Graphene composite thermosetting material, and preparation method therefor and use thereof in front cover of camera device

Abstract

Disclosed in the present invention is a graphene composite thermosetting material characterized by comprising the following raw materials in parts by mass: 17-25 parts of an unsaturated polyester resin; 0.5-3 parts of a toughening agent; 5-13 parts of polystyrene; 0.3-0.5 parts of an organic peroxide; 10-40 parts of a graphene material; 15-35 parts of aluminum hydroxide; 0.5-0.06 parts of calcium hydroxide; and 10-35 parts of carbon fiber. Further disclosed are a preparation method for the graphene composite thermosetting material and the use thereof in a front cover of a camera device. Compared with the prior art, the present invention can improve the thermal conductivity while ensuring high strength.

Description

A graphene composite thermosetting material, its preparation method, and its application in the front cover of a camera device. Technical Field

[0001] This invention relates to the field of composite material technology, specifically to a graphene composite thermosetting material, its preparation method, and its application in the front cover of a camera device. Background Technology

[0002] In existing technologies, cameras can be used in fields such as intelligent transportation, security monitoring, and live streaming of cultural tourism and sports. Their main function is ultra-high-definition shooting, combined with features such as large aperture, ultra-wide angle, and ultra-low dispersion lenses. However, during use, the internal components of the camera generate a large amount of heat. This heat cannot be dissipated within the camera, easily leading to overheating and damage, reducing its lifespan, and compromising the normal operation of the device.

[0003] Therefore, the applicant's earlier Chinese utility model patent application, CN202320225975.9 (publication number CN219322499U), describes a camera device that uses a front cover made of graphene plastic to transfer heat in a timely manner.

[0004] However, for composite materials that can improve thermal conductivity, the strength decreases due to the increase in thermally conductive fillers. Summary of the Invention

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

[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 in the front cover of a camera device.

[0008] The technical solution adopted by this invention to solve the first technical problem mentioned above is: a graphene composite thermosetting material, characterized in that, by mass fraction, its raw materials include:

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

[0010] Preferably, the toughening agent is a polyether ester multiblock copolymer composed of aliphatic polyether blocks and aliphatic polyester blocks, and the general formula of the polyether ester multiblock copolymer is:

[0011] Where a is any integer from 2 to 6;

[0012] b is any integer from 2 to 11;

[0013] c is any integer from 2 to 4;

[0014] d is any integer from 13 to 68;

[0015] e and f are determined by the content of aliphatic polyester blocks and aliphatic polyether blocks, respectively;

[0016] The number-average molecular weight of the polyether ester multiblock copolymer is 8,000 to 50,000 g / mol.

[0017] 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%.

[0018] Furthermore, the aliphatic polyester block is at least one of polyethylene adipate, polybutylene succinate, and polyethylene tridecanoate.

[0019] Furthermore, the value of c is 2 or 4.

[0020] Preferably, the organic peroxide is at least one selected from di-tert-butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, benzoyl peroxide, and tert-butyl peroxide.

[0021] Preferably, the graphene material is graphite powder containing single-layer graphene and multi-layer graphene, wherein the single-layer graphene accounts for 2-5 wt% and the multi-layer graphene accounts for 10-15 wt%.

[0022] Preferably, the carbon fiber is at least one of polyacrylonitrile-based carbon fiber and pitch-based carbon fiber, and the fiber length of the carbon fiber is 3 to 15 mm.

[0023] The technical solution adopted by the present invention to solve the second technical problem mentioned above is: a method for preparing the above-mentioned graphene composite thermosetting material, characterized by comprising the following steps:

[0024] (1) The toughening agent is dispersed with unsaturated polyester resin to obtain a first dispersion, and the toughening agent is dispersed with polystyrene to obtain a second dispersion;

[0025] (2) Mix the first dispersion and the second dispersion, then add organic peroxide and calcium hydroxide and stir to obtain a colloid;

[0026] (3) Aluminum hydroxide and graphene materials are mixed to obtain a mixed filler;

[0027] (4) Knead the mixed filler and colloid, and then add carbon fiber and knead further to obtain a kneaded compound;

[0028] (5) Place the kneaded material into a mold to form the desired graphene composite thermosetting material.

[0029] The technical solution adopted by the present invention to solve the third technical problem mentioned above is: the application of the above-mentioned graphene composite thermosetting material on the front cover of a camera device.

[0030] Preferably, the camera device includes a housing and a camera module disposed inside the housing. The housing includes a front cover and a rear cover that are connected in a front-to-back manner. The front cover is made of the graphene composite thermosetting material and surrounds the outer periphery of the camera module.

[0031] Compared with the prior art, the advantages of the present invention are as follows:

[0032] (1) This invention uses unsaturated polyester resin as the molding matrix resin, polyether ester multiblock copolymer as the toughening agent, polystyrene as the low shrinkage agent, organic peroxide as the curing agent, graphene material as the thermally conductive filler, aluminum hydroxide as the flame retardant filler, calcium hydroxide as the thickener, and carbon fiber as the reinforcing filler. The composition is made into a lumpy mud through dispersion and mixing processes and finally molded to obtain the desired graphene composite thermosetting material, which can improve thermal conductivity while ensuring high strength.

[0033] (2) The toughening agent of the present invention is a polyether ester multiblock copolymer composed of aliphatic polyether blocks and aliphatic polyester blocks. On the one hand, the aliphatic polyether blocks have good compatibility with the unsaturated polyester resin matrix, providing good flexibility and impact strength. Thus, the toughening agent of the present invention can be well dissolved in the unsaturated polyester resin matrix and uniformly dispersed. On the other hand, during the curing process, the polyether ester multiblock copolymer can undergo microphase separation, and a small amount of polyether ester multiblock copolymer can achieve the toughening effect.

[0034] When 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. The toughness, impact strength and tensile strength of the cured unsaturated polyester resin are significantly improved. It can be applied to various components that require heat dissipation, such as the front cover of a camera device, LED lights, inverter heat dissipation housings and vehicle light housings. Attached Figure Description

[0035] Figure 1 is a three-dimensional structural schematic diagram of an embodiment of the camera device of the present invention;

[0036] Figure 2 is a three-dimensional exploded view of Figure 1;

[0037] Figure 3 is a longitudinal sectional view of Figure 1. Detailed Implementation

[0038] The present invention will be further described in detail below with reference to the embodiments.

[0039] Example 1:

[0040] The toughening agent used in this embodiment is a polyether ester multiblock copolymer mBCP-1 composed of polyethylene tridecanoate (PEB) and polyethylene oxide (PEO, with a molecular weight of 2000 g / mol); wherein the content of PEB is 22 wt%, the content of PEO is 78 wt%, and the molecular weight is 18.7 kg / mol.

[0041] The unsaturated polyester resin used in this embodiment is isophthalic-neopentyl glycol resin (manufacturer: Xinyang Technology Group, model: 9058);

[0042] The organic peroxide used in this embodiment is 1,1-bis(tert-butylperoxide)-3,3,5-trimethylcyclohexane;

[0043] The graphene material used in this embodiment is graphite micro powder containing 2 wt% single-layer graphene and 10 wt% multilayer graphene.

[0044] The carbon fiber used in this embodiment is PAN-type carbon fiber with a fiber length of 6mm;

[0045] (1) Toughening agent dispersion:

[0046] 0.3 parts by weight of toughening agent and 17 parts by weight of unsaturated polyester resin were mixed and dispersed in a high-speed disperser (3200 rpm) for 10 minutes to obtain the first dispersion;

[0047] 0.2 parts by weight of toughening agent and 10 parts by weight of polystyrene were mixed and dispersed in a high-speed disperser (3200 rpm) for 10 minutes to obtain a second dispersion;

[0048] (2) Colloidal mixing:

[0049] The first and second dispersions were mixed, and 0.33 parts by weight of organic peroxide and 0.47 parts by weight of calcium hydroxide were added. The mixture was stirred at room temperature for 10 minutes to obtain a colloid.

[0050] (3) Filler mixing:

[0051] 20 parts by weight of aluminum hydroxide and 31.7 parts by weight of graphene material were mixed for 5 minutes using a high-speed mixer (stirring speed 1200 rpm) to obtain a mixed filler.

[0052] (4) Kneading the dough:

[0053] The mixed filler and colloid are placed in a kneader and kneaded thoroughly for 25 minutes. Then, 20 parts by weight of carbon fiber are added and kneaded for another 10 minutes to obtain a kneaded compound. During the kneading stage, the temperature inside the kneader is kept below 40°C.

[0054] (5) Molding:

[0055] First, adjust the mold temperature to 145℃, then place the kneaded material into the mold, and mold it under a clamping pressure of 120MPa to obtain the desired graphene composite thermosetting material.

[0056] Example 2:

[0057] The toughening agent used in this embodiment is a polyether ester multiblock copolymer mBCP-1 composed of polyethylene tridecanoate (PEB) and polyethylene oxide (PEO, with a molecular weight of 2000 g / mol); wherein the content of PEB is 22 wt%, the content of PEO is 78 wt%, and the molecular weight is 18.7 kg / mol.

[0058] The unsaturated polyester resin used in this embodiment is isophenylene-neopentyl glycol resin;

[0059] The organic peroxide used in this embodiment is 1,1-bis(tert-butylperoxide)-3,3,5-trimethylcyclohexane;

[0060] The graphene material used in this embodiment is graphite micro powder containing 2 wt% single-layer graphene and 10 wt% multilayer graphene.

[0061] The carbon fiber used in this embodiment is PAN-type carbon fiber with a fiber length of 6mm;

[0062] (1) Toughening agent dispersion:

[0063] 1.5 parts by weight of toughening agent and 20 parts by weight of unsaturated polyester resin were mixed and dispersed in a high-speed disperser (3200 rpm) for 10 minutes to obtain the first dispersion;

[0064] 0.5 parts by weight of toughening agent and 10 parts by weight of polystyrene were mixed and dispersed in a high-speed disperser (3200 rpm) for 10 minutes to obtain a second dispersion;

[0065] (2) Colloidal mixing:

[0066] The first and second dispersions were mixed, and 0.33 parts by weight of organic peroxide and 0.47 parts by weight of calcium hydroxide were added. The mixture was stirred at room temperature for 10 minutes to obtain a colloid.

[0067] (3) Filler mixing:

[0068] 21.5 parts by weight of aluminum hydroxide and 31.7 parts by weight of graphene material were mixed for 5 minutes using a high-speed mixer (stirring speed 1200 rpm) to obtain a mixed filler.

[0069] (4) Kneading the dough:

[0070] The mixed filler and colloid are placed in a kneader and kneaded thoroughly for 25 minutes. Then, 20 parts by weight of carbon fiber are added and kneaded for another 10 minutes to obtain a kneaded compound. During the kneading stage, the temperature inside the kneader is kept below 40°C.

[0071] (5) Molding:

[0072] First, adjust the mold temperature to 145℃, then place the kneaded material into the mold, and mold it under a clamping pressure of 120MPa to obtain the desired graphene composite thermosetting material.

[0073] Example 3:

[0074] The toughening agent used in this embodiment is a polyether ester multiblock copolymer mBCP-1 composed of polyethylene tridecanoate (PEB) and polyethylene oxide (PEO, with a molecular weight of 2000 g / mol); wherein the content of PEB is 22 wt%, the content of PEO is 78 wt%, and the molecular weight is 18.7 kg / mol.

[0075] The unsaturated polyester resin used in this embodiment is isophenylene-neopentyl glycol resin;

[0076] The organic peroxide used in this embodiment is 1,1-bis(tert-butylperoxide)-3,3,5-trimethylcyclohexane;

[0077] The graphene material used in this embodiment is graphite micro powder containing 2 wt% single-layer graphene and 10 wt% multilayer graphene.

[0078] The carbon fiber used in this embodiment is PAN-type carbon fiber with a fiber length of 6mm;

[0079] (1) Toughening agent dispersion:

[0080] Two parts by weight of toughening agent and 25 parts by weight of unsaturated polyester resin were mixed and dispersed for 10 minutes using a high-speed disperser (3200 rpm) to obtain the first dispersion.

[0081] One part by weight of toughening agent and ten parts by weight of polystyrene were mixed and dispersed in a high-speed disperser (3200 rpm) for 10 minutes to obtain a second dispersion;

[0082] (2) Colloidal mixing:

[0083] Mix the first dispersion and the second dispersion, and add 0.4 parts by mass of organic peroxide and 0.48 parts by mass of calcium hydroxide. Stir at room temperature for 10 minutes to obtain a colloid.

[0084] (3) Filler mixing:

[0085] 20 parts by weight of aluminum hydroxide and 21.12 parts by weight of graphene material were mixed for 5 minutes using a high-speed mixer (stirring speed 1200 rpm) to obtain a mixed filler.

[0086] (4) Kneading the dough:

[0087] The mixed filler and colloid are placed in a kneader and kneaded thoroughly for 25 minutes. Then, 20 parts by weight of carbon fiber are added and kneaded for another 10 minutes to obtain a kneaded compound. During the kneading stage, the temperature inside the kneader is kept below 40°C.

[0088] (5) Molding:

[0089] First, adjust the mold temperature to 145℃, then place the kneaded material into the mold, and mold it under a clamping pressure of 120MPa to obtain the desired graphene composite thermosetting material.

[0090] Comparative Example 1:

[0091] The difference from Example 1 is that no toughening agent was added in this comparative example.

[0092] Comparative Example 2:

[0093] The difference from Example 1 is that the toughening agent used in this comparative example is a polyether ester multiblock copolymer mBCP-2 composed of polyethylene terephthalate (PET) and polytetrahydrofuran (PTMO, with a molecular weight of 2000 g / mol); wherein the PET content is 33 wt% and the PTMO content is 67 wt%.

[0094] During the dispersion process of the toughening agent and unsaturated polyester resin, it was found that mBCP-2 is incompatible with the unsaturated polyester resin, making it difficult to toughen and modify the unsaturated polyester resin.

[0095] The performance testing equipment and methods are shown in Table 1.

[0096] Table 1

[0097] The test results of the graphene composite thermosetting materials obtained in all the above embodiments and Comparative Example 1 are shown in Table 2.

[0098] Table 2

[0099] As can be seen from the table above:

[0100] (1) Tensile strength can be improved by adding the toughening agent used in this invention while keeping the thermal conductivity constant.

[0101] (2) The increase in elongation at break indicates that the material has better ductility than the material without the addition; at the same time, the decrease in flexural modulus highlights that the material with the addition has a certain degree of elasticity, and when it is impacted, the impact energy can be more effectively absorbed by a larger area around the impact point.

[0102] (3) Due to the improvement of bending strength and elasticity, the relative impact strength is improved.

[0103] The aforementioned graphene composite thermosetting material can be applied to various components that require heat dissipation, such as the front cover of a camera device, LED lights, inverter heat dissipation housings, and vehicle headlight housings. In this embodiment, the application to the front cover of a camera device is used as an example for detailed explanation.

[0104] Figures 1 to 3 show a preferred embodiment of the camera device of the present invention. The camera device includes a housing 1, a camera module 2, a semiconductor cooling chip 3, a heat sink 4, an exhaust fan 5, and a heat insulation pad 6.

[0105] The housing 1 includes a front cover 11 and a rear cover 12 that are connected front to back, and the junction 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 opened on the side wall of the rear cover 12, and an air outlet 122 is opened 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.

[0106] The camera module 2 is located in the middle of the inner cavity of the front cover 11. In other words, the front cover 11 surrounds the outer periphery of the camera module 2. This way, when the front cover 11 cools down or heats up, it can create a suitable working environment for the entire camera module 2.

[0107] The semiconductor cooling chip 3 is ring-shaped and is located in the periphery of the inner cavity of the front cover 11, and surrounds the outer periphery of the camera module 2, with its front end wall tightly attached to the front end wall of the front cover 11.

[0108] The heat sink 4 is located inside the rear cover 12, and its front wall is in close contact with the rear wall of the aforementioned semiconductor cooling chip 3.

[0109] The exhaust fan 5 is located inside the rear cover 12 and at the rear of the radiator 4. The exhaust fan 5 can draw air in from the air inlet 121 and exhaust it through the air outlet 122, thereby accelerating the heat dissipation efficiency of the radiator 4.

[0110] The heat insulation pad 6 is placed between the heat sink 4 and the camera module 2 to prevent the heat or cold energy of the heat sink 4 from being transferred to the camera module 2.

[0111] It should be noted that one end of the thermoelectric cooler 3 is the hot end and the other end is the cold end. The hot end and cold end can be switched by reversing the positive and negative terminals: when the positive and negative terminals of the thermoelectric cooler 3 are connected in the correct direction, its front end is the cold end, which can cool the front cover 11; when the positive and negative terminals of the thermoelectric cooler 3 are reversed, its front end is the hot end, which can heat the front cover 11.

Claims

1. A graphene composite thermoset material, characterized in that, The raw materials thereof include, by mass parts:

2. The graphene composite thermoset material of claim 1, wherein: The unsaturated polyester resin is at least one of the following: phthalic anhydride-neopentyl glycol resin, tetrahydrophthalic anhydride-neopentyl glycol resin, phthalic anhydride-diphenyl glycol resin, phthalic anhydride-diphenyl glycol resin, phthalic anhydride-diphenyl glycol resin, and phthalic anhydride-diphenyl glycol resin.

3. The graphene composite thermoset material of claim 1, wherein: The toughening agent is a polyether ester multi-block copolymer composed of aliphatic polyether blocks and aliphatic polyester blocks, the general formula of the polyether ester multi-block copolymer is: Where a is any integer from 2 to 6; b is any integer from 2 to 11; c is any integer from 2 to 4; d is any integer from 13 to 68; e and f are determined by the content of aliphatic polyester blocks and aliphatic polyether blocks, respectively; The number-average molecular weight of the polyether ester multiblock copolymer is 8,000 to 50,000 g / mol.

4. The graphene composite thermoset material of claim 3, wherein: The aliphatic polyether block content is 30-85 wt%, the aliphatic polyester block content is 15-70 wt%, and the sum of the aliphatic polyether block and the aliphatic polyester block content is 100 wt%.

5. The graphene composite thermoset material of claim 3, wherein: The aliphatic polyester block is at least one of polyethylene adipate, polybutylene succinate, and polyethylene tridecanoate.

6. The graphene composite thermoset material of claim 3, wherein: The value of c is 2 or 4.

7. The graphene composite thermoset material of claim 1, wherein: 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 peroxide. The graphene material is graphite powder containing single-layer graphene and multi-layer graphene, wherein the single-layer graphene accounts for 2-5 wt% and the multi-layer graphene accounts for 10-15 wt%. The carbon fiber is at least one of polyacrylonitrile-based carbon fiber and pitch-based carbon fiber, and the fiber length of the carbon fiber is 3 to 15 mm.

8. A method of producing the graphene composite thermoset material according to any one of claims 1 to 7, characterized in that It includes the following steps: (1) The toughening agent is dispersed with unsaturated polyester resin to obtain a first dispersion, and the toughening agent is dispersed with polystyrene to obtain a second dispersion; (2) Mix the first dispersion and the second dispersion, then add organic peroxide and calcium hydroxide and stir to obtain a colloid; (3) Aluminum hydroxide and graphene materials are mixed to obtain a mixed filler; (4) Knead the mixed filler and colloid, and then add carbon fiber and knead further to obtain a kneaded compound; (5) Place the kneaded material into a mold to form the desired graphene composite thermosetting material.

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

10. Use according to claim 9, characterized in that: The camera device includes a housing (1) and a camera module (2) disposed inside the housing (1). The housing (1) includes a front cover (11) and a rear cover (12) that are connected in a front-to-back manner. The front cover (11) is made of the graphene composite thermosetting material and surrounds the outer periphery of the camera module (2).

Images