of a common grinding equipment, and then add 0.4 L of acetone into the grinding chamber. Add 61 g of 100 nm silica particles into the grinding chamber, and then start stirring for 20 minutes.

[0065] Step 2: Add 1.2 g of the modifier phenyltrimethoxysilane to the uniformly mixed system in the grinding chamber, set the sand mill temperature to 60° C., the grinding speed to 12 m / s, and keep stirring for 30 min.

[0066] Step 3: Transfer the stirred system to a rotary evaporator, set the temperature to 60°C and the vacuum degree to 95 kPa, recover the solvent, and obtain the modified powder.

[0067] Example 6

[0068] Step 1: Add 0.45 L of 0.1 mm grinding beads into the grinding chamber of a common grinding equipment, and then add 0.4 L of a 1:1 mixed solution of methanol and HMDSO into the grinding chamber. Add 61 g of 500 nm silica particles into the grinding chamber, and then start stirring for 40 minutes.

[0069] Step 2: Add 2.4 g of the modifier phenyltrimethoxysilane to the uniformly mixed system in the grinding chamber, set the sand mill temperature to 60° C., the grinding speed to 12 m / s, and keep stirring for 30 min.

[0070] Step 3: Transfer the stirred system to a rotary evaporator, set the temperature to 60°C and the vacuum degree to 95 kPa, recover the solvent, and obtain the modified powder.

[0071] Example 7

[0072] Step 1: Add 0.45 L of 0.1 mm grinding beads into the grinding chamber of a common grinding equipment, and then add 0.4 L of butanone into the grinding chamber. Add 122 g of 1 μm silica particles into the grinding chamber, and then start stirring for 10 minutes.

[0073] Step 2: Add 4 g of the modifier phenyltrimethoxysilane to the uniformly mixed system in the grinding chamber, set the sand mill temperature to 60° C., the grinding speed to 18 m / s, and keep stirring for 30 min.

[0074] Step 3: Transfer the stirred system to a rotary evaporator, set the temperature to 90°C and the vacuum degree to 95 kPa, recover the solvent, and obtain the modified powder.

[0075] Comparative Example 1

[0076] The preparation method of the modified powder imported from abroad is as follows: commercially available silicon dioxide is used as a raw material. 100 parts by weight of silicon dioxide is placed in a mixer, stirred and passed through nitrogen, heated to 250°C and kept for 30 minutes. The mixer is then sealed, and 20 parts by weight of silane coupling agent A is sprayed into the mixer using a single-fluid nozzle. It is then stirred for 60 minutes. Then, nitrogen is passed through again and water vapor is introduced into the mixer to replace about 60% of the nitrogen, the mixer is sealed, and 30 parts by weight of hexamethyldisilazane (HMDS) are sprayed and stirred for 30 minutes for hydrophobic treatment.

[0077] Comparative Example 2

[0078] The preparation method of domestic hydrophobic modified powder is as follows: ① Add 100 parts by weight of silicon dioxide to the mixer and mix, atomize 1.5 parts by weight of hydrophobic modifier A and spray it evenly into the mixer, and keep stirring for 50 minutes; ② Atomize 1.0 parts by weight of hydrophobic modifier B and spray it into the mixer, and keep stirring for 2 hours; ③ After the mixing is completed, the material is aged at 85°C for 8 hours. After the aging is completed, it is ultra-finely crushed to obtain the finished product.

[0079] Verification of hydrophobic effect: 500mL beaker, with 100mL deionized water inside, take 0.5g of modified silica product, float on the water surface, and titrate methanol into the beaker while stirring the water with magnetic force. Compare the hydrophobic effect according to the amount of methanol titrated. After the methanol is titrated, the powder in the system is dissolved in the water, and the titration is completed when there is no powder on the surface of the water. Count the methanol titration amount and use the formula:

[0080]

[0081] The greater the hydrophobicity, the better the hydrophobic effect.

[0082] Appearance Particle size Hydrophobicity Example 1 Fluffy powder without agglomeration 10nm 69 Example 2 Fluffy powder without agglomeration 10nm 66 Example 3 Fluffy powder without agglomeration 50nm 68 Example 4 Fluffy powder without agglomeration 50nm 66 Example 5 Fluffy powder without agglomeration 100nm 65 Example 6 Fluffy powder without agglomeration 500nm 66 Example 7 Fluffy powder without agglomeration 1μm 60 Comparative Example 1 The powder is fluffy with slight agglomeration 120nm 54 Comparative Example 2 The powder is fluffy with slight agglomeration 80nm 55

[0083] In summary, the modified silica obtained in Examples 1-7 of the present invention has good hydrophobicity in powder, and the powder is fluffy and free of agglomerates. When the special grinding equipment of the present invention is used, the hydrophobicity is even better.

[0084] Finally, the method of the present invention is only a preferred embodiment and is not intended to limit the protection scope of the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

[0085] In addition, it should be understood that although the present specification is described according to implementation modes, not every implementation mode contains only one independent technical solution. This description of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment may also be appropriately combined to form other implementation modes that can be understood by those skilled in the art.

Claims

1. A method for modifying spherical silicon dioxide, characterized in that: The following steps are involved: Step a: mixing spherical silica and a solvent by mechanical stirring, wherein the solvent is siloxane or a composite solution of siloxane and other organic reagents; Step b: Add slurry into the grinding chamber and start the equipment. After the equipment runs stably, set the reaction temperature of the grinder to between 0 and 60°C. Control the grinding temperature so that the temperature change of the grinding chamber is less than 3°C / min. Start grinding after the temperature stabilizes. Step c: adding silazane or other modifiers and compound modifiers to the grinding chamber for use, the modifiers are quantitatively added to the grinding chamber in batches, and the modifiers are added to the grinding chamber in sequence according to actual needs; Step d: Take a small amount of slurry at intervals for particle size monitoring. When the equipment setting time is reached and the particle size is within 2 times the target median particle size, the grinding is completed. The interval time is 5-10 minutes; Step e: filtering the slurry after grinding with a filter element, and performing solid-liquid separation on the filtered slurry, wherein the solid-liquid separation method includes but is not limited to centrifugation, rotary evaporation, and suction filtration, preferably rotary evaporation; Step f: After the solid-liquid separation, the powder is collected and transferred to a vacuum drying oven for drying for more than 12 hours.

2. A method for modifying spherical silicon dioxide as claimed in claim 1, characterized in that: Step a: After the silica and the solvent are evenly mixed, the stirring speed is set to 200 rpm-1500 rpm, and all stirring is performed under ultrasonic conditions.

3. A method for modifying spherical silicon dioxide as claimed in claim 1, characterized in that: The particle size of the silicon dioxide in step a is 0.01-1 μm.

4. A method for modifying spherical silicon dioxide as claimed in claim 1, characterized in that: The number of carbon atoms in the siloxane in step a is less than 7, and the boiling point of other organic reagents is lower than 150°C.

5. A method for modifying spherical silicon dioxide as claimed in claim 1, characterized in that: Step a: 20%-40% by volume of grinding beads are added into the grinding chamber, and the particle size of the grinding beads is 0.1mm-0.6mm.

6. A method for modifying spherical silicon dioxide as claimed in claim 1, characterized in that: The amount of solvent added in step b is 40%-60% of the volume of the grinding chamber, the amount of silica powder added in step c is 15%-50% of the weight of the solvent, and the amount of modifier added in step d is calculated based on the theoretical surface hydroxyl number of silica, specifically 0.5-6 times the theoretical surface hydroxyl number of silica.

7. A method for modifying spherical silicon dioxide as claimed in claim 1, characterized in that: The ultrasonic frequency is 25KHZ-130KHZ, and the grinding speed is 3-18m / s.

8. A method for modifying spherical silicon dioxide as claimed in claim 3, characterized in that: The particle size of the silicon dioxide in step a is preferably 0.01-0.5 μm, more preferably 0.01-0.15 μm.

9. A ball milling device, comprising a supporting body (1), a frame (12), a control cabinet (2), a driving motor (4) and a grinding chamber, wherein the control cabinet (2) is provided with a controller (3), the supporting body (1) is mounted with a frame (12), a driving motor (4) is provided in the frame (12), a pulley a (5) is provided on the output shaft of the driving motor (4), the pulley a (5) is fixedly connected to the pulley b (6), a supporting frame (11) is provided on the frame (12), and a modified grinding chamber is provided on the supporting frame (11), wherein the modified grinding chamber is provided, characterized in that: The modified grinding chamber comprises a cover plate (13), the cover plate (13) is provided with a feed port (7-1) and a detection port (7-6), the cover plate (13) is sealedly connected to a shell (7), a stirring and mixing device is provided in the shell (7), the stirring and mixing device comprises a cylindrical stirring component (10), the upper part of the cylindrical stirring component (10) is fixedly connected to a rotating shaft a (7), a cylindrical through hole (9) is provided in the rotating shaft a (7), a plurality of sealed bearings are provided in the cylindrical through hole (9), the sealed bearings are movably connected to a rotating shaft b (8), a screw rod (8-1) is provided at the lower part of the rotating shaft b (8), the lower part of the screw rod (8-1) is fixedly connected to a stirring blade (8-2), the upper part of the rotating shaft a (7) is connected to a pulley c (5-1), the upper part of the rotating shaft b (8) is connected to a rotating shaft b (8), and the upper part of the rotating shaft b (8) is connected to a rotating shaft b (8). The cylindrical stirring assembly (10) is connected to a pulley d (6-1), the pulley a (5) is connected to the pulley c (5-1) by a belt, the pulley b (6) is connected to the pulley d (6-1) by a belt, a cylindrical cavity (10-4) is arranged in the middle of the cylindrical stirring assembly (10), a screw (8-1) is arranged in the cylindrical cavity, a plurality of diversion channels (10-2) are arranged on the cylindrical stirring assembly (10), the diversion channels (10-2) are connected to the cylindrical cavity (10-4), a plurality of stirring rods (10-1) are arranged outside the cylindrical stirring assembly (10), a discharge port (7-4) is arranged at the lower part of the shell (7), an inner cavity (7-5) is arranged in the shell (7), and the inner cavity (7-5) is respectively connected to the water inlet (7-2) and the water outlet (7-3).

10. A ball milling device as claimed in claim 9, characterized in that: A diversion cap (10-3) is provided outside the diversion channel (10-2).

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