Graphene composite polymer toughening material of epoxy resin and preparation method of graphene composite polymer toughening material

Abstract

The invention discloses a graphene composite polymer toughening material of epoxy resin and a preparation method thereof, and belongs to the field of toughening agents, the toughening material is prepared from the following raw materials by mass: 15-40% of graphene nanosheets, 15-35% of rubber, 15-40% of polyvinyl alcohol, 5-15% of inorganic nanoparticles, 1-3% of a coupling agent, and 1-3% of an antifoaming agent. The toughening material disclosed by the invention has a remarkable toughening effect, and can be used for remarkably improving the mechanical property of the epoxy resin, improving the tensile strength of the epoxy resin, reducing the impact strength of the epoxy resin, improving the strength, toughness and ductility of a resin system and promoting the strengthening and toughening of the resin system.

Description

Technical Field

[0001] The invention relates to the field of toughening agents, and in particular to an epoxy resin graphene composite polymer toughening material and a preparation method thereof. Background Art

[0002] Epoxy resin is one of the commonly used thermosetting resin matrices in resin-based composite materials. It has the advantages of high bonding strength, low curing shrinkage, no small molecule volatiles, good process formability, good heat resistance, good chemical stability and low cost. After curing, epoxy resin has a highly cross-linked spatial network structure and a small plastic deformation space, which leads to the shortcomings of epoxy resin such as poor impact resistance, low fracture toughness, and high brittleness, which restricts its application and development in the fields of high impact resistance and high fracture resistance. Graphene has excellent mechanical, electrical and thermal properties, and is suitable as a reinforcement for resin-based composite materials. It has great potential in improving the comprehensive performance of resin-based composite materials. At present, the most commonly used toughening method for epoxy resin is to directly modify it with a toughening agent, that is, by introducing a toughening agent, the epoxy groups in the epoxy resin react with certain groups in the toughening agent to form a cross-linked network structure, and the epoxy resin changes from a single component to a multi-phase component, thereby increasing its adhesion and elongation at break, and improving its toughness. To this end, the present invention provides an epoxy resin graphene composite polymer toughening material and a preparation method thereof. Summary of the invention

[0003] In view of the above-mentioned problems, the present invention proposes a graphene composite polymer toughening material of epoxy resin and a preparation method thereof, which can significantly toughen epoxy resin and improve its mechanical properties.

[0004] In order to achieve the above-mentioned purpose, the present invention adopts the following technical solutions: A graphene composite polymer toughening material of epoxy resin, wherein the toughening material comprises the following raw materials in percentage by mass: Graphene nanosheets 15-40%, rubber 15-35%, polyvinyl alcohol 15-40%, inorganic nanoparticles 5-15%, coupling agent 1-3%, defoaming agent 1-3%; Wherein, the graphene nanosheet has a thickness of 1-5 nm and a sheet diameter of 1 μm; Wherein, the particle size of the inorganic nanoparticles is 10-500nm.

[0005] Preferably, the toughening material comprises the following raw materials in percentage by mass: Graphene nanosheets 20-35%, rubber 20-30%, polyvinyl alcohol 20-35%, inorganic nanoparticles 8.5-12%, coupling agent 1.5-2.5%, defoaming agent 1.5-2.5%.

[0006] Preferably, the toughening material comprises the following raw materials in percentage by mass: Graphene nanosheets 30%, rubber 25%, polyvinyl alcohol 30%, inorganic nanoparticles 11%, coupling agent 2%, defoaming agent 2%.

[0007] Preferably, the coupling agent is coupling agent KH550; and the defoaming agent is KS-603 epoxy silicone oil defoaming agent.

[0008] Preferably, the rubber is hydroxy-terminated nitrile rubber.

[0009] Preferably, the hydroxyl content of the hydroxy-terminated nitrile rubber is 52.5-56.0 mg / g.

[0010] Preferably, the hydroxyl content in the hydroxy-terminated nitrile rubber is 55.0 mg / g; Preferably, the inorganic nanoparticles are nano-silicon dioxide, nano-titanium dioxide, nano-calcium carbonate, or carbon nanotubes.

[0011] Preferably, the mass ratio of the nano-silicon dioxide, nano-titanium dioxide, nano-calcium carbonate and carbon nanotubes is 2:1:1:1.

[0012] Preferably, the method for preparing the epoxy resin graphene composite polymer toughening material comprises the following steps: (1) First, graphene nanosheets are added into an acetone solution with a concentration of 7.5 mol / L and mixed, the temperature is controlled at 40-50° C. during the mixing process under a vacuum environment, and then ultrasonic treatment is applied for 1.5-2 h; (2) adding polyvinyl alcohol, inorganic nanoparticles and hydroxy-terminated nitrile rubber, mixing them evenly with a high-speed stirrer at a stirring speed of 3000-4000 rpm, and then applying ultrasonic treatment for 1-1.5 hours; (3) Finally, a coupling agent and a defoaming agent are added, mixed and heated to 85-105°C, reacted for 15-20 minutes, and then kept at a constant temperature of 60-65°C for 3-5 hours to obtain the toughened material.

[0013] Due to the adoption of the above technical solution, the beneficial effects of the present invention are as follows: the toughening material of the present invention can significantly improve the mechanical properties of epoxy resin, improve the intermolecular forces within the system, graphene can improve the tensile strength of epoxy resin, refine the grains, and reduce the impact strength of epoxy resin; the present invention adds four kinds of inorganic nanoparticles that can not only form a bond with the groups of the substrate to improve the hardness and strength of the resin system. The inorganic nanoparticles also have good fluidity and can be better distributed in the gaps of the polymer bonds, thereby improving the strength, toughness and ductility of the resin system and promoting the toughening of the resin system. DETAILED DESCRIPTION

[0014] To make the purpose, technical solution and advantages of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention will be clearly and completely described below in combination with the embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0015] Carbon fiber, graphene nanosheets and inorganic nanoparticles (nano-silicon dioxide, nano-titanium dioxide, nano-calcium carbonate, carbon nanotubes) were purchased from Nanjing Xianfeng Nanomaterial Technology Co., Ltd.; coupling agent KH550 was purchased from Wuhan Huaxiang Kejie Biotechnology Co., Ltd.; rubber was purchased from Shanghai Fuyou International Trading Co., Ltd. in the form of hydroxy-terminated nitrile rubber and styrene-butadiene rubber; polyvinyl alcohol and polyvinyl pyrrolidone were purchased from TCI (Shanghai) Chemical Industry Development Co., Ltd.; phenolic resin, polyethylene, and polystyrene were purchased from Nanjing Jike Biotechnology Co., Ltd. Embodiment 1:

[0016] 1. Preparation of toughened materials The raw material table of the epoxy resin graphene composite polymer toughening material of this embodiment 1 is as follows:

[0017] Among them, the graphene nanosheet thickness is 1-5nm; the sheet diameter is 1μm; The particle size of the inorganic nanoparticles is 10-500nm.

[0018] Among them, the hydroxyl content in the hydroxy-terminated nitrile rubber is 55.0 mg / g.

[0019] The preparation method of the epoxy resin graphene composite polymer toughening material of this embodiment 1 comprises the following steps: (1) First, graphene nanosheets were added into an acetone solution with a concentration of 7.5 mol / L and mixed. The temperature was controlled at 45 °C during the mixing process under a vacuum environment, and then ultrasonic treatment was applied for 2 h. (2) adding polyvinyl alcohol, inorganic nanoparticles and hydroxy-terminated nitrile rubber, mixing them evenly with a high-speed stirrer at a stirring speed of 4000 rpm, and then applying ultrasonic treatment for 1.5 h; (3) Finally, add coupling agent and defoaming agent, mix and heat to 95°C, react for 20 minutes, and then keep at a constant temperature of 65°C for 5 hours to obtain the toughened material.

[0020] 2. Toughening of epoxy resin The toughening material prepared above is used to toughen the epoxy resin. The specific steps for preparing the toughened epoxy resin system are as follows: (1) Add the graphene composite polymer toughening material into a stirrer, add epoxy resin, ultrasonicate for 1-1.5h, and then adjust the speed to 1500-2000rpm for mixing and stirring; (2) Add curing agent and defoaming agent, increase the stirring speed to 4000rpm, stir at high speed for 10-20 minutes, then discharge the material into the mold and cure at 85℃ for 8-9 hours to obtain the toughened resin. Embodiment 2:

[0021] 1. Preparation of toughened materials The raw material table of the epoxy resin graphene composite polymer toughening material of this embodiment 2 is as follows:

[0022] Among them, the thickness of the graphene nanosheet is 1-5nm; the sheet diameter is 1μm.

[0023] The particle size of the inorganic nanoparticles is 10-500nm.

[0024] Among them, the hydroxyl content in the hydroxy-terminated nitrile rubber is 52.5 mg / g.

[0025] The preparation method of the epoxy resin graphene composite polymer toughening material of this embodiment 2 comprises the following steps: (1) First, graphene nanosheets were added into an acetone solution with a concentration of 7.5 mol / L and mixed. The temperature was controlled at 45 °C during the mixing process under a vacuum environment, and then ultrasonic treatment was applied for 1.5 h. (2) adding polyvinyl alcohol, inorganic nanoparticles and hydroxy-terminated nitrile rubber, mixing them evenly with a high-speed stirrer at a stirring speed of 3500 rpm, and then applying ultrasonic treatment for 1.5 h; (3) Finally, add coupling agent and defoaming agent, mix and heat to 105°C, react for 20 minutes, and then keep at a constant temperature of 65°C for 5 hours to obtain the toughened material.

[0026] 2. Toughening of epoxy resin The toughening material prepared above is used to toughen the epoxy resin. The specific steps for preparing the toughened epoxy resin system are as follows: (1) Add the graphene composite polymer toughening material into a stirrer, add epoxy resin, ultrasonicate for 1-1.5h, and then adjust the speed to 2000rpm for mixing and stirring; (2) Add curing agent and defoaming agent, increase the stirring speed to 4000 rpm, stir at high speed for 10-20 minutes, then discharge the material into a mold and cure at 85°C for 8-9 hours to obtain the toughened resin. Embodiment 3:

[0027] 1. Preparation of toughened materials The raw material table of the epoxy resin graphene composite polymer toughening material of this embodiment 3 is as follows:

[0028] Among them, the graphene nanosheet thickness is 1-5nm; the sheet diameter is 1μm; The particle size of the inorganic nanoparticles is 10-500nm.

[0029] Among them, the hydroxyl content in the hydroxy-terminated nitrile rubber is 56.0 mg / g.

[0030] The preparation method of the epoxy resin graphene composite polymer toughening material of this embodiment 3 comprises the following steps: (1) First, graphene nanosheets were added into an acetone solution with a concentration of 7.5 mol / L and mixed. The temperature was controlled at 40 °C during the mixing process under a vacuum environment, and then ultrasonic treatment was applied for 2 h. (2) adding polyvinyl alcohol, inorganic nanoparticles and hydroxy-terminated nitrile rubber, mixing them evenly with a high-speed stirrer at a stirring speed of 3000 rpm, and then applying ultrasonic treatment for 1.5 h; (3) Finally, add coupling agent and defoaming agent, mix and heat to 85°C, react for 15 minutes, and then keep at a constant temperature of 60°C for 4 hours to obtain the toughened material.

[0031] 2. Toughening of epoxy resin The toughening material prepared above is used to toughen the epoxy resin. The specific steps for preparing the toughened epoxy resin system are as follows: (1) Add the graphene composite polymer toughening material into a stirrer, add epoxy resin, ultrasonicate for 1-1.5h, and then adjust the speed to 2000rpm for mixing and stirring; (2) Add curing agent and defoaming agent, increase the stirring speed to 4000rpm, stir at high speed for 10-20 minutes, then discharge the material into the mold and cure at 85℃ for 8-9 hours to obtain the toughened resin. The toughened resins of the above examples 1-3 and the following comparative examples 1-7 were tested for mechanical properties at room temperature to test the influence of the toughening material on the mechanical properties of the epoxy resin; the resins of the blank groups 1-4 were cured by adding a curing agent, and the mechanical properties were tested at room temperature after curing, and the test results and statistics were recorded. The test was specifically carried out in accordance with the GB / T 1843-2008 test standard.

[0032] Table 1: Mechanical property test data of toughened resin in Examples 1-3.

[0033]

[0034] Comparative Example 1:

[0035] 1. Preparation of toughened materials The raw material table of the toughening material of the epoxy resin in this comparative example 1 is as follows:

[0036] The particle size of the inorganic nanoparticles is 10-500nm.

[0037] Among them, the hydroxyl content in the hydroxy-terminated nitrile rubber is 55.0 mg / g.

[0038] The preparation method of the epoxy resin toughening material of this comparative example 1 comprises the following steps: (1) First, carbon fiber was added into an acetone solution with a concentration of 7.5 mol / L and mixed. The temperature was controlled at 45 °C during the mixing process under a vacuum environment, and then ultrasonic treatment was applied for 2 h. (2) adding polyvinyl alcohol, inorganic nanoparticles and hydroxy-terminated nitrile rubber, mixing them evenly with a high-speed stirrer at a stirring speed of 4000 rpm, and then applying ultrasonic treatment for 1.5 h; (3) Finally, add coupling agent and defoaming agent, mix and heat to 95°C, react for 20 minutes, and then keep at a constant temperature of 65°C for 5 hours to obtain the toughened material.

[0039] 2. Toughening of epoxy resin The toughening material prepared above is used to toughen the epoxy resin. The specific steps for preparing the toughened epoxy resin system are as follows: (1) Add the toughening material and epoxy resin into a stirrer, ultrasonicate for 1-1.5 hours, and then adjust the speed to 2000 rpm for mixing and stirring; (2) Add curing agent and defoaming agent, increase the stirring speed to 4000rpm, stir at high speed for 10-20 minutes, then discharge the material into the mold and cure at 85℃ for 8-9 hours to obtain the toughened resin. Comparative Example 2: 1. Preparation of toughened materials The raw material table of the toughening material of the epoxy resin in this comparative example 2 is as follows:

[0040] Among them, the graphene nanosheet thickness is 1-5nm; the sheet diameter is 1μm; The particle size of the inorganic nanoparticles is 10-500nm.

[0041] The preparation method of the epoxy resin toughening material of this comparative example 2 comprises the following steps: (1) First, graphene nanosheets were added into an acetone solution with a concentration of 7.5 mol / L and mixed. The temperature was controlled at 45 °C during the mixing process under a vacuum environment, and then ultrasonic treatment was applied for 2 h. (2) Polyvinyl alcohol, inorganic nanoparticles and styrene-butadiene rubber are then added and mixed evenly using a high-speed stirrer at a stirring speed of 4000 rpm, and then subjected to ultrasonic treatment for 1.5 h; (3) Finally, add coupling agent and defoaming agent, mix and heat to 95°C, react for 20 minutes, and then keep at a constant temperature of 65°C for 5 hours to obtain the toughened material.

[0042] Comparative Example 3: 1. Preparation of toughened materials The raw material table of the toughening material of the epoxy resin in this comparative example 3 is as follows:

[0043] Among them, the graphene nanosheet thickness is 1-5nm; the sheet diameter is 1μm; Among them, the hydroxyl content in the hydroxy-terminated nitrile rubber is 55.0 mg / g.

[0044] The preparation method of the epoxy resin toughening material of this comparative example 3 comprises the following steps: (1) First, graphene nanosheets were added into an acetone solution with a concentration of 7.5 mol / L and mixed. The temperature was controlled at 45 °C during the mixing process under a vacuum environment, and then ultrasonic treatment was applied for 2 h. (2) adding polyvinyl alcohol and hydroxy-terminated nitrile rubber, mixing them evenly with a high-speed stirrer at a stirring speed of 4000 rpm, and then applying ultrasonic treatment for 1.5 hours; (3) Finally, add coupling agent and defoaming agent, mix and heat to 95°C, react for 20 minutes, and then keep at a constant temperature of 65°C for 5 hours to obtain the toughened material.

[0045] 2. Toughening of epoxy resin The toughening material prepared above is used to toughen the epoxy resin. The specific steps for preparing the toughened epoxy resin system are as follows: (1) Add the polymer toughening material into a stirrer, add epoxy resin, ultrasonicate for 1-1.5h, and then adjust the speed to 2000rpm for mixing and stirring; (2) Add curing agent and defoaming agent, increase the stirring speed to 4000rpm, stir at high speed for 10-20 minutes, then discharge the material into the mold and cure at 85℃ for 8-9 hours to obtain the toughened resin. Comparative Example 4: 1. Preparation of toughened materials The raw material table of the graphene composite polymer toughening material of epoxy resin in this comparative example 4 is as follows:

[0046] Among them, the graphene nanosheet thickness is 1-5nm; the sheet diameter is 1μm; The particle size of the inorganic nanoparticles is 10-500nm.

[0047] Among them, the hydroxyl content in the hydroxy-terminated nitrile rubber is 55.0 mg / g.

[0048] The preparation method of the epoxy resin graphene composite polymer toughening material of this comparative example 4 comprises the following steps: (1) First, graphene nanosheets were added into an acetone solution with a concentration of 7.5 mol / L and mixed. The temperature was controlled at 45 °C during the mixing process under a vacuum environment, and then ultrasonic treatment was applied for 2 h. (2) polyvinyl pyrrolidone, inorganic nanoparticles and hydroxy-terminated nitrile rubber were added, mixed evenly with a high-speed stirrer at a stirring speed of 4000 rpm, and then subjected to ultrasonic treatment for 1.5 h; (3) Finally, add coupling agent and defoaming agent, mix and heat to 95°C, react for 20 minutes, and then keep at a constant temperature of 65°C for 5 hours to obtain the toughened material.

[0049] 2. Toughening of epoxy resin The toughening material prepared above is used to toughen the epoxy resin. The specific steps for preparing the toughened epoxy resin system are as follows: (1) Add the toughening material and epoxy resin into a stirrer, ultrasonicate for 1-1.5 hours, and then adjust the speed to 2000 rpm for mixing and stirring; (2) Add curing agent and defoaming agent, increase the stirring speed to 4000rpm, stir at high speed for 10-20 minutes, then discharge the material into the mold and cure at 85℃ for 8-9 hours to obtain the toughened resin. Table 2: Mechanical property test data of toughened resin in Comparative Examples 1-4.

[0050]

[0051] Based on Table 1 and Table 2, we can conclude that: (1) Compared with the commonly used toughening filler (carbon fiber), graphene nanosheets can significantly improve the toughening effect of toughening materials on epoxy resin; (2) Compared with other rubbers such as styrene-butadiene rubber, hydroxy-terminated nitrile rubber significantly improves the toughening effect of the toughening material on epoxy resin and improves the fracture toughness of epoxy resin. Hydroxyl-terminated nitrile rubber has higher compatibility with epoxy resin, allowing epoxy resin to absorb more energy and thus improve the toughness of epoxy resin. (3) Adding to the four inorganic nanoparticles has a good dispersion effect, refines the grains, and enhances the toughness of the toughened epoxy resin; (4) Compared with polyvinyl pyrrolidone, polyvinyl alcohol can more significantly increase the dispersibility of graphene nanosheets, thereby affecting the toughening effect of the toughening material.

[0052] Comparative Example 5: 1. Preparation of toughened materials The raw material table of toughening material of this comparative example 5 is:

[0053] Among them, the graphene nanosheet thickness is 1-5nm; the sheet diameter is 1μm; The particle size of the inorganic nanoparticles is 10-500nm.

[0054] Among them, the hydroxyl content in the hydroxy-terminated nitrile rubber is 55.0 mg / g.

[0055] The preparation method of the toughened material of this comparative example 5 comprises the following steps: (1) First, graphene nanosheets were added into an acetone solution with a concentration of 7.5 mol / L and mixed. The temperature was controlled at 45 °C during the mixing process under a vacuum environment, and then ultrasonic treatment was applied for 2 h. (2) adding polyvinyl alcohol, inorganic nanoparticles and hydroxy-terminated nitrile rubber, mixing them evenly with a high-speed stirrer at a stirring speed of 4000 rpm, and then applying ultrasonic treatment for 1.5 h; (3) Finally, add coupling agent and defoaming agent, mix and heat to 95°C, react for 20 minutes, and then keep at a constant temperature of 65°C for 5 hours to obtain the toughened material.

[0056] 2. Toughening of phenolic resin The toughening material prepared above is used to toughen the phenolic resin. The specific steps for preparing the toughened phenolic resin system are as follows: (1) Add the toughening material into a stirrer, add phenolic resin, ultrasonicate for 1-1.5 hours, and then adjust the speed to 2000 rpm for mixing and stirring; (2) Add curing agent and defoaming agent, increase the stirring speed to 4000rpm, stir at high speed for 10-20 minutes, then discharge the material into the mold and cure at 85℃ for 8-9 hours to obtain the toughened resin. Comparative Example 6: 1. Preparation of toughened materials The raw material table of toughening material of this comparative example 6 is as follows:

[0057] Among them, the graphene nanosheet thickness is 1-5nm; the sheet diameter is 1μm; The particle size of the inorganic nanoparticles is 10-500nm.

[0058] Among them, the hydroxyl content in the hydroxy-terminated nitrile rubber is 55.0 mg / g.

[0059] The preparation method of the toughened material of Comparative Example 6 comprises the following steps: (1) First, graphene nanosheets were added into an acetone solution with a concentration of 7.5 mol / L and mixed. The temperature was controlled at 45 °C during the mixing process under a vacuum environment, and then ultrasonic treatment was applied for 2 h. (2) adding polyvinyl alcohol, inorganic nanoparticles and hydroxy-terminated nitrile rubber, mixing them evenly with a high-speed stirrer at a stirring speed of 4000 rpm, and then applying ultrasonic treatment for 1.5 h; (3) Finally, add coupling agent and defoaming agent, mix and heat to 95°C, react for 20 minutes, and then keep at a constant temperature of 65°C for 5 hours to obtain the toughened material.

[0060] 2. Toughening of polyethylene resin The toughening material prepared above is used to toughen the polyethylene resin. The specific steps for preparing the toughened polyethylene resin system are as follows: (1) Add the toughening material into a stirrer and add polyethylene resin, perform ultrasonic treatment for 1-1.5 hours, and then adjust the speed to 2000 rpm for mixing and stirring; (2) Add curing agent and defoaming agent, increase the stirring speed to 4000rpm, stir at high speed for 10-20 minutes, then discharge the material into the mold and cure at 85℃ for 8-9 hours to obtain the toughened resin. Comparative Example 7: 1. Preparation of toughened materials The raw material table of toughening material of this comparative example 7 is:

[0061] Among them, the graphene nanosheet thickness is 1-5nm; the sheet diameter is 1μm; The particle size of the inorganic nanoparticles is 10-500nm.

[0062] Among them, the hydroxyl content in the hydroxy-terminated nitrile rubber is 55.0 mg / g.

[0063] The preparation method of the epoxy resin graphene composite polymer toughening material of this comparative example 7 comprises the following steps: (1) First, graphene nanosheets were added into an acetone solution with a concentration of 7.5 mol / L and mixed. The temperature was controlled at 45 °C during the mixing process under a vacuum environment, and then ultrasonic treatment was applied for 2 h. (2) adding polyvinyl alcohol, inorganic nanoparticles and hydroxy-terminated nitrile rubber, mixing them evenly with a high-speed stirrer at a stirring speed of 4000 rpm, and then applying ultrasonic treatment for 1.5 h; (3) Finally, add coupling agent and defoaming agent, mix and heat to 95°C, react for 20 minutes, and then keep at a constant temperature of 65°C for 5 hours to obtain the toughened material.

[0064] 2. Toughening of polystyrene resin The toughening material prepared above is used to toughen the polystyrene resin. The specific steps for preparing the toughened polystyrene resin system are as follows: (1) Add the toughening material into a stirrer and add the polystyrene resin, perform ultrasonic treatment for 1-1.5 hours, and then adjust the speed to 2000 rpm for mixing and stirring; (2) Add curing agent and defoaming agent, increase the stirring speed to 4000rpm, stir at high speed for 10-20 minutes, then discharge the material into the mold and cure at 85℃ for 8-9 hours to obtain the toughened resin. Blank group 1: epoxy resin without toughening.

[0065] Blank group 2: phenolic resin without toughening.

[0066] Blank group 3: polyethylene without toughening.

[0067] Blank group 4: non-toughened polystyrene.

[0068] Table 3: Mechanical property test data of toughened resins of comparative examples 5-7 and blank groups 1-4 without toughened resins.

[0069]

[0070] Based on Tables 1 and 3 above, it can be concluded that the toughening material also has a good toughening effect on phenolic resin, but the toughening effect of phenolic resin is obviously not as good as that of phenolic resin epoxy resin; the toughening effect of the toughening material on thermoplastic resin polyethylene resin and polystyrene is not significant enough.

[0071] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that the technical solutions described in the aforementioned embodiments may still be modified, or some of the technical features may be replaced by equivalents. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.

[0072] It should be noted that, in this article, the terms "comprises", "includes" or any other variations thereof are intended to cover non-exclusive inclusion, so that a process, method, article or apparatus that includes a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or apparatus.

[0073] This article uses specific examples to illustrate the principles and implementation methods of the present invention. The above examples are only used to help understand the method and core ideas of the present invention. The above is only a preferred implementation of the present invention. It should be pointed out that due to the limitations of textual expression and the objective existence of infinite specific structures, ordinary technicians in this technical field can make several improvements, modifications or changes without departing from the principles of the present invention, and can also combine the above technical features in an appropriate manner; these improvements, modifications, changes or combinations, or the direct application of the inventive concept and technical solution to other occasions without improvement, should be regarded as the protection scope of the present invention.

Claims

1. A graphene composite polymer toughening material of epoxy resin, characterized in that: The toughening material comprises the following raw materials in percentage by mass: Graphene nanosheets 15-40%, rubber 15-35%, polyvinyl alcohol 15-40%, inorganic nanoparticles 5-15%, coupling agent 1-3%, defoaming agent 1-3%; Wherein, the graphene nanosheet has a thickness of 1-5 nm and a sheet diameter of 1 μm; Wherein, the particle size of the inorganic nanoparticles is 10-500nm.

2. The epoxy resin graphene composite polymer toughening material according to claim 1, characterized in that: The toughening material comprises the following raw materials in percentage by mass: Graphene nanosheets 20-35%, rubber 20-30%, polyvinyl alcohol 20-35%, inorganic nanoparticles 8.5-12%, coupling agent 1.5-2.5%, defoaming agent 1.5-2.5%.

3. The epoxy resin graphene composite polymer toughening material according to claim 2, characterized in that: The toughening material comprises the following raw materials in percentage by mass: Graphene nanosheets 30%, rubber 25%, polyvinyl alcohol 30%, inorganic nanoparticles 11%, coupling agent 2%, defoaming agent 2%.

4. The epoxy resin graphene composite polymer toughening material according to claim 1, characterized in that: The coupling agent is coupling agent KH550, and the defoaming agent is KS-603 epoxy silicone oil defoaming agent.

5. The epoxy resin graphene composite polymer toughening material according to claim 1, characterized in that: The rubber is hydroxy-terminated nitrile rubber.

6. The epoxy resin graphene composite polymer toughening material according to claim 5, characterized in that: The hydroxyl content of the hydroxy-terminated nitrile rubber is 52.5-56.0 mg / g.

7. The epoxy resin graphene composite polymer toughening material according to claim 6, characterized in that: The hydroxyl content of the hydroxy-terminated nitrile rubber is 55.0 mg / g.

8. The epoxy resin graphene composite polymer toughening material according to claim 1, characterized in that: The inorganic nanoparticles are nano silicon dioxide, nano titanium dioxide, nano calcium carbonate and carbon nanotubes.

9. The epoxy resin graphene composite polymer toughening material according to claim 8, characterized in that: The mass ratio of the nano silicon dioxide, nano titanium dioxide, nano calcium carbonate and carbon nanotube is 2:1:1:

1.

10. The method for preparing the epoxy resin-graphene composite polymer toughening material according to any one of claims 1 to 9, characterized in that: The preparation of the toughened material comprises the following steps: (1) First, graphene nanosheets are added into an acetone solution with a concentration of 7.5 mol / L and mixed, the temperature is controlled at 40-50° C. during the mixing process under a vacuum environment, and then ultrasonic treatment is applied for 1.5-2 h; (2) adding polyvinyl alcohol, inorganic nanoparticles and hydroxy-terminated nitrile rubber, mixing them evenly with a high-speed stirrer at a stirring speed of 3000-4000 rpm, and then applying ultrasonic treatment for 1-1.5 hours; (3) Finally, a coupling agent and a defoaming agent are added, mixed and heated to 85-105°C, reacted for 15-20 minutes, and then kept at a constant temperature of 60-65°C for 3-5 hours to obtain the toughened material.

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