Composite material preparation method, composite material and composite material product

Abstract

The embodiment of the invention discloses a composite material preparation method, a composite material and a composite material product, the composite material is prepared by carrying out surface modification on hollow glass beads and mixing the surface modified hollow glass beads with matrix resin, so that the toughness of the composite material is effectively improved while the lightweight of the composite material is realized, and the composite material has good mechanical properties. The quality of a composite material product is favorably improved. Moreover, the preparation method of the composite material is simple and easy to implement, is suitable for large-scale industrial production, and meets the requirements of various engineering applications.

Description

Technical Field

[0001] The present invention relates to the technical field of composite materials, and more particularly to a method for preparing a composite material, a composite material and a composite material product. Background Art

[0002] As modern industry develops towards high efficiency and energy conservation, lightweighting of materials has become one of the key technologies to enhance product competitiveness. In the fields of consumer electronics, new energy vehicles, aerospace, etc., reducing the weight of materials can not only optimize product performance, but also significantly reduce energy consumption, which is in line with the global sustainable development strategy. Polymer composite materials are widely used in various fields due to their excellent comprehensive performance. In the fields of consumer electronics, etc., the requirements for lightweight materials are particularly stringent, and there is an urgent need to reduce the material density without affecting product performance. As the main material for the housings, decorations and structural parts of electronic products and vehicles, the lightweight modification technology of polymer composite materials is particularly important, especially for areas that need to strictly control the overall weight, such as high-end smart phones, tablet computers, new energy vehicles, etc., the demand for lightweight polymer composite materials is even more urgent.

[0003] Hollow glass microspheres are widely used in lightweight modification of polymer composite materials due to their unique hollow structure. They can reduce the density while maintaining the material strength to a certain extent. However, the existing solution of adding hollow glass microspheres to resin has defects: the mechanical properties of the material (such as impact resistance and tensile strength) are greatly reduced after lightweighting, and the surface quality is deteriorated. The molding accuracy cannot meet the requirements of high-end products. Summary of the Invention

[0004] In view of this, embodiments of the present invention provide a composite material preparation method, a composite material, and a composite material product, which are conducive to solving at least some of the above problems existing in the prior art.

[0005] In a first aspect, an embodiment of the present invention provides a method for preparing a composite material, comprising: pre-treating hollow glass microspheres, wherein the pre-treatment includes cleaning and drying; placing the pre-treated hollow glass microspheres in a plasma treatment device, performing plasma treatment in a working gas with a power of 5-15 kW and a flow rate of 100-1000 ml / min for 3-20 minutes, and obtaining activated hollow glass microspheres after drying; adding the activated hollow glass microspheres to an organic solvent, adding a silane coupling agent for dispersion at a stirring speed of 300-500 r / min to obtain a dispersion, adding a flexible polymer long chain and an initiator to the dispersion for grafting treatment to graft the flexible polymer long chain on the surface of the activated hollow glass microspheres to obtain a reaction liquid; passing the reaction liquid through a granulation device to obtain a dry powder, and performing roller grinding or ball milling dispersion on the dry powder to obtain surface-modified hollow glass microspheres; and mixing the surface-modified hollow glass microspheres with a matrix resin and an additive to granulate to prepare a granular composite material.

[0006] Furthermore, after the pretreated hollow glass microspheres are placed in the plasma treatment equipment, the pressure in the chamber of the plasma treatment equipment is pumped down to a vacuum degree of 10-3-10-1 Pa, and then the working gas is introduced into the chamber to perform plasma treatment.

[0007] Furthermore, the diameter of the hollow glass microspheres is 5-20 μm, the wall thickness of the hollow glass microspheres is 0.3-2.5 μm, and the density of the hollow glass microspheres is 0.1-0.5 g / cm 3 .

[0008] Furthermore, the silane coupling agent includes at least one of γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane; the flexible polymer long chain includes at least one of long-chain polyether, long-chain polyester, and long-chain polyvinyl alcohol; and the organic solvent includes at least one of acetone, dimethyl sulfoxide, and ethyl acetate.

[0009] Furthermore, the reaction liquid is dried by a spray granulation device to obtain the dry powder, the drying temperature is 100-200 degrees Celsius, and the spray pressure is 0.5-2 MPa.

[0010] Furthermore, adding flexible polymer long chains and initiators to the dispersion for grafting treatment includes: adding flexible polymer long chains and initiators to the dispersion, heating and stirring in a water bath at 50-90 degrees Celsius, stirring at a speed of 500-800 r / min, and reacting for 2-5 hours.

[0011] Further, the base resin comprises at least one of polyamide, polycarbonate, polypropylene and acrylonitrile-butadiene-styrene; and the auxiliary agent comprises at least one of coupling agent, stabilizer, lubricant, pigment and filler.

[0012] In a second aspect, the embodiments of the present application further provide a composite material, which is prepared by the composite material preparation method as described in the first aspect.

[0013] In a third aspect, the embodiments of the present application further provide a composite material product, which is prepared by at least one of injection molding, extrusion and compression molding on the composite material as described in the second aspect.

[0014] Further, the composite material product is at least a part of a head-mounted device.

[0015] The embodiments of the present application provide a composite material preparation method, a composite material and a composite material product. The surface of hollow glass microspheres is modified, and the surface-modified hollow glass microspheres are mixed with a base resin to prepare a composite material. The lightweight composite material is prepared, and the toughness of the composite material is effectively improved, which is conducive to improving the quality of the composite material product. Moreover, the composite material preparation method is simple and easy to implement, and is suitable for large-scale industrial production, and meets the needs of various engineering applications. BRIEF DESCRIPTION OF DRAWINGS

[0016] The above and other objects, features and advantages of the present application will become more apparent from the following description of the embodiments of the present application taken with reference to the accompanying drawings, in which:

[0017] Figure 1 is a flowchart of a composite material preparation method according to an embodiment of the present application. DETAILED DESCRIPTION

[0018] The present application is described below based on the embodiments. However, the present application is not limited to these embodiments. In the following detailed description of the present application, some specific details are described in detail. The present application can also be understood without the description of these details by those skilled in the art. In order to avoid confusion of the essence of the present application, well-known methods, processes, procedures, elements and circuits are not described in detail.

[0019] In addition, those of ordinary skill in the art will understand that the drawings provided herein are for illustrative purposes only and are not necessarily drawn to scale.

[0020] Unless the context clearly requires otherwise, throughout the description, the words "comprise", "comprising", and the like are to be construed in an inclusive sense as opposed to an exclusive or exhaustive sense; that is to say, in the sense of "including, but not limited to".

[0021] In the description of this application, it should be understood that the terms "first", "second", etc. are used for descriptive purposes only and should not be understood to indicate or imply relative importance. In addition, in the description of this application, unless otherwise specified, "plurality" means two or more.

[0022] The embodiment of the present invention provides a composite material, which is composed of at least surface-modified hollow glass microspheres and a matrix resin, and has a low density and good toughness and mechanical properties. In the embodiment of the present invention, the composite material can be prepared by the following preparation method. Figure 1 The preparation method includes the following steps S100 to S500:

[0023] Step S100: pre-treating the hollow glass microspheres.

[0024] In step S100, the pretreatment may include cleaning the hollow glass microspheres with organic solvents, ultrasonic cleaning, and other methods to remove oil, dust, and impurities, and then drying the cleaned hollow glass microspheres. The diameter of the hollow glass microspheres can be in the range of 5-20 μm, the wall thickness can be in the range of 0.3-2.5 μm, and the density of the hollow glass microspheres can be in the range of 0.1-0.5 g / cm 3 .

[0025] Step S200: placing the pretreated hollow glass microspheres in a plasma treatment device for plasma treatment for 3-20 minutes, and obtaining activated hollow glass microspheres after drying.

[0026] In step S200, after the pretreated hollow glass microspheres are placed in a plasma treatment device, the pressure in the plasma treatment device chamber is evacuated to a vacuum degree of 10-3-10-1Pa (Pascals), and then a working gas is introduced into the chamber. At the same time, a high-frequency electric field or a microwave electric field is applied to ionize the working gas to generate plasma that interacts with the surface of the pretreated hollow glass microspheres to achieve surface activation. The power of the plasma treatment can be 5-15kW (kilowatts), and the flow rate of the working gas can be 100-1000ml / min (milliliters per minute). The plasma treatment activation time can be 3-20 minutes. The working gas can include argon, nitrogen, oxygen, etc. The activated hollow glass microspheres can be vacuum dried to obtain activated hollow glass microspheres.

[0027] Step S300, adding activated hollow glass microspheres to an organic solvent, adding a silane coupling agent at a stirring speed of 300-500 r / min to disperse to obtain a dispersion, adding a flexible polymer long chain and an initiator to the dispersion to perform a grafting treatment to graft the flexible polymer long chain on the surface of the activated hollow glass microspheres to obtain a reaction solution.

[0028] Flexible polymer long chains can be grafted onto the surface of activated hollow glass microspheres by solution polymerization or sol-gel method. In step S300, the activated hollow glass microspheres obtained in step S200 are added to an organic solvent, and a silane coupling agent is added at a stirring speed of 300-500 r / min (revolutions per minute) to disperse the mixture to obtain a dispersion. The organic solvent may include at least one of acetone, dimethyl sulfoxide, and ethyl acetate. The silane coupling agent includes one or more of γ-aminopropyltriethoxysilane (KH550), γ-glycidoxypropyltrimethoxysilane (KH560), γ-methacryloxypropyltrimethoxysilane (KH570), and other silane coupling agents. Flexible polymer long chains and an initiator are added to the dispersion for grafting treatment to graft flexible polymer long chains onto the surface of the activated hollow glass microspheres. Grafting a long polymer chain can enhance the toughening effect. Optionally, the grafted flexible polymer long chain can include at least one of a long-chain polyether, a long-chain polyester, and a long-chain polyvinyl alcohol. For example, polyethylene glycol, polyvinyl alcohol, hexamethylenediamine, isocyanate, or other flexible polymer long chains can be used. The type of initiator is specifically determined according to the flexible polymer long chain used. After adding the flexible polymer long chain and the initiator to the dispersion, the reaction is heated and stirred in a water bath at 50-90 degrees Celsius, the stirring speed is 500-800r / min, and the reaction time is 2-5 hours to obtain a reaction solution of hollow glass microspheres containing surface-grafted flexible polymer long chains.

[0029] Step S400: The reaction liquid is passed through a granulation device to obtain dry powder, and the dry powder is subjected to roller grinding or ball milling dispersion to obtain surface-modified hollow glass microspheres.

[0030] In step S400, for example, the reaction solution can be dried using a spray granulation device to obtain a dry powder. Spray granulation is a process that integrates atomization, drying, and granulation of a solution, suspension, or molten material. The liquid material is dispersed into tiny droplets by an atomizer, which are then rapidly dried under hot air to form uniform particles. The drying temperature is 100-200 degrees Celsius, and the spray pressure is 0.5-2 MPa. The spray-granulated dry powder is then drum-milled or ball-milled to obtain uniformly dispersed surface-modified hollow glass microspheres.

[0031] Step S500: mixing the surface-modified hollow glass microspheres with the matrix resin and the additives to form granules to prepare a granular composite material.

[0032] In step S500, the matrix resin can be selected according to the characteristics required for the composite material. For example, it can be at least one of polyamide (PA), polycarbonate (PC), polypropylene (PP) and acrylonitrile-butadiene-styrene (ABS). The auxiliary agent may include at least one of a coupling agent, a stabilizer, a lubricant, a pigment and a filler to improve the processing performance, mechanical properties, durability and appearance quality of the obtained composite material. In actual formulation design, it is necessary to optimize the ratio of various auxiliary agents by orthogonal tests and other methods according to the matrix resin characteristics, processing conditions and final application requirements. The coupling agent is used to bridge the inorganic filler and the organic matrix, enhance the interfacial bonding strength or improve the filler dispersibility. The stabilizer may include at least one of a heat stabilizer, a light stabilizer, an antioxidant, etc., and the stabilization of the material is achieved by capturing free radicals, decomposing peroxides, etc. The lubricant may include an internal lubricant (such as stearic acid) for reducing friction between molecular chains and / or an external lubricant (such as PE wax) for reducing adhesion to processing equipment. Pigments are used to adjust the color of the composite material. For example, inorganic pigments (such as titanium dioxide, red iron oxide), organic pigments (such as phthalocyanine), or special effect pigments (such as pearlescent powder, fluorescent powder), etc. can be used.

[0033] Example 1

[0034] A composite material is prepared by the following method:

[0035] (1) Hollow glass microspheres with a diameter of 5-20 μm and a wall thickness of 0.3-2.5 μm are selected, and the hollow glass microspheres are cleaned and dried by ultrasonic cleaning to obtain pretreated hollow glass microspheres.

[0036] (2) After the pretreated hollow glass microspheres are placed in a plasma treatment device, the plasma treatment device chamber is closed, the vacuum pump is started, the pressure in the chamber is evacuated to a vacuum degree of 10-Pa, and argon gas is introduced into the chamber at a flow rate of 100-1000 ml / min. At the same time, a high-frequency electric field with a power of 5-15 kW is applied to activate the pretreated hollow glass microspheres for 3 minutes to obtain activated hollow glass microspheres.

[0037] (3) Adding the activated hollow glass microspheres to acetone, adding 0.5-1 wt% of a silane coupling agent KH550 at a stirring speed of 350 / min, and stably dispersing to obtain a dispersion. Adding 1-5 wt% of polyethylene glycol or 1-5 wt% of a hydroxyl-terminated polyether to the dispersion, heating and stirring the dispersion in a water bath at a temperature of 50-90 degrees Celsius, stirring at a speed of 700 r / min, and reacting for 2-5 hours to obtain a reaction solution containing hollow glass microspheres grafted with polyethylene glycol or hydroxyl-terminated polyether.

[0038] (4) The reaction solution is dried by a spray granulation device to obtain dry powder, the drying temperature is 100 degrees Celsius, and the spray pressure is 0.5 MPa. Then, the dry powder after spray granulation is subjected to ball milling dispersion at a ball milling speed of 100-500 r / min to obtain the surface-modified hollow glass microspheres.

[0039] (5) The surface-modified hollow glass microspheres are mixed with polyamide (matrix resin) and 1-3 wt% lubricant (auxiliary) to prepare composite material granules by blending through a double-screw extruder, and the mass ratio of polyamide to surface-modified hollow glass microspheres is 1:0.2.

[0040] Example 2

[0041] A composite material, the steps (1)-(4) in the preparation method are the same as those in Example 1. The difference between Example 2 and Example 1 is that the matrix resin in step (5) is replaced by polypropylene, and the mass ratio of polypropylene to surface-modified hollow glass microspheres is 1:0.2.

[0042] Example 3

[0043] A composite material, the steps (1)-(4) in the preparation method are the same as those in Example 1. The difference between Example 3 and Example 1 is that the matrix resin in step (5) is replaced by polycarbonate, and the mass ratio of polycarbonate to surface-modified hollow glass microspheres is 1:0.2.

[0044] Example 4

[0045] A composite material, the steps (1)-(4) in the preparation method are the same as those in Example 1. The difference between Example 3 and Example 1 is that the mass ratio of polyamide to surface-modified hollow glass microspheres in step (5) is 1:0.15.

[0046] Example 5

[0047] A composite material, the steps (1)-(4) in the preparation method are the same as those in Example 1. The difference between Example 3 and Example 1 is that the mass ratio of polyamide to surface-modified hollow glass microspheres in step (5) is 1:0.25.

[0048] Comparative Example

[0049] A composite material, the difference between the comparative example and Example 1 is that the hollow glass microspheres in the comparative example are not surface-modified by the method of the present application. The hollow glass microspheres selected in step (1) in Example 1 are mixed with polyamide and lubricant to prepare composite material granules by blending through a double-screw extruder to obtain the composite material of the comparative example. The mass ratio of polyamide to surface-modified hollow glass microspheres is 1:0.2.

[0050] The following Table 1 is a performance comparison of the composite materials of the above-mentioned Examples 1-5 and the Comparative Example:

[0051] Table 1

[0052]

[0053] According to the performance comparison of Table 1, the density of the composite material of the Comparative Example is 0.87 g / cm 3 , the tensile modulus is 2500 MPa, the tensile strength is 43 MPa, the elongation at break is 8%, and the notched impact strength is in the range of 6-14 kJ / m 2 . The density of the composite material of the present application can reach 0.9 g / cm 3 . For the composite material of Example 1, the density is 0.85 g / cm 3 , which is lower than that of the composite material of the Comparative Example; the tensile modulus of the composite material of Example 1 is 2200 MPa, and the tensile strength is 45 MPa, which is close to the corresponding performance parameters of the Comparative Example; the elongation at break of the composite material of Example 1 is 36%, and the notched impact strength is 12 kJ / m 2 , which is significantly better than the corresponding performance of the composite material of the Comparative Example. This shows that after the hollow glass microspheres are subjected to surface modification treatment, the compatibility with the matrix resin is significantly improved, and the flexible high molecular material grafted on the surface toughens the entire system, so that the notched impact strength of the composite material reaches 10 kJ / m 2 and above. The polymer composite material prepared by filling the matrix resin with the surface-modified hollow glass microspheres not only realizes the lightweight of the composite material, but also effectively improves the problem of decreased toughness of the finished product due to the rigidity and brittleness of the hollow glass microspheres. For the composite materials of Examples 2-5, the tensile modulus is above 1300 or even close to 2700, the tensile strength is 25-66 MPa, the elongation at break is above 10%, and the notched impact strength is in the range of 6-14 kJ / m 2 , which shows good toughness. Moreover, the elastic modulus of the composite material can reach about 2 GPa, the preparation process is simple and easy to implement, is suitable for large-scale industrial production, and meets the needs of various engineering applications.

[0054] The embodiments of the present application also relate to a composite material product, which is made by at least one of injection molding, extrusion and molding from the composite material prepared by the above preparation method. In one use scenario, the composite material can be applied to the shell or other components of a consumer electronic product, which has good toughness and mechanical properties while reducing the weight of the product, thereby ensuring the durability of the product. Alternatively, the composite material product is at least a part of a head-mounted device, which is beneficial to reduce the weight of the product to improve the user wearing experience, while having stronger toughness and good appearance. The head-mounted device can be a virtual reality (VR) device, an augmented reality (AR) device, a mixed reality (MR) device, smart glasses, a helmet, an earphone, etc.

[0055] The above only describes the preferred embodiments of the present application and is not intended to limit the present application. For those skilled in the art, the present application can have various modifications and changes. Any modification, equivalent replacement, improvement, etc. within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. A method for preparing a composite material, characterized in that: The method comprises: Pre-treating the hollow glass microspheres, wherein the pre-treatment includes cleaning and drying; The pretreated hollow glass microspheres are placed in a plasma treatment device and subjected to plasma treatment at a power of 5-15 kW and a flow rate of 100-1000 ml / min of working gas for 3-20 minutes, and then dried to obtain activated hollow glass microspheres; adding the activated hollow glass microspheres to an organic solvent, adding a silane coupling agent for dispersion at a stirring speed of 300-500 r / min to obtain a dispersion liquid, adding a flexible polymer long chain and an initiator to the dispersion liquid for grafting treatment to graft the flexible polymer long chain onto the surface of the activated hollow glass microspheres, and obtaining a reaction liquid; Passing the reaction solution through a granulation device to obtain dry powder, and performing roller grinding or ball milling on the dry powder to obtain surface-modified hollow glass microspheres; and The surface-modified hollow glass microspheres are mixed with a matrix resin and an auxiliary agent to form granules to prepare a granular composite material.

2. The method for preparing a composite material according to claim 1, wherein: After the pretreated hollow glass microspheres are placed in the plasma treatment equipment, the pressure in the chamber of the plasma treatment equipment is pumped down to a vacuum degree of 10<-3 >-10<-1> Pa, and then the working gas is introduced into the chamber to perform plasma treatment.

3. The method for preparing a composite material according to claim 1, wherein: The diameter of the hollow glass microspheres is 5-20 μm, the wall thickness of the hollow glass microspheres is 0.3-2.5 μm, and the density of the hollow glass microspheres is 0.1-0.5 g / cm 3 .

4. The method for preparing a composite material according to claim 1, wherein: The silane coupling agent includes at least one of γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane; The flexible polymer long chain includes at least one of long-chain polyether, long-chain polyester and long-chain polyvinyl alcohol; The organic solvent includes at least one of acetone, dimethyl sulfoxide and ethyl acetate.

5. The method for preparing a composite material according to claim 1, wherein: The reaction solution is dried by a spray granulation device to obtain the dry powder, the drying temperature is 100-200 degrees Celsius, and the spray pressure is 0.5-2 MPa.

6. The method for preparing a composite material according to claim 1, wherein: Adding a flexible polymer long chain and an initiator to the dispersion for grafting treatment includes: After adding the flexible polymer long chain and the initiator to the dispersion, the mixture is heated and stirred in a water bath at 50-90 degrees Celsius for reaction at a stirring speed of 500-800 r / min and the reaction time is 2-5 hours.

7. The method for preparing a composite material according to claim 1, wherein: The matrix resin includes at least one of polyamide, polycarbonate, polypropylene and acrylonitrile-butadiene-styrene; The auxiliary agent includes at least one of a coupling agent, a stabilizer, a lubricant, a pigment and a filler.

8. A composite material, characterized in that The composite material is prepared by the composite material preparation method according to any one of claims 1 to 7.

9. A composite material product, characterized in that: The composite material according to claim 8 is manufactured by at least one of injection molding, extrusion and molding.

10. The composite material product according to claim 9, characterized in that: The composite article is at least a portion of a head-mounted device.

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