Head care appliance preparation method based on filler modified polyolefin master batch
By using filler-modified polyolefin masterbatches that chemically connect graphene and titanium dioxide in head care appliances, the problem of insufficient surface smoothness in the prior art is solved, and higher comfort and cleanliness are achieved.
Patent Information
- Application Number
- CN202510181484.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-02-19
- Publication Date
- 2025-06-06
AI Technical Summary
Existing head care appliances are difficult to achieve smoothness on the surface after forming, resulting in high friction during use, which can easily lead to frizz and breakage of hair, and it is difficult to clean.
Using a preparation method based on filler-modified polyolefin masterbatch, graphene-titanium dioxide graft composite filler is formed by chemically connecting graphene to titanium dioxide, and mixed with matrix resin, reinforcing fibers, antioxidants and other components, and molded through a screw extruder.
It effectively improves the smoothness of the instrument surface, reduces the roughness caused by titanium dioxide particles, and improves the comfort and cleanliness of the product.
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Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of modified polymer material processing, and in particular relates to a method for preparing a head care appliance based on filler-modified polyolefin masterbatch. Background Art
[0002] As the name implies, head care appliances are appliances that directly act on the head for care, the most common of which are combs. Considering that this type of appliance is in direct contact with the hair and head skin, the smoothness of the surface of such products is very important for the user experience and the health of the user's skin and hair. When the surface of the product is smooth, the friction when it comes into contact with the hair is small, which can reduce the friction on the hair, reduce the wear on the hair scales, be more friendly to the hair and scalp, and reduce the frizziness and breakage of the hair. At the same time, the smooth surface can also help reduce the generation of static electricity, avoid the discomfort caused by hair knots and static electricity, and the product itself is easier to clean and stains are not easy to adhere. On the contrary, if the surface of the product is too rough, it will increase friction, which may cause the hair to become frizzy and easy to break. In order to promote the smoothness of the product surface, so far, many such products still choose to be finely polished by hand after molding, which not only significantly increases the production process and cost, but also the narrow gap between the comb teeth makes it very inconvenient to operate. Summary of the invention
[0003] In order to solve the above technical problems, the present invention provides a method for preparing a head care appliance based on filler-modified polyolefin masterbatch. The head care appliance is specifically an integrally formed comb. Calculated by weight, the filler-modified polyolefin masterbatch includes
[0004] Base resin 100
[0005] Graphene-titanium dioxide grafted composite filler 6~12
[0006] Reinforcement fiber 4~8
[0007] Antioxidant 1~2
[0008] Lubricant 2~3
[0009] Plasticizer 1~5
[0010] Silicone oil 2~5.
[0011] Preferably, the base resin includes polyethylene, polypropylene and the like.
[0012] As a preferred embodiment: the graphene-titanium dioxide grafted composite filler is obtained by reacting amino graphene with titanium dioxide grafted with KH570, wherein:
[0013] The amination graphene is obtained by subjecting the graphene to an ammonia plasma surface treatment: the graphene is placed in a plasma surface treatment instrument and ammonia is introduced for low-temperature plasma surface treatment, the power is 100 to 300 W, the ammonia pressure is 0.1 to 0.2 KPa, and the treatment time is 15 to 30 minutes;
[0014] KH570 grafted titanium dioxide is prepared by ultrasonically dispersing titanium dioxide in deionized water, then dropping KH570 thereinto in a stirring state at a mass ratio of KH570 to titanium dioxide of 15 to 30:1, heating to 50 to 80°C after completion of the dropping and reacting for 5 to 10 hours, filtering, washing and drying the solid product.
[0015] Then, the amination graphene and the titanium dioxide grafted with KH570 are mixed in ethanol in a weight ratio of 2 to 5:10 to 20, and then the mixture is heated to 40 to 60°C under the action of a catalyst for 0.5 to 2 hours, and then the solid product is filtered, washed and dried. Here, the graphene and the titanium dioxide are chemically connected by a Michael addition reaction between the amino groups on the graphene surface and the carbon-carbon double bonds of KH570 grafted on the titanium dioxide surface.
[0016] Preferably, the graphene is obtained by reducing graphene oxide prepared by the Hummers method; and the particle size of titanium dioxide is 1 to 3 um.
[0017] Preferably, the reinforcing fibers are glass fibers, carbon fibers, and the like.
[0018] Preferably, the antioxidants include antioxidant 1010, antioxidant 168, antioxidant 1076, antioxidant 245, etc.
[0019] Preferably, the lubricant includes zinc stearate, calcium stearate, magnesium stearate, lead stearate and the like.
[0020] Preferably, the plasticizer includes dioctyl phthalate, dibutyl phthalate, diisobutyl phthalate and the like.
[0021] Preferably, the preparation method of the head care appliance is as follows: a matrix resin, a graphene-titanium dioxide grafted composite filler, reinforcing fiber, an antioxidant, a lubricant, a plasticizer, and silicone oil are added together into a high-speed mixer and mixed sufficiently, and then blended, extruded, and granulated through a screw extruder at 150°C to 230°C to obtain a filler-modified polyolefin masterbatch; the obtained filler-modified polyolefin masterbatch is melt-extruded and molded through a screw extruder at 150°C to 230°C.
[0022] The beneficial effects of the present invention are:
[0023] Titanium dioxide powder is dispersed in the product, which can fill and cover the small pits formed inside or on the surface of the product during the molding process, and is used to address the reduction in smoothness caused by the pits of the product; however, when titanium dioxide particles fill the pits, especially for the pits on the surface of the product, few particles can just fill the pits, and many particles will extend from the pits due to their own volume and shape, which will cause the roughness of the distribution surface of titanium dioxide to increase, even more serious than when titanium dioxide particles are not introduced. In response to this, this solution chemically combines graphene fillers with very ideal smoothness and coats them on the titanium dioxide surface, effectively reducing the surface roughness caused by the titanium dioxide particles themselves. In summary, the smoothness modification of the product is more comprehensive and more targeted.
[0024] The combined graphene and titanium dioxide are both inorganic fillers, so the compatibility between the two and the organic matrix resin is limited. This enables a portion of the graphene-titanium dioxide composite filler to migrate to the surface of the product, thereby better improving the surface smoothness of the product and reducing the amount of composite filler used. DETAILED DESCRIPTION
[0025] Example 1
[0026] Preparation of graphene-titanium dioxide grafted composite filler:
[0027] (1) Placing reduced graphene (Guangdong Innovation Materials (Shenzhen) Co., Ltd., hereinafter the same) in a plasma surface treatment apparatus, and introducing ammonia gas at 30°C for plasma surface treatment, maintaining the ammonia gas pressure at 0.2 KPa, the power at 200 W, and the treatment time at 30 min to obtain amino-modified graphene;
[0028] (2) Ultrasonic dispersion of titanium dioxide with an average particle size of 1.2 μm (uniformly distributed in the particle size range of 1.2±0.2 μm) in deionized water at a mass ratio of 1:50 to deionized water to obtain a titanium dioxide dispersion; ultrasonic dispersion of KH570 in anhydrous ethanol at a mass ratio of 1:100 to anhydrous ethanol to obtain a KH570 dispersion; at a mass ratio of KH570 to titanium dioxide of 15:1, the KH570 dispersion was added dropwise to the titanium dioxide dispersion at room temperature (25°C, the same below) under stirring for 45 minutes. After the addition was completed, the resulting mixed system was heated to 65°C and stirred for 8 hours, then cooled to room temperature, centrifuged, and the solid was collected. The solid was fully washed with anhydrous ethanol, centrifuged, and dried at 75°C to obtain KH570-grafted titanium dioxide;
[0029] (3) 2 parts by weight of the amino graphene obtained in step (1) and 10 parts by weight of the KH570-grafted titanium dioxide obtained in step (2) are added to 110 parts by weight of anhydrous ethanol, and 1 part by weight of sodium ethoxide is added thereto. The mixture is heated to 50° C. and stirred for 2 hours. The mixture is cooled to room temperature and the solid is collected by centrifugation. The solid is washed thoroughly with deionized water, centrifuged, and dried at 75° C. to obtain a graphene-titanium dioxide grafted composite filler.
[0030] Preparation of head care appliances:
[0031] Calculated by weight, 100 parts of polypropylene (Taihua K1035, the same below), 8 parts of the graphene-titanium dioxide grafted composite filler prepared in this embodiment, 5 parts of glass fiber, 1.5 parts of antioxidant 1010, 3 parts of zinc stearate, 5 parts of dioctyl phthalate, and 3 parts of silicone oil (JH-2700, the same below) were added to a high-speed mixer and mixed thoroughly, and then extruded through a twin-screw extruder at 155°C to 205°C (155 in the first zone) and heated to 400°C. The obtained filler-modified polyolefin masterbatch is melt-extruded through a twin-screw extruder at 155°C-205°C (zone 1 155°C, zone 2 170°C, zone 3 185°C, zone 4 195°C, zone 5 205°C, die 200°C, the same below) to form a comb shape.
[0032] Example 2
[0033] Preparation of graphene-titanium dioxide grafted composite filler:
[0034] (1) Placing the reduced graphene in a plasma surface treatment apparatus, and introducing ammonia gas at 30°C for plasma surface treatment, maintaining the ammonia gas pressure at 0.15 KPa, the power at 270 W, and the treatment time at 30 min, to obtain amino-modified graphene;
[0035] (2) Ultrasonic dispersion of titanium dioxide with an average particle size of 1.2 μm (uniformly distributed in the particle size range of 1.2±0.2 μm) in deionized water at a mass ratio of 1:80 to deionized water to obtain a titanium dioxide dispersion; ultrasonic dispersion of KH570 in anhydrous ethanol at a mass ratio of 1:50 to anhydrous ethanol to obtain a KH570 dispersion; at a mass ratio of KH570 to titanium dioxide of 20:1, the KH570 dispersion was added dropwise to the titanium dioxide dispersion under stirring at room temperature for 25 minutes. After the addition was completed, the resulting mixed system was heated to 60°C and stirred for 10 hours, then cooled to room temperature, centrifuged, and the solid was collected. The solid was fully washed with anhydrous ethanol, centrifuged, and dried at 75°C to obtain KH570-grafted titanium dioxide;
[0036] (3) 5 parts by weight of the amino graphene obtained in step (1) and 15 parts by weight of the KH570-grafted titanium dioxide obtained in step (2) are added to 150 parts by weight of anhydrous ethanol, and 1.5 parts by weight of sodium ethoxide is added thereto. The mixture is heated to 45° C. and stirred for 2 hours. The mixture is cooled to room temperature and the solid is collected by centrifugation. The solid is washed thoroughly with deionized water, centrifuged, and dried at 75° C. to obtain a graphene-titanium dioxide grafted composite filler.
[0037] Preparation of head care appliances:
[0038] Calculated by weight, 100 parts of polypropylene, 10 parts of the graphene-titanium dioxide grafted composite filler prepared in this embodiment, 4 parts of glass fiber, 1 part of antioxidant 1076, 2 parts of calcium stearate, 4 parts of diisobutyl phthalate, and 4 parts of silicone oil are added together into a high-speed mixer and mixed thoroughly, and then blended, extruded, and granulated through a twin-screw extruder at 155° C. to 205° C. to serve as a filler-modified polyolefin masterbatch; the obtained filler-modified polyolefin masterbatch is melt-extruded through a twin-screw extruder at 155° C. to 205° C. to form a comb shape.
[0039] Example 3
[0040] Preparation of graphene-titanium dioxide grafted composite filler:
[0041] (1) Placing the reduced graphene in a plasma surface treatment apparatus, and introducing ammonia gas at 25°C for plasma surface treatment, maintaining the ammonia gas pressure at 0.15 KPa, the power at 300 W, and the treatment time at 20 min, to obtain amino-modified graphene;
[0042] (2) Ultrasonic dispersion of titanium dioxide with an average particle size of 1.2 μm (uniformly distributed in the particle size range of 1.2±0.2 μm) in deionized water at a mass ratio of 1:100 to deionized water was used as a titanium dioxide dispersion; KH570 and anhydrous ethanol were ultrasonically dispersed in anhydrous ethanol at a mass ratio of 1:60 to obtain a KH570 dispersion; the KH570 dispersion was added dropwise to the titanium dioxide dispersion at a mass ratio of KH570 to titanium dioxide of 25:1 under stirring at room temperature for 30 minutes. After the addition was completed, the resulting mixed system was heated to 65°C and stirred for 7 hours, then cooled to room temperature, centrifuged, and the solid was collected. The solid was fully washed with anhydrous ethanol, centrifuged, and dried at 75°C to obtain KH570-grafted titanium dioxide;
[0043] (3) 4 parts by weight of the amino graphene obtained in step (1) and 15 parts by weight of the KH570-grafted titanium dioxide obtained in step (2) are added to 200 parts by weight of anhydrous ethanol, and 2 parts by weight of sodium ethoxide is added thereto. The mixture is heated to 55° C. and stirred for 2 hours. The mixture is cooled to room temperature and the solid is collected by centrifugation. The solid is washed thoroughly with deionized water, centrifuged, and dried at 75° C. to obtain a graphene-titanium dioxide grafted composite filler.
[0044] Preparation of head care appliances:
[0045] Calculated by weight, 100 parts of polypropylene, 9 parts of the graphene-titanium dioxide grafted composite filler prepared in this embodiment, 6 parts of glass fiber, 2 parts of antioxidant 168, 1 part of zinc stearate, 2 parts of magnesium stearate, 3 parts of dibutyl phthalate, and 3 parts of silicone oil are added together into a high-speed mixer and mixed thoroughly, and then blended, extruded, and granulated through a twin-screw extruder at 155°C to 205°C to use as a filler-modified polyolefin masterbatch; the obtained filler-modified polyolefin masterbatch is melt-extruded through a twin-screw extruder at 155°C to 205°C to form a comb shape.
[0046] Blank control example
[0047] No amino graphene was introduced, and no KH570-grafted titanium dioxide was introduced. The remaining components and operations were the same as those in Example 2:
[0048] Preparation of head care appliances:
[0049] Calculated by weight, 100 parts of polypropylene, 4 parts of glass fiber, 1 part of antioxidant 1076, 2 parts of calcium stearate, 4 parts of diisobutyl phthalate, and 4 parts of silicone oil are added together into a high-speed mixer and mixed thoroughly, and then blended, extruded, and granulated through a twin-screw extruder at 155° C. to 205° C. to serve as a filler-modified polyolefin masterbatch; the obtained filler-modified polyolefin masterbatch is melt-extruded through a twin-screw extruder at 155° C. to 205° C. to be formed into a comb shape.
[0050] Comparative Example 1
[0051] KH570-grafted titanium dioxide was not introduced, and the remaining components and operations were the same as those in Example 2:
[0052] (1) Placing the reduced graphene in a plasma surface treatment apparatus, and introducing ammonia gas at 30°C for plasma surface treatment, maintaining the ammonia gas pressure at 0.15 KPa, the power at 270 W, and the treatment time at 30 min, to obtain amino-modified graphene.
[0053] Preparation of head care appliances:
[0054] Calculated by weight, 100 parts of polypropylene, 2.5 parts of amino graphene prepared in step (1) of this comparative example, 4 parts of glass fiber, 1 part of antioxidant 1076, 2 parts of calcium stearate, 4 parts of diisobutyl phthalate, and 4 parts of silicone oil are added together into a high-speed mixer and mixed thoroughly, and then blended, extruded, and granulated through a twin-screw extruder at 155° C. to 205° C. to obtain a filler-modified polyolefin masterbatch; the obtained filler-modified polyolefin masterbatch is melt-extruded through a twin-screw extruder at 155° C. to 205° C. to form a comb shape.
[0055] Comparative Example 2
[0056] The amination graphene and the KH570-grafted titanium dioxide were not chemically combined together, but added separately, and the remaining components and operations were the same as in Example 2:
[0057] (1) Placing the reduced graphene in a plasma surface treatment apparatus, and introducing ammonia gas at 30°C for plasma surface treatment, maintaining the ammonia gas pressure at 0.15 KPa, the power at 270 W, and the treatment time at 30 min, to obtain amino-modified graphene;
[0058] (2) Titanium dioxide with an average particle size of 1.2 μm (uniformly distributed in the particle size range of 1.2±0.2 μm) was ultrasonically dispersed in deionized water at a mass ratio of 1:80 to deionized water to obtain a titanium dioxide dispersion; KH570 was ultrasonically dispersed in anhydrous ethanol at a mass ratio of 1:50 to anhydrous ethanol to obtain a KH570 dispersion; the KH570 dispersion was added dropwise to the titanium dioxide dispersion at a mass ratio of KH570 to titanium dioxide of 20:1 under stirring at room temperature for 25 minutes. After the addition was completed, the resulting mixed system was heated to 60°C and stirred for 10 hours, then cooled to room temperature, centrifuged, and the solid was collected. The solid was fully washed with anhydrous ethanol, centrifuged, and dried at 75°C to obtain KH570-grafted titanium dioxide.
[0059] Preparation of head care appliances:
[0060] Calculated by weight, 100 parts of polypropylene, 2.5 parts of amino graphene prepared in step (1) of this comparative example, 7.5 parts of KH570 grafted titanium dioxide prepared in step (2) of this comparative example, 4 parts of glass fiber, 1 part of antioxidant 1076, 2 parts of calcium stearate, 4 parts of diisobutyl phthalate, and 4 parts of silicone oil are added together into a high-speed mixer and mixed thoroughly, and then blended, extruded, and granulated through a twin-screw extruder at 155° C. to 205° C. to obtain a filler-modified polyolefin masterbatch; the obtained filler-modified polyolefin masterbatch is melt-extruded through a twin-screw extruder at 155° C. to 205° C. to form a comb shape.
[0061] Comparative Example 3
[0062] Nano-sized titanium dioxide was used instead, and the remaining components and operations were the same as those in Example 2:
[0063] Preparation of graphene-titanium dioxide grafted composite filler:
[0064] (1) Placing the reduced graphene in a plasma surface treatment apparatus, and introducing ammonia gas at 30°C for plasma surface treatment, maintaining the ammonia gas pressure at 0.15 KPa, the power at 270 W, and the treatment time at 30 min, to obtain amino-modified graphene;
[0065] (2) Titanium dioxide with an average particle size of 120 nm (uniformly distributed in the particle size range of 120±20 nm) was ultrasonically dispersed in deionized water at a mass ratio of 1:80 to deionized water to obtain a titanium dioxide dispersion; KH570 was ultrasonically dispersed in anhydrous ethanol at a mass ratio of 1:50 to anhydrous ethanol to obtain a KH570 dispersion; the KH570 dispersion was added dropwise to the titanium dioxide dispersion at a mass ratio of KH570 to titanium dioxide of 20:1 under stirring at room temperature for 25 minutes. After the addition was completed, the resulting mixed system was heated to 60°C and stirred for 10 hours, then cooled to room temperature, centrifuged, and the solid was collected. The solid was fully washed with anhydrous ethanol, centrifuged, and dried at 75°C to obtain KH570-grafted titanium dioxide;
[0066] (3) 5 parts by weight of the amino graphene obtained in step (1) and 15 parts by weight of the KH570-grafted titanium dioxide obtained in step (2) are added to 150 parts by weight of anhydrous ethanol, and 1.5 parts by weight of sodium ethoxide is added thereto. The mixture is heated to 45° C. and stirred for 2 hours. The mixture is cooled to room temperature and the solid is collected by centrifugation. The solid is washed thoroughly with deionized water, centrifuged, and dried at 75° C. to obtain a graphene-titanium dioxide grafted composite filler.
[0067] Preparation of head care appliances:
[0068] Calculated by weight, 100 parts of polypropylene, 10 parts of the graphene-titanium dioxide grafted composite filler prepared in this comparative example, 4 parts of glass fiber, 1 part of antioxidant 1076, 2 parts of calcium stearate, 4 parts of diisobutyl phthalate, and 4 parts of silicone oil are added together into a high-speed mixer and mixed thoroughly, and then blended, extruded, and granulated through a twin-screw extruder at 155° C. to 205° C. to serve as a filler-modified polyolefin masterbatch; the obtained filler-modified polyolefin masterbatch is melt-extruded through a twin-screw extruder at 155° C. to 205° C. to form a comb shape.
[0069] Comparative Example 4
[0070] In the preparation process of the head care appliance, the amount of the added KH570 grafted titanium dioxide is kept unchanged, and the amount of the amino graphene is increased. The other components and operations are the same as those in Example 2:
[0071] Preparation of graphene-titanium dioxide grafted composite filler:
[0072] (1) Placing the reduced graphene in a plasma surface treatment apparatus, and introducing ammonia gas at 30°C for plasma surface treatment, maintaining the ammonia gas pressure at 0.15 KPa, the power at 270 W, and the treatment time at 30 min, to obtain amino-modified graphene;
[0073] (2) Ultrasonic dispersion of titanium dioxide with an average particle size of 1.2 μm (uniformly distributed in the particle size range of 1.2±0.2 μm) in deionized water at a mass ratio of 1:80 to deionized water to obtain a titanium dioxide dispersion; ultrasonic dispersion of KH570 in anhydrous ethanol at a mass ratio of 1:50 to anhydrous ethanol to obtain a KH570 dispersion; at a mass ratio of KH570 to titanium dioxide of 20:1, the KH570 dispersion was added dropwise to the titanium dioxide dispersion under stirring at room temperature for 25 minutes. After the addition was completed, the resulting mixed system was heated to 60°C and stirred for 10 hours, then cooled to room temperature, centrifuged, and the solid was collected. The solid was fully washed with anhydrous ethanol, centrifuged, and dried at 75°C to obtain KH570-grafted titanium dioxide;
[0074] (3) 20 parts by weight of the amino graphene obtained in step (1) and 15 parts by weight of the KH570-grafted titanium dioxide obtained in step (2) are added to 150 parts by weight of anhydrous ethanol, and 1.5 parts by weight of sodium ethoxide is added thereto. The mixture is heated to 45° C. and stirred for 2 hours. The mixture is cooled to room temperature and the solid is collected by centrifugation. The solid is washed thoroughly with deionized water, centrifuged, and dried at 75° C. to obtain a graphene-titanium dioxide grafted composite filler.
[0075] Preparation of head care appliances:
[0076] Calculated by weight, 100 parts of polypropylene, 17.5 parts of the graphene-titanium dioxide grafted composite filler prepared in this comparative example, 4 parts of glass fiber, 1 part of antioxidant 1076, 2 parts of calcium stearate, 4 parts of diisobutyl phthalate, and 4 parts of silicone oil are added together into a high-speed mixer and mixed thoroughly, and then blended, extruded, and granulated through a twin-screw extruder at 155° C. to 205° C. to serve as a filler-modified polyolefin masterbatch; the obtained filler-modified polyolefin masterbatch is melt-extruded through a twin-screw extruder at 155° C. to 205° C. to form a comb shape.
[0077] The surfaces of the comb products extruded in the above-mentioned embodiments, comparative embodiments and control examples were tested using a surface roughness measuring instrument (the surfaces to be tested of the products were cleaned with ethanol before testing, and the test was performed after the ethanol was fully evaporated). The test results are shown in Table 1:
[0078] Table 1
[0079]
[0080] From the above table, compared with the blank control example, after adding graphene filler in Comparative Example 1, the graphene affects the product based on the smoothness of its own texture, so that its roughness decreases and the surface smoothness improves;
[0081] Comparative Example 2 further adds titanium dioxide powder on the basis of Comparative Example 1, and the surface smoothness of the product does not change significantly; but in contrast, in Example 2 representing the present solution, the surface smoothness of the product is effectively improved after only chemically connecting the graphene filler and the titanium dioxide powder. In this regard, the applicant believes that after introducing titanium dioxide particles, some small pits inside or on the surface of the product can be filled, which is beneficial to improving the smoothness of the product, at least eliminating the influence of the pits. Otherwise, Example 2 would not have such a significant improvement in the surface smoothness of the product compared to Comparative Example 1. However, after the titanium dioxide particles partially emerge from the pits, the roughness of the distribution surface where the titanium dioxide is located will increase. Therefore, the overall surface smoothness of the product in Comparative Example 2 in which titanium dioxide particles are simply introduced is not effectively improved. In Example 2, graphene and titanium dioxide are specifically chemically connected together. Without affecting the filling of the product pits by titanium dioxide particles, the graphene filler directly lubricates the rough distribution surface caused by titanium dioxide. That is, at this time, the lubrication modification of the graphene filler on the product is more targeted in terms of position, which greatly eliminates the negative impact of the introduction of titanium dioxide particles, further improves the overall smoothness of the product, and increases the comfort of the product.
[0082] In Comparative Example 3, nano-scale titanium dioxide particles are grafted with graphene fillers. Since the particle size is significantly reduced, the titanium dioxide particles are loaded on the graphene, which is similar to the appendages on the graphene filler. Therefore, when repairing the resin product, the graphene plays a leading role, which correspondingly weakens the repair tendency of the titanium dioxide particles to the pits on the product; this is also reflected in Comparative Example 4: as the amount of graphene increases, the graphene gradually replaces the titanium dioxide particles and plays a leading role, thereby correspondingly weakening the repair tendency of the titanium dioxide particles to the pits. In Example 2 representing this solution, when the amount is moderate and the titanium dioxide particles are large, the graphene is equivalent to being attached to the particles, and the titanium dioxide particles play a leading role, so that the repair of the pits in the product is more effective.
[0083] In addition, according to GB / T 1040.1-2006, the tensile strength of the extruded comb products in the above embodiments, comparative embodiments and control examples is 34MPa-41MPa, and the elongation at break is 205%-262%, which fully meets the requirements of daily use.
Claims
1. A method for preparing a head care appliance based on filler-modified polyolefin masterbatch, characterized in that: Calculated by weight, the filler-modified polyolefin masterbatch comprises Base resin 100 Graphene-titanium dioxide grafted composite filler 6~12 Reinforcement fiber 4~8 Antioxidant 1~2 Lubricant 2~3 Plasticizer 1~5 Silicone oil 2~5.
2. The method for preparing a head care appliance based on filler-modified polyolefin masterbatch according to claim 1, characterized in that: The base resin is polyethylene or polypropylene.
3. The method for preparing a head care appliance based on filler-modified polyolefin masterbatch according to claim 1, characterized in that: The graphene-titanium dioxide grafted composite filler is obtained by reacting amino graphene with titanium dioxide grafted with KH570. The reaction operation is as follows: the amino graphene and the titanium dioxide grafted with KH570 are fully mixed in ethanol at a weight ratio of 2-5:10-20, and then the mixture is heated to 40-60° C. under the action of a catalyst and reacted for 0.5-2 hours, and then the solid product is filtered, washed and dried.
4. The method for preparing a head care appliance based on filler-modified polyolefin masterbatch according to claim 3, characterized in that: The amination graphene is obtained by subjecting graphene to ammonia plasma surface treatment. The operation of the ammonia plasma surface treatment is to place the graphene in a plasma surface treatment instrument and introduce ammonia for low-temperature plasma surface treatment. The power is 100 to 300 W, the pressure of the introduced ammonia is 0.1 to 0.2 KPa, and the treatment time is 15 to 30 minutes.
5. The method for preparing a head care appliance based on filler-modified polyolefin masterbatch according to claim 3, characterized in that: The preparation method of the KH570-grafted titanium dioxide is as follows: after fully dispersing titanium dioxide in deionized water with ultrasonic wave, KH570 is added dropwise under stirring at a mass ratio of KH570 to titanium dioxide of 15 to 30:1, and after the addition is completed, the temperature is raised to 50 to 80° C. for reaction for 5 to 10 hours, and then the solid product is filtered, washed and dried; the particle size of the titanium dioxide is 1 to 3 μm.
6. The method for preparing a head care appliance based on filler-modified polyolefin masterbatch according to claim 1, characterized in that: The reinforcing fibers are glass fibers or carbon fibers.
7. The method for preparing a head care appliance based on filler-modified polyolefin masterbatch according to claim 1, characterized in that: The antioxidant is antioxidant 1010, antioxidant 168, antioxidant 1076 or antioxidant 245.
8. The method for preparing a head care appliance based on filler-modified polyolefin masterbatch according to claim 1, characterized in that: The lubricant is zinc stearate, calcium stearate, magnesium stearate or lead stearate.
9. The method for preparing a head care appliance based on filler-modified polyolefin masterbatch according to claim 1, characterized in that: The plasticizer is dioctyl phthalate, dibutyl phthalate or diisobutyl phthalate.
10. The method for preparing a head care appliance based on filler-modified polyolefin masterbatch according to claim 1, characterized in that: The preparation method comprises the following steps: adding the matrix resin, the graphene-titanium dioxide grafted composite filler, the reinforcing fiber, the antioxidant, the lubricant, the plasticizer and the silicone oil into a high-speed mixer and mixing them sufficiently, and then extruding and granulating the mixture through a screw extruder at 150° C. to 230° C. to obtain the filler-modified polyolefin masterbatch; and then melt-extruding the filler-modified polyolefin masterbatch through a screw extruder at 150° C. to 230° C. to form the masterbatch into a comb shape.