Graphene composite thermosetting material, preparation method thereof and application of graphene composite thermosetting material to front cover of camera device

Abstract

The invention discloses a graphene composite thermosetting material which is characterized by comprising the following raw materials in parts by mass: 17-25 parts of unsaturated polyester resin; 0.5 to 3 parts of a toughening agent; 5 to 13 parts of polystyrene; 0.3 to 0.5 part of an organic peroxide; 10 to 40 parts of a graphene material; 15 to 35 parts of aluminum hydroxide; 0.5 to 0.06 part of calcium hydroxide; and 10-35 parts of carbon fiber. The invention further discloses a preparation method of the graphene composite thermosetting material and application of the graphene composite thermosetting material to a front cover of a camera device. Compared with the prior art, the heat conductivity can be improved while high strength is guaranteed.

Description

Technical Field

[0001] The invention relates to the technical field of composite materials, and in particular to a graphene composite thermosetting material and a preparation method thereof, and application of the graphene composite thermosetting material to a front cover of a camera device. Background Art

[0002] In the prior art, cameras can be used in the fields of intelligent transportation, security monitoring, cultural tourism, sports and slow live broadcast, etc. The main function is ultra-high-definition shooting, combined with large aperture, ultra-wide angle, ultra-low dispersion lens and other features. However, when the camera is in use, a large amount of heat is generated when the internal components of the camera are running. This heat cannot be discharged inside the camera, which can easily cause the internal temperature of the camera to be too high, causing damage, reducing its service life, and failing to ensure the normal operation of the device.

[0003] To this end, the applicant's previously applied Chinese utility model patent with patent application number CN202320225975.9 (publication number CN219322499U) is a camera device that uses graphene plastic to make a front cover to transfer heat in a timely manner.

[0004] However, for composite materials that can improve thermal conductivity, the increase in thermally conductive fillers leads to a decrease in strength. Summary of the invention

[0005] The first technical problem to be solved by the present invention is to provide a graphene composite thermosetting material based on the current status of the prior art, which can improve thermal conductivity while ensuring high strength.

[0006] The second technical problem to be solved by the present invention is to provide a method for preparing the above-mentioned graphene composite thermosetting material.

[0007] The third technical problem to be solved by the present invention is to provide an application of the above-mentioned graphene composite thermosetting material on the front cover of a camera device.

[0008] The technical solution adopted by the present invention to solve the above-mentioned first technical problem is: a graphene composite thermosetting material, characterized in that, by weight, its raw materials include: Unsaturated polyester resin 17-25 parts; Toughening agent 0.5~3 parts; Polystyrene 5-13 parts; 0.3~0.5 parts of organic peroxide; 10~40 parts of graphene material; 15-35 parts of aluminum hydroxide; 0.5~0.06 parts of calcium hydroxide; 10~35 parts of carbon fiber.

[0009] Preferably, the unsaturated polyester resin is at least one of o-phthalic / isophthalic / terephthalic-neopentyl glycol resin, tetrahydrophthalic anhydride-neopentyl glycol resin, o-phthalic / isophthalic / terephthalic acid resin, o-phthalic / isophthalic / terephthalic-propylene glycol resin, and o-phthalic / isophthalic / terephthalic-dipropylene glycol resin.

[0010] Preferably, the toughening agent is a polyetherester multi-block copolymer composed of aliphatic polyether blocks and aliphatic polyester blocks, and the general formula of the polyetherester multi-block copolymer is: ; Wherein, a is any integer from 2 to 6; b is any integer between 2 and 11; c is any integer from 2 to 4; d is any integer between 13 and 68; e and f are determined by the contents of aliphatic polyester block and aliphatic polyether block, respectively; The number average molecular weight of the polyetherester multi-block copolymer is 8000-50000 g / mol.

[0011] Furthermore, the content of the aliphatic polyether block is 30-85 wt %, the content of the aliphatic polyester block is 15-70 wt %, and the sum of the contents of the aliphatic polyether block and the aliphatic polyester block is 100 wt %.

[0012] Furthermore, the aliphatic polyester block is at least one of polyethylene adipate, polybutylene succinate, and polyethylene tridecanoate.

[0013] Furthermore, the value of c is 2 or 4.

[0014] Preferably, the organic peroxide is at least one of di-tert-butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, benzoyl peroxide, and tert-butyl perbenzoate.

[0015] Preferably, the graphene material is graphite powder containing single-layer graphene and multi-layer graphene, the single-layer graphene accounts for 2-5wt%, and the multi-layer graphene accounts for 10-15wt%.

[0016] Preferably, the carbon fiber is at least one of polyacrylonitrile-based carbon fiber and asphalt-based carbon fiber, and the fiber length of the carbon fiber is 3 to 15 mm.

[0017] The technical solution adopted by the present invention to solve the above second technical problem is: a method for preparing the above graphene composite thermosetting material, characterized by comprising the following steps: (1) dispersing the toughening agent and the unsaturated polyester resin to obtain a first dispersion, and dispersing the toughening agent and the polystyrene to obtain a second dispersion; (2) mixing the first dispersion and the second dispersion, and then adding an organic peroxide and calcium hydroxide and stirring to obtain a colloid; (3) mixing aluminum hydroxide and graphene material to obtain a mixed filler; (4) kneading the mixed filler and the colloid, and then adding the carbon fiber and further kneading to obtain a kneaded product; (5) Placing the kneaded product into a mold to form the desired graphene composite thermosetting material.

[0018] The technical solution adopted by the present invention to solve the third technical problem is: an application of the above-mentioned graphene composite thermosetting material on the front cover of a camera device.

[0019] Preferably, the camera device includes a shell and a camera module arranged inside the shell, the shell includes a front cover and a rear cover that are matched and connected front and back, the front cover is made of the graphene composite thermosetting material and surrounds the periphery of the camera module.

[0020] Compared with the prior art, the advantages of the present invention are: (1) The present invention uses unsaturated polyester resin as a molding matrix resin, polyether ester multi-block copolymer as a toughening agent, polystyrene as a low shrinkage agent, organic peroxide as a curing agent, graphene material as a thermal conductive filler, aluminum hydroxide as a flame retardant filler, calcium hydroxide as a thickener, and carbon fiber as a reinforcing filler. The composition is made into a mass mud by a dispersion and mixing process and finally molded into the desired graphene composite thermosetting material, which can improve thermal conductivity while ensuring high strength; (2) The toughening agent of the present invention is a polyether ester multi-block copolymer composed of an aliphatic polyether block and an aliphatic polyester block. On the one hand, the aliphatic polyether block has good compatibility with the unsaturated polyester resin matrix, providing good flexibility and impact strength. Therefore, the toughening agent of the present invention can be well dissolved in the unsaturated polyester resin matrix and evenly dispersed. On the other hand, during the curing process, the polyether ester multi-block copolymer can undergo microphase separation, and a relatively small amount of the polyether ester multi-block copolymer can achieve a toughening effect. After the toughening agent of the present invention is added to the unsaturated polyester resin matrix, the energy dissipation pathway is improved due to the microphase separation generated in the system, and the toughness, impact strength and tensile strength of the unsaturated polyester resin cured product are significantly improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 is a schematic diagram of the three-dimensional structure of an embodiment of a camera device of the present invention; Figure 2 for Figure 1 Schematic diagram of the three-dimensional decomposition of Figure 3 for Figure 1 Longitudinal section view of . DETAILED DESCRIPTION

[0022] The present invention is further described in detail below with reference to the embodiments. Embodiment 1:

[0023] The toughening agent used in this embodiment is a polyether ester multi-block copolymer mBCP-1 composed of polyethylene tridecanoate (PEB) and polyethylene oxide (PEO, molecular weight of 2000 grams per mol); wherein the PEB content is 22wt%, the PEO content is 78wt%, and the molecular weight is 18.7 kilograms per mol (kg / mol); The unsaturated polyester resin used in this embodiment is isophthalic acid-neopentyl glycol resin (manufactured by Xinyang Technology Group, model 9058); The organic peroxide used in this example is 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane; The graphene material used in this embodiment is graphite powder containing 2wt% single-layer graphene and 10wt% multi-layer graphene; The carbon fiber used in this embodiment is PAN type carbon fiber, and the fiber length is 6mm; (1) Toughening agent dispersion: 0.3 parts by mass of a toughening agent and 17 parts by mass of an unsaturated polyester resin were mixed and dispersed in a high-speed disperser (rotation speed 3200 rpm) for 10 minutes to obtain a first dispersion; 0.2 parts by mass of toughening agent and 10 parts by mass of polystyrene were mixed and dispersed in a high-speed disperser (rotation speed 3200 rpm) for 10 minutes to obtain a second dispersion; (2) Colloid mixing: The first dispersion and the second dispersion were mixed, and 0.33 parts by mass of organic peroxide and 0.47 parts by mass of calcium hydroxide were added, and stirred at room temperature for 10 minutes to obtain a colloid; (3) Filler mixing: 20 parts by mass of aluminum hydroxide and 31.7 parts by mass of graphene material were mixed for 5 minutes using a high mixing device (stirring speed 1200 rpm) to obtain a mixed filler; (4) Kneading of dough: The mixed filler and colloid were put into a kneader and kneaded for 25 minutes, and then 20 parts by mass of carbon fiber were added and kneaded for 10 minutes to obtain a kneaded product. During the kneading stage, the temperature in the kneader was maintained at less than 40°C. (5) Molding: First, the mold temperature is adjusted to 145° C., and then the kneaded material is placed in the mold, and molded at a mold pressure of 120 MPa to obtain the desired graphene composite thermosetting material. Embodiment 2:

[0024] The toughening agent used in this embodiment is a polyether ester multi-block copolymer mBCP-1 composed of polyethylene tridecanoate (PEB) and polyethylene oxide (PEO, molecular weight of 2000 grams per mol); wherein the PEB content is 22wt%, the PEO content is 78wt%, and the molecular weight is 18.7 kilograms per mol (kg / mol); The unsaturated polyester resin used in this embodiment is isophthalic acid-neopentyl glycol resin; The organic peroxide used in this example is 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane; The graphene material used in this embodiment is graphite powder containing 2wt% single-layer graphene and 10wt% multi-layer graphene; The carbon fiber used in this embodiment is PAN type carbon fiber, and the fiber length is 6mm; (1) Toughening agent dispersion: 1.5 parts by mass of a toughening agent and 20 parts by mass of an unsaturated polyester resin were mixed and dispersed in a high-speed disperser (rotation speed 3200 rpm) for 10 minutes to obtain a first dispersion; 0.5 parts by mass of toughening agent and 10 parts by mass of polystyrene were mixed and dispersed in a high-speed disperser (rotation speed 3200 rpm) for 10 minutes to obtain a second dispersion; (2) Colloid mixing: The first dispersion and the second dispersion were mixed, and 0.33 parts by mass of organic peroxide and 0.47 parts by mass of calcium hydroxide were added, and stirred at room temperature for 10 minutes to obtain a colloid; (3) Filler mixing: 21.5 parts by mass of aluminum hydroxide and 31.7 parts by mass of graphene material were mixed for 5 minutes using a high mixing device (stirring speed 1200 rpm) to obtain a mixed filler; (4) Kneading of dough: The mixed filler and colloid were put into a kneader and kneaded for 25 minutes, and then 20 parts by mass of carbon fiber were added and kneaded for 10 minutes to obtain a kneaded product. During the kneading stage, the temperature in the kneader was maintained at less than 40°C. (5) Molding: First, the mold temperature is adjusted to 145° C., and then the kneaded material is placed in the mold, and molded at a mold pressure of 120 MPa to obtain the desired graphene composite thermosetting material. Embodiment 3:

[0025] The toughening agent used in this embodiment is a polyether ester multi-block copolymer mBCP-1 composed of polyethylene tridecanoate (PEB) and polyethylene oxide (PEO, molecular weight of 2000 grams per mol); wherein the PEB content is 22wt%, the PEO content is 78wt%, and the molecular weight is 18.7 kilograms per mol (kg / mol); The unsaturated polyester resin used in this embodiment is isophthalic acid-neopentyl glycol resin; The organic peroxide used in this example is 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane; The graphene material used in this embodiment is graphite powder containing 2wt% single-layer graphene and 10wt% multi-layer graphene; The carbon fiber used in this embodiment is PAN type carbon fiber, and the fiber length is 6mm; (1) Toughening agent dispersion: 2 parts by mass of a toughening agent and 25 parts by mass of an unsaturated polyester resin were mixed and dispersed in a high-speed disperser (rotation speed 3200 rpm) for 10 minutes to obtain a first dispersion; 1 part by mass of toughening agent and 10 parts by mass of polystyrene were mixed and dispersed in a high-speed disperser (rotation speed 3200 rpm) for 10 minutes to obtain a second dispersion; (2) Colloid mixing: The first dispersion and the second dispersion are mixed, and 0.4 parts by mass of an organic peroxide and 0.48 parts by mass of calcium hydroxide are added, and stirred at room temperature for 10 minutes to obtain a colloid; (3) Filler mixing: 20 parts by mass of aluminum hydroxide and 21.12 parts by mass of graphene material were mixed for 5 minutes using a high mixing device (stirring speed 1200 rpm) to obtain a mixed filler; (4) Kneading of dough: The mixed filler and colloid were put into a kneader and kneaded for 25 minutes, and then 20 parts by mass of carbon fiber were added and kneaded for 10 minutes to obtain a kneaded product. During the kneading stage, the temperature in the kneader was maintained at less than 40°C. (5) Molding: First, the mold temperature is adjusted to 145° C., and then the kneaded material is placed in the mold, and molded at a mold pressure of 120 MPa to obtain the desired graphene composite thermosetting material.

[0026] Comparative Example 1: The difference from Example 1 is that no toughening agent is added in this comparative example.

[0027] Comparative Example 2: The difference from Example 1 is that the toughening agent used in this comparative example is a polyether ester multi-block copolymer mBCP-2 composed of polyethylene terephthalate (PET) and polytetramethylene oxide (PTMO, molecular weight of 2000 g / mol); wherein the PET content is 33wt% and the PTMO content is 67wt%; During the dispersion process of the toughening agent and the unsaturated polyester resin, it was found that mBCP-2 was incompatible with the unsaturated polyester resin, so it was difficult to toughen the unsaturated polyester resin.

[0028] The performance test equipment and methods are shown in Table 1.

[0029] Table 1

[0030] The test results of the graphene composite thermosetting materials obtained in all the above embodiments and Comparative Example 1 are shown in Table 2.

[0031] Table 2

[0032] It can be seen from the above table: (1) When the thermal conductivity remains unchanged, the tensile strength can be improved by adding the toughening agent used in the present invention; (2) The increase in elongation at break indicates that the material has better ductility than the material without additives. At the same time, the decrease in bending modulus highlights that the material has a certain elasticity after addition. When impacted, the impact energy can be more effectively absorbed by a larger area around the impact point. (3) Due to the increase in bending strength and elasticity, the relative impact strength is improved.

[0033] The graphene composite thermosetting material can be applied to the front cover of a camera device.

[0034] like Figures 1 to 3 FIG. 1 is a preferred embodiment of the camera device of the present invention, wherein the camera device comprises a housing 1 , a camera module 2 , a semiconductor cooling sheet 3 , a radiator 4 , an exhaust fan 5 and a heat insulation pad 6 .

[0035] The housing 1 includes a front cover 11 and a rear cover 12 which are connected front and back, and the joint of the front cover 11 and the rear cover 12 is sealed by a sealing ring 13. Specifically, a lens 111 is installed on the front end wall of the front cover 11, and the lens 111 faces the lens of the camera module 2 described below; an air inlet 121 is provided on the side wall of the rear cover 12, and an air outlet 122 is provided on the rear end wall of the rear cover 12. In this embodiment, the front cover 11 is made of the above-mentioned graphene composite thermosetting material, which can improve thermal conductivity while ensuring high strength.

[0036] The camera module 2 is arranged in the middle position of the inner cavity of the front cover 11, that is, the front cover 11 surrounds the outer periphery of the camera module 2, so that when the front cover 11 cools down or heats up, it can create a working environment with suitable temperature for the entire camera module 2.

[0037] The semiconductor cooling sheet 3 is annular in shape, disposed around the inner cavity of the front cover 11 , and surrounding the outer periphery of the camera module 2 , with its front end wall in close contact with the front end wall of the front cover 11 .

[0038] The radiator 4 is located in the rear cover 12 , and its front end wall is in close contact with the rear end wall of the semiconductor cooling plate 3 .

[0039] The exhaust fan 5 is disposed in the rear cover 12 and is located at the rear side of the radiator 4 . The exhaust fan 5 can inhale air from the air inlet 121 and discharge it through the air outlet 122 , thereby accelerating the heat dissipation efficiency of the radiator 4 .

[0040] The heat insulation pad 6 is separated between the radiator 4 and the camera module 2 to prevent the heat or cold of the radiator 4 from being transferred to the camera module 2 .

[0041] It should be noted that one end of the semiconductor refrigeration chip 3 is a hot end and the other end is a cold end. The hot end and the cold end can be converted by reversing the positive and negative poles: when the positive and negative poles of the semiconductor refrigeration chip 3 are positively connected, its front end is a cold end, which can cool the front cover 11; when the positive and negative poles of the semiconductor refrigeration chip 3 are reversed, its front end is a hot end, which can heat the front cover 11.

Claims

1. A graphene composite thermosetting material, characterized in that: The raw materials include: Unsaturated polyester resin 17-25 parts; Toughening agent 0.5~3 parts; Polystyrene 5-13 parts; 0.3~0.5 parts of organic peroxide; 10~40 parts of graphene material; 15-35 parts of aluminum hydroxide; 0.5~0.06 parts of calcium hydroxide; 10~35 parts of carbon fiber.

2. The graphene composite thermosetting material according to claim 1, characterized in that: The unsaturated polyester resin is at least one of o-phthalate / isophthalate / terephthalate-neopentyl glycol resin, tetrahydrophthalic anhydride-neopentyl glycol resin, o-phthalate / isophthalate / terephthalate / dicarboxylic acid resin, o-phthalate / isophthalate / terephthalate-propylene glycol resin, and o-phthalate / isophthalate / terephthalate-dipropylene glycol resin.

3. The graphene composite thermosetting material according to claim 1, characterized in that: The toughening agent is a polyether ester multi-block copolymer composed of aliphatic polyether blocks and aliphatic polyester blocks, and the general formula of the polyether ester multi-block copolymer is: ； Wherein, a is any integer from 2 to 6; b is any integer between 2 and 11; c is any integer from 2 to 4; d is any integer between 13 and 68; e and f are determined by the contents of aliphatic polyester block and aliphatic polyether block, respectively; The number average molecular weight of the polyetherester multi-block copolymer is 8000-50000 g / mol.

4. The graphene composite thermosetting material according to claim 3, characterized in that: The content of the aliphatic polyether block is 30-85 wt %, the content of the aliphatic polyester block is 15-70 wt %, and the sum of the contents of the aliphatic polyether block and the aliphatic polyester block is 100 wt %.

5. The graphene composite thermosetting material according to claim 3, characterized in that: The aliphatic polyester block is at least one of polyethylene adipate, polybutylene succinate and polyethylene tridecanoate.

6. The graphene composite thermosetting material according to claim 3, characterized in that: The value of c is 2 or 4.

7. The graphene composite thermosetting material according to claim 1, characterized in that: The organic peroxide is at least one of di-tert-butyl peroxide, diisopropylbenzene peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, benzoyl peroxide, and tert-butyl perbenzoate; The graphene material is graphite powder containing single-layer graphene and multi-layer graphene, wherein the single-layer graphene accounts for 2-5wt% and the multi-layer graphene accounts for 10-15wt%; The carbon fiber is at least one of polyacrylonitrile-based carbon fiber and asphalt-based carbon fiber, and the fiber length of the carbon fiber is 3-15 mm.

8. A method for preparing a graphene composite thermosetting material according to any one of claims 1 to 7, characterized in that The following steps are included: (1) dispersing the toughening agent and the unsaturated polyester resin to obtain a first dispersion, and dispersing the toughening agent and the polystyrene to obtain a second dispersion; (2) mixing the first dispersion and the second dispersion, and then adding an organic peroxide and calcium hydroxide and stirring to obtain a colloid; (3) mixing aluminum hydroxide and graphene material to obtain a mixed filler; (4) kneading the mixed filler and the colloid, and then adding the carbon fiber and further kneading to obtain a kneaded product; (5) Placing the kneaded product into a mold to form the desired graphene composite thermosetting material.

9. Use of the graphene composite thermosetting material according to any one of claims 1 to 7 on a front cover of a camera device.

10. The use according to claim 9, characterized in that: The camera device comprises a shell (1) and a camera module (2) arranged inside the shell (1); the shell (1) comprises a front cover (11) and a rear cover (12) which are connected front and back in a matching manner; the front cover (11) is made of the graphene composite thermosetting material and surrounds the periphery of the camera module (2).

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