Flame-retardant wear-resistant epoxy resin cable material and preparation method thereof

Abstract

The invention discloses a flame-retardant wear-resistant epoxy resin cable material and a preparation method thereof, and relates to the technical field of cable sheaths and insulating materials. The formula comprises bisphenol A epoxy resin, a curing agent, a hyperbranched polymer, a reactive nano mica sheet, phosphorus-nitrogen flame-retardant core-shell microspheres, an accelerant and a wetting dispersant. According to the invention, the technical contradiction that the toughness, wear resistance and flame retardance of the epoxy resin are difficult to synergistically improve is effectively improved by using the three self-prepared components, namely the hyperbranched polymer containing the dynamic disulfide bond, the nano mica sheet of which the surface is grafted with the liquid crystal unit and the phosphorus-nitrogen flame-retardant microsphere with the core-shell packaging structure. The material disclosed by the invention has high toughness, high wear resistance and excellent flame retardance while keeping good processability and electrical insulating property, and is suitable for sheaths and insulating layers of high-performance cables.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of cable sheath and insulation materials, in particular to a flame-retardant wear-resistant epoxy resin cable material and a preparation method thereof. BACKGROUND

[0002] Epoxy resin plays an important role in the field of cable sheath and insulation materials due to its excellent bonding strength, electrical insulation, chemical stability and molding process. However, the cured product of unmodified epoxy resin has inherent brittleness, poor impact resistance, and is prone to micro-cracks under installation and external impact. At the same time, its surface hardness and wear resistance also cannot meet the long-term use requirements under harsh working conditions. In addition, the flame-retardant performance of epoxy resin itself is limited, and it relies on the addition of flame retardants to meet the fire safety standards.

[0003] To improve the brittleness of epoxy resin, rubber elastomers (such as nitrile rubber) or thermoplastic plastics are usually used for toughening. Although this method can improve the impact strength, it often comes at the cost of significantly reducing the rigidity, strength, modulus and heat resistance of the material, and has limited contribution to wear resistance. To improve rigidity, hardness and wear resistance, rigid inorganic fillers (such as silicon dioxide, silicon carbide, etc.) are often introduced, but this usually leads to further increase in material brittleness and processing viscosity. In terms of flame retardation, direct addition of halogen-based, phosphorus-based, nitrogen-based or inorganic hydroxide flame retardants is a common means. However, high addition amount often damages the mechanical properties, electrical properties and processing fluidity of the material, and there are problems such as migration, precipitation or premature decomposition of the flame retardant.

[0004] Based on the current situation that the improvement of a certain performance of epoxy resin in the prior art often cannot take into account or even damage other key performance contradictions, the industry urgently needs to develop a cable material that can simultaneously improve the toughness, wear resistance and flame retardance of epoxy resin without affecting its basic mechanical strength, electrical insulation and process adaptability. SUMMARY

[0005] The purpose of the present application is to provide a flame-retardant wear-resistant epoxy resin cable material and a preparation method thereof to solve the problems raised in the background art.

[0006] In a first aspect of the present application, a flame-retardant wear-resistant epoxy resin cable material is provided, which comprises the following raw materials in parts by weight: Bisphenol A type epoxy resin 80-120 parts; Curing agent 25-35 parts; Hyperbranched polymer 5-15 parts; Reaction type nano mica flake 8-20 parts; Phosphorus-nitrogen flame-retardant core-shell microspheres 10-25 parts; Promoter 0.5-2 parts; Wetting dispersant 0.5-1.5 parts.

[0007] As a preferred technical solution of the present application, the curing agent is 4,4'-diamino diphenyl sulfone.

[0008] As a preferred technical solution of the present application, the preparation method of the hyperbranched polymer is as follows: Pentaerythritol, thiodiglycol, p-toluenesulfonic acid and tetrahydrofuran are added to a reaction bottle, refluxed at 110℃ for 6h to obtain a hyperbranched polyester with hydroxyl groups at the end; cooled to 70℃, glycidyl methacrylate and hydroquinone are added, and the reaction is continued for 8h; after the reaction is completed, the product is dropped into ice ether for precipitation, filtered, and vacuum dried to obtain a hyperbranched polymer; The mass ratio of the pentaerythritol, thiodiglycol, p-toluenesulfonic acid, tetrahydrofuran, glycidyl methacrylate and hydroquinone is 1:2:0.1:80:15:0.05.

[0009] It should be noted that the preparation method constructs a hyperbranched skeleton with a three-dimensional structure through polyol and polycondensation reaction of a disulfide bond-containing diol, which contains a dynamic disulfide bond inside, and the hydroxyl groups at the end of the molecule can undergo ring-opening esterification with glycidyl methacrylate, thereby introducing a side chain containing a carbon-carbon double bond. The obtained hyperbranched polymer itself can be used as a reactive toughening phase containing a dynamic covalent bond. When applied to cable materials, the polar groups such as hydroxyl groups contained in the molecular structure of the hyperbranched polymer can produce strong interaction with the epoxy resin system and can partially participate in the curing reaction; and the dynamic disulfide bond in the molecular chain can reversibly break and recombine under external force, effectively dissipating energy and improving the fracture toughness of the material. The design of introducing dynamic covalent chemistry into the rigid epoxy network provides a way to improve the toughness and maintain the interfacial strength of the material.

[0010] As a preferred technical solution of the present application, the preparation method of the reactive nano-mica sheet is as follows: A1, the mica sheet and KH560 silane coupling agent are refluxed in toluene for silanization treatment to obtain an epoxy-functionalized mica; The mass ratio of the mica sheet, KH560 silane coupling agent and toluene is 100:5:1000; A2, the epoxy-functionalized mica obtained in step A1 is dispersed in N,N-dimethylformamide, 4-hydroxybenzoic acid, N,N'-dicyclohexyl carbodiimide and 4-dimethylamino pyridine are added, and the mixture is stirred at room temperature for 24h, centrifuged, and dried to obtain a reactive nano-mica sheet; The mass ratio of the epoxy-functionalized mica, N,N-dimethylformamide, 4-hydroxybenzoic acid, N,N'-dicyclohexyl carbodiimide and 4-dimethylamino pyridine is 100:500:8:10:0.5.

[0011] It should be noted that the preparation method first grafts epoxy groups on the surface of nanometer mica sheet through silanization reaction, and then bonds 4-hydroxybenzoic acid (liquid crystal precursor) on it through esterification reaction. The obtained reactive nanometer mica sheet has rigidity of inorganic nanosheet, reactivity of surface epoxy group, and polarity and potential ordered arrangement ability of grafted benzoate group. In cable materials, the surface epoxy group can be covalently connected with the resin matrix, greatly enhancing the interfacial bonding force; and the grafted benzoate group can promote the ordered arrangement of molecular chains in the interface region of the filler and the matrix when the material is processed or subjected to external stress / thermal field, thereby helping to adjust the friction and wear properties and mechanical properties of the material. This surface functionalization strategy realizes the transformation of the filler from passive addition to active response.

[0012] As a preferred technical scheme of the present application, the preparation method of the phosphorus-nitrogen flame-retardant core-shell microspheres is as follows: B1, polystyrene microspheres, tetraethyl orthosilicate, cetyltrimethylammonium bromide are added into a mixture of ethanol and water, ammonia water is added dropwise, and stirring reaction is carried out at room temperature for 24 h to obtain a core-shell microsphere precursor, which is centrifuged, washed and dried; The concentration of the ammonia water is 20-30%; The mass ratio of the polystyrene microspheres, tetraethyl orthosilicate, cetyltrimethylammonium bromide, ethanol, water and ammonia water is 10:20:2:200:100:5; B2, the microsphere precursor obtained in step B1 is placed in a muffle furnace, heated to 550℃ at 2℃ / min under air atmosphere, and heat treated for 4 h, and then cooled in the furnace to obtain hollow mesoporous silica microspheres; B3, the hollow mesoporous silica microspheres obtained in step B2 are mixed with an ammonium polyphosphate / melamine cyanurate eutectic mixture, and vacuum impregnation treatment is carried out in a vacuum oven at 180℃ for 2 h, and then cooled to obtain phosphorus-nitrogen flame-retardant core-shell microspheres; The mass ratio of the hollow mesoporous silica microspheres and the ammonium polyphosphate / melamine cyanurate eutectic mixture is 10:15.

[0013] It should be noted that the preparation method takes polystyrene balls as templates, coats mesoporous silica shell layer through sol-gel method, removes the templates through calcination to obtain hollow mesoporous structure, and finally encapsulates the phosphorus-nitrogen synergistic flame retardant therein through vacuum impregnation. The obtained core-shell microspheres take silica as shell and flame retardant as core. The structure itself provides physical encapsulation effect, which can delay the migration and premature decomposition of the flame retardant. When applied to cable materials, the dense silica shell layer plays a physical barrier role in the initial stage of combustion; after heating, the flame retardant in the shell layer is released by heat, and the hollow structure may promote the expansion of the carbon layer when heated. This core-shell encapsulation design helps to reduce the negative impact of the flame retardant on the mechanical properties of the matrix while improving the flame retardant efficiency, and the relatively hard silica shell layer itself can serve as a reinforcing point to contribute to the mechanical properties of the material.

[0014] As a preferred technical solution of the present application, the accelerator is 2-ethyl-4-methylimidazole.

[0015] As a preferred technical solution of the present application, the wet dispersant is a polyether-modified polysiloxane copolymer.

[0016] In a second aspect of the present application, a preparation method of a flame-retardant and wear-resistant epoxy resin cable material is provided, which specifically comprises the following steps: S1, adding bisphenol A type epoxy resin and wet dispersant into a high-speed disperser, and stirring at 60 DEG C and 800 r / min for 10 min; S2, sequentially adding hyperbranched polymer, reactive nano-mica sheet and phosphorus-nitrogen flame-retardant core-shell microspheres, increasing the stirring speed to 1500 r / min, and continuously stirring and mixing at 70 DEG C for 30 min to obtain uniform resin premix; S3, cooling the resin premix obtained in S2 to 50 DEG C, adding curing agent and accelerator, and stirring at 400 r / min for 5 min, then transferring to a vacuum degassing machine and degassing at-0.098 MPa and 50 DEG C for 20 min; S4, pouring the degassed mixture into a mold preheated to 60 DEG C, and placing it in a vacuum oven for secondary degassing at-0.095 MPa for 10 min; S5, placing the mold in an oven for programmed curing: first increasing the temperature to 80 DEG C at 1 DEG C / min, and keeping the temperature for 2 h; then increasing the temperature to 120 DEG C at 2 DEG C / min, and keeping the temperature for 2 h; finally increasing the temperature to 150 DEG C at 2 DEG C / min, and keeping the temperature for 1 h; after curing, naturally cooling to below 60 DEG C to demold, thereby obtaining the flame-retardant and wear-resistant epoxy resin cable material.

[0017] It needs to be particularly pointed out that when the hyperbranched polymer exists alone in the cable material formula, it mainly acts as a dynamic toughening phase, consumes energy to improve toughness through disulfide bond exchange, but may cause a certain degree of modulus decline. When the reactive nano-mica sheet exists alone, it acts as a reinforcing filler, strengthens the interface through the surface epoxy group and improves the stiffness and wear resistance, but may affect the processing fluidity at high content. When the phosphorus-nitrogen flame-retardant core-shell microspheres exist alone, they act as high-efficiency flame retardants, but the interfacial compatibility between inorganic fillers and organic matrix may become a weak point of mechanical properties. However, when the hyperbranched polymer and the reactive nano-mica sheet act together, the flexible segment of the hyperbranched polymer can improve the local stress distribution around the mica sheet, and the rigid surface of the mica sheet can provide topological constraints for the exchange and recombination of disulfide bonds, and the combination of the two enables the material to maintain high modulus and unique stress-induced hardening behavior under high toughness. When the hyperbranched polymer and the phosphorus-nitrogen flame-retardant core-shell microspheres act together, the interpenetrating network formed by the hyperbranched polymer can wrap and anchor the core-shell microspheres, improving their dispersibility; under burning conditions, the thermal decomposition products of the hyperbranched polymer and the components released by the flame retardant may interact in the gas phase or the carbon layer, forming a more dense protective layer. When the reactive nano-mica sheet and the phosphorus-nitrogen flame-retardant core-shell microspheres act together, the mica sheet can act as a two-dimensional bridge to connect multiple core-shell microspheres and build a more perfect reinforcing and heat transfer network in the matrix; when heated, the high-temperature stability of the mica sheet itself and its lamellar structure help to form a more continuous and strong carbon layer or ceramic protective layer.

[0018] Compared with the prior art, the present application has the following beneficial effects: (1) Through the synergistic cooperation of the hyperbranched polymer, the reactive nano-mica sheet and the phosphorus-nitrogen flame-retardant core-shell microspheres, the comprehensive balance and improvement of the toughness, stiffness, wear resistance and flame retardance of the epoxy resin cable material are realized, and the technical contradiction that single performance improvement often leads to the decline of other performances is overcome.

[0019] (2) Each functional component is endowed with reactivity or dynamic response characteristics through chemical design, so that it forms a strong interfacial bond or intelligent response mechanism with the matrix, improving the structural uniformity, use reliability and long-term stability of the material.

[0020] (3) The flame-retardant system uses core-shell encapsulation and synergistic compounding to achieve high-efficiency flame retardation (such as high oxygen index, low smoke density) while minimizing the negative impact on the mechanical properties, electrical insulation properties and processing properties of the matrix. DETAILED DESCRIPTION

[0021] The technical solutions in the embodiments of the present application will be described clearly and completely below. Obviously, the described embodiments are only a part but not all of the embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative work fall within the scope of the present application.

[0022] Preparation Example 1 The preparation method of the hyperbranched polymer is as follows: 1g pentaerythritol, 2g thiodiglycol, 0.1g p-toluenesulfonic acid and 80g tetrahydrofuran were added into a reaction bottle, and refluxed at 110℃ for 6h to obtain a hyperbranched polyester with hydroxyl groups at the end; the temperature was lowered to 70℃, 15g glycidyl methacrylate and 0.05g hydroquinone were added, and the reaction was continued for 8h; after the reaction was completed, the product was dropped into ice ethyl ether for precipitation, filtered, and vacuum dried to obtain the hyperbranched polymer.

[0023] Preparation Example 2 The preparation method of the reactive nanometer mica sheet is as follows: A1. 100g mica sheet and 5g KH560 silane coupling agent were refluxed in 1000g toluene for silanization treatment to obtain epoxy-functionalized mica; A2. 100g epoxy-functionalized mica obtained in step A1 was dispersed in 500g N,N-dimethylformamide, 8g 4-hydroxybenzoic acid, 10g N,N'-dicyclohexyl carbodiimide and 0.5g 4-dimethylaminopyridine were added, and the reaction was stirred at room temperature for 24h, centrifuged, and dried to obtain the reactive nanometer mica sheet; Preparation Example 3 The preparation method of the phosphorus-nitrogen flame-retardant core-shell microsphere is as follows: B1. 10g polystyrene microsphere, 20g tetraethyl orthosilicate and 2g hexadecyl trimethyl ammonium bromide were added into a mixture of 200g ethanol and 100g water, 5g 25% ammonia water was added dropwise, and the reaction was stirred at room temperature for 24h to obtain a core-shell microsphere precursor, which was centrifuged, washed and dried; B2. The microsphere precursor obtained in step B1 was placed in a muffle furnace, and heated to 550℃ at a rate of 2℃ / min under air atmosphere, and kept for 4h to obtain hollow mesoporous silica microspheres; B3. The hollow mesoporous silica microspheres obtained in step B2 were mixed with an ammonium polyphosphate / melamine cyanurate eutectic mixture, and vacuum impregnated at 180℃ for 2h in a vacuum oven to obtain the phosphorus-nitrogen flame-retardant core-shell microsphere after cooling; The ammonium polyphosphate / melamine cyanurate eutectic mixture was obtained by mixing ammonium polyphosphate and melamine cyanurate at a mass ratio of 2:1, and blending in a high-speed mixer at a speed of 3000r / min for 15-20min.

[0024] The mass ratio of the hollow mesoporous silica microspheres to the ammonium polyphosphate / melamine cyanurate eutectic mixture is 10:15.

[0025] Example 1 A preparation method of a flame-retardant wear-resistant epoxy resin cable material, comprising the following steps: S1, 100 parts of bisphenol A type epoxy resin, 1 part of polyether modified polysiloxane copolymer wet dispersant are added into a high-speed dispersing machine, and stirred at 60 DEG C, 800 r / min for 10 min; S2, 10 parts of hyperbranched polymer, 14 parts of reactive nanometer mica sheet, 18 parts of phosphorus-nitrogen flame-retardant core-shell microspheres are added in sequence, the stirring speed is increased to 1500 r / min, and the mixing is continuously stirred at 70 DEG C for 30 min, to obtain a uniform resin premix; S3, the resin premix obtained in S2 is cooled to 50 DEG C, 30 parts of 4,4'-diamino diphenyl sulfone curing agent and 1.3 parts of 2-ethyl-4-methyl imidazole accelerator are added, and stirred at 400 r / min for 5 min, then transferred to a vacuum defoaming machine, and defoamed at-0.098 MPa, 50 DEG C for 20 min; S4, the defoamed mixture is poured into a mold preheated to 60 DEG C, and placed in a vacuum oven for secondary defoaming at-0.095 MPa for 10 min; S5, the mold is placed in an oven for programmed curing: first heated to 80 DEG C at 1 DEG C / min, and kept for 2 h; then heated to 120 DEG C at 2 DEG C / min, and kept for 2 h; finally heated to 150 DEG C at 2 DEG C / min, and kept for 1 h; after curing, naturally cooled to below 60 DEG C, and demolded, to obtain the flame-retardant wear-resistant epoxy resin cable material.

[0026] Some raw materials involved in the present embodiment are prepared by Preparation Examples 1-3, and other embodiments are the same.

[0027] Example 2 A preparation method of a flame-retardant wear-resistant epoxy resin cable material, comprising the following steps: S1, 80 parts of bisphenol A type epoxy resin, 0.5 parts of polyether modified polysiloxane copolymer wet dispersant are added into a high-speed dispersing machine, and stirred at 60 DEG C, 800 r / min for 10 min; S2, 5 parts of hyperbranched polymer, 8 parts of reactive nanometer mica sheet, 10 parts of phosphorus-nitrogen flame-retardant core-shell microspheres are added in sequence, the stirring speed is increased to 1500 r / min, and the mixing is continuously stirred at 70 DEG C for 30 min, to obtain a uniform resin premix; S3. Cool the resin premix obtained in S2 to 50°C, add 25 parts of 4,4'-diaminodiphenyl sulfone curing agent and 0.5 parts of 2-ethyl-4-methylimidazolium accelerator, stir at low speed at 400 r / min for 5 min, and then transfer to a vacuum degassing machine for degassing at -0.098 MPa and 50°C for 20 min. S4. Pour the completely degassed mixture into a mold preheated to 60°C and place it in a vacuum oven for a second degassed at -0.095MPa for 10 minutes. S5. Place the mold in an oven for programmed curing: first, heat to 80℃ at 1℃ / min and hold for 2 hours; then heat to 120℃ at 2℃ / min and hold for 2 hours; finally, heat to 150℃ at 2℃ / min and hold for 1 hour; after curing, allow it to cool naturally to below 60℃ before demolding to obtain the flame-retardant and wear-resistant epoxy resin cable material.

[0028] Example 3 A method for preparing a flame-retardant and wear-resistant epoxy resin cable material includes the following steps: S1. Add 120 parts of bisphenol A type epoxy resin and 1.5 parts of polyether modified polysiloxane copolymer wetting and dispersing agent to a high-speed disperser and stir for 10 min at 60℃ and 800 r / min. S2. Add 15 parts of hyperbranched polymer, 20 parts of reactive nano-mica sheets, and 25 parts of phosphorus-nitrogen flame-retardant core-shell microspheres in sequence. Increase the stirring speed to 1500 r / min and continue stirring and mixing at 70℃ for 30 min to obtain a uniform resin premix. S3. Cool the resin premix obtained in S2 to 50°C, add 35 parts of 4,4'-diaminodiphenyl sulfone curing agent and 2 parts of 2-ethyl-4-methylimidazolium accelerator, stir at low speed at 400 r / min for 5 min, and then transfer to a vacuum degassing machine for degassing at -0.098 MPa and 50°C for 20 min. S4. Pour the completely degassed mixture into a mold preheated to 60°C and place it in a vacuum oven for a second degassed at -0.095MPa for 10 minutes. S5. Place the mold in an oven for programmed curing: first, heat to 80℃ at 1℃ / min and hold for 2 hours; then heat to 120℃ at 2℃ / min and hold for 2 hours; finally, heat to 150℃ at 2℃ / min and hold for 1 hour; after curing, allow it to cool naturally to below 60℃ before demolding to obtain the flame-retardant and wear-resistant epoxy resin cable material.

[0029] Comparative Example 1 The difference between this comparative example and Example 1 is that the hyperbranched polymer prepared in Example 1 was not added; instead, a commercially available end-hydroxyl hyperbranched polyester was added.

[0030] Comparative Example 2 The difference between this comparative example and Example 1 is that the reaction-type nanometer mica sheet prepared in Preparation Example 2 is not added, but a commercially available hollow mesoporous silica is added instead.

[0031] Comparative Example 3 The difference between this comparative example and Example 1 is that the phosphorus-nitrogen flame-retardant core-shell microspheres prepared in Preparation Example 3 are not added, but a commercially available hollow mesoporous silica is added instead.

[0032] Test: I. Flame Retardant Performance Test The limiting oxygen index (LOI) is determined according to GB / T 2406.2-2009 Plastics Determination of the Burning Behavior of Plastics Part 2: Guidance on the Measurement of Flame Retardant Properties; the burning grade and afterflame time are determined according to the vertical burning method in GB / T 2408-2021 Plastics Determination of the Burning Behavior of Plastics Horizontal and Vertical Methods.

[0033] II. Wear Resistance Test Taber abrasion test is carried out according to GB / T 5478-2008 Plastics Method of Test for Abrasion Resistance by the Rotating Cylindrical Abraser, CS-10 abrasive wheel is used, 1 kg load is applied, after 1000 rotations, the mass loss (abrasion amount) of the sample is determined.

[0034] III. Impact Toughness Test The notched sample's Izod impact strength is determined according to GB / T 1843-2008 Plastics Determination of the Izod Charpy Impact Strength.

[0035] IV. Tensile Property Test Tensile strength and elongation at break are determined according to GB / T 1040.2-2006 Plastics Determination of the Tensile Properties Part 2: Test Conditions for Moulded and Extruded Plastics.

[0036] V. Thermal Property Test The heat distortion temperature under 1.8 MPa bending stress is determined according to GB / T 1634.2-2019 Plastics Determination of the Heat Distortion Temperature Part 2: Plastics and Ebonite.

[0037] VI. Performance Retention Rate Test after Long-term Thermal Aging The sample is placed in a 125℃ air oven for 168 hours thermal air aging, and the retention rate of tensile strength and impact strength before and after aging is tested according to GB / T 7141-2008 Plastics Method of Test for Heat Aging. The calculation formula is as follows: Tensile strength retention rate = tensile strength after aging / tensile strength before aging x 100%; Impact strength retention rate = impact strength after aging / impact strength before aging x 100%.

[0038] Seven, result summary Table 1

[0039] Eight, result discussion From Table 1, it can be seen that the flame-retardant wear-resistant epoxy resin cable material prepared in Examples 1-3 has excellent comprehensive performance, and is outstanding in flame retardancy, wear resistance, toughness (high impact strength), mechanical strength and thermal stability.

[0040] Compared with Examples 1-3, the notched impact strength, elongation at break and performance retention rate after aging of Comparative Example 1 decreased significantly. This shows that the dynamic disulfide bond in the preparation of the hyperbranched polymer plays a key role in achieving efficient energy dissipation, improving toughness and long-term thermal stability.

[0041] Compared with Examples 1-3, the wear amount of Comparative Example 2 increased significantly, and the tensile strength and impact strength also decreased. This confirms that the reactive nano-mica sheet is functionalized with the liquid crystal unit through the surface epoxy group, realizing strong interfacial bonding and stress response characteristics with the matrix, which is the core of simultaneously improving the wear resistance and mechanical properties of the material.

[0042] Compared with Examples 1-3, the limiting oxygen index of Comparative Example 3 is the lowest, only reaching V-2 level, and the improvement of mechanical properties is limited. This proves the effectiveness of the core-shell encapsulation structure of phosphorus-nitrogen flame retardant, which, while giving the material excellent flame retardancy, reduces the negative impact on the mechanical properties of the matrix through physical confinement and synergistic effect, and may improve the heat distortion temperature through interfacial effect.

[0043] In the description of the specification, the description of the reference terms "one embodiment", "example", "specific example" and the like means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present application. In the present specification, the illustrative description of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0044] The above is only an example and description of the present application, and those skilled in the art can make various modifications or supplements to the described specific embodiments or use similar ways to replace, as long as they do not deviate from the scope defined by the invention, which shall belong to the protection scope of the present application.

Claims

1. A flame-retardant and wear-resistant epoxy resin cable material, characterized in that: Including the following parts by weight of raw materials: 80-120 parts of bisphenol A type epoxy resin; 25-35 parts of curing agent; 5-15 parts of hyperbranched polymer; 8-20 parts of reactive nano-mica sheets; 10-25 parts of phosphorus-nitrogen flame-retardant core-shell microspheres; Accelerator 0.5-2 parts; 0.5-1.5 parts of wetting and dispersing agent.

2. The flame-retardant and wear-resistant epoxy resin cable material according to claim 1, characterized in that: The preparation method of hyperbranched polymers is as follows: Pentaerythritol, thiodiethylene glycol, p-toluenesulfonic acid, and tetrahydrofuran were added to a reaction flask and refluxed at 110°C for 6 hours to obtain a hyperbranched polyester with hydroxyl groups at the end. The temperature was lowered to 70°C, glycidyl methacrylate and hydroquinone were added, and the reaction was continued for 8 hours. After the reaction was completed, the product was dropped into ice-cold ether to precipitate, filtered, and dried under vacuum to obtain the hyperbranched polymer.

3. The flame-retardant and wear-resistant epoxy resin cable material according to claim 2, characterized in that: The mass ratio of pentaerythritol, thiodiethylene glycol, p-toluenesulfonic acid, tetrahydrofuran, glycidyl methacrylate, and hydroquinone is 1:2:0.1:80:15:0.

05.

4. The flame-retardant and wear-resistant epoxy resin cable material according to claim 1, characterized in that: The preparation method of the reactive nano-mica sheet is as follows: A1. Mica sheets and KH560 silane coupling agent were refluxed in toluene for silanization treatment to obtain epoxy-functionalized mica. A2. Disperse the epoxy-functionalized mica obtained in step A1 in N,N-dimethylformamide, add 4-hydroxybenzoic acid, N,N'-dicyclohexylcarbodiimide and 4-dimethylaminopyridine, stir the reaction at room temperature for 24 h, centrifuge and dry to obtain reactive nano-mica sheets.

5. The flame-retardant and wear-resistant epoxy resin cable material according to claim 4, characterized in that: In step A1, the mass ratio of the mica sheet, KH560 silane coupling agent, and toluene is 100:5:1000; in step A2, the mass ratio of the epoxy-functionalized mica, N,N-dimethylformamide, 4-hydroxybenzoic acid, N,N'-dicyclohexylcarbodiimide, and 4-dimethylaminopyridine is 100:500:8:10:0.

5.

6. The flame-retardant and wear-resistant epoxy resin cable material according to claim 1, characterized in that... B1. Polystyrene microspheres, tetraethyl orthosilicate, and hexadecyltrimethylammonium bromide were added to a mixture of ethanol and water, and ammonia was added dropwise. The mixture was stirred at room temperature for 24 hours to obtain a core-shell microsphere precursor, which was then centrifuged, washed, and dried. B2. Place the microsphere precursor obtained in step B1 in a muffle furnace, heat it to 550°C at 2°C / min in air atmosphere, keep it at the temperature for 4 hours, and cool it with the furnace to obtain hollow mesoporous silica microspheres. B3. The hollow mesoporous silica microspheres obtained in step B2 are mixed with the ammonium polyphosphate / melamine cyanurate eutectic mixture and placed in a vacuum oven for vacuum impregnation treatment at 180°C for 2 hours. After cooling, phosphorus-nitrogen flame-retardant core-shell microspheres are obtained.

7. The flame-retardant and wear-resistant epoxy resin cable material according to claim 6, characterized in that: In step B1, the mass ratio of the polystyrene microspheres, tetraethyl orthosilicate, hexadecyltrimethylammonium bromide, ethanol, water, and ammonia is 10:20:2:200:100:5; in step B3, the mass ratio of the hollow mesoporous silica microspheres to the ammonium polyphosphate / melamine cyanurate eutectic mixture is 10:

15.

8. The flame-retardant and wear-resistant epoxy resin cable material according to claim 1, characterized in that: The accelerator is 2-ethyl-4-methylimidazole.

9. The flame-retardant and wear-resistant epoxy resin cable material according to claim 1, characterized in that: The wetting and dispersing agent is a polyether-modified polysiloxane copolymer.

10. A method for preparing the flame-retardant and wear-resistant epoxy resin cable material as described in any one of claims 1-9, characterized in that: Specifically, the following steps are included: S1. Add bisphenol A type epoxy resin and wetting dispersant to a high-speed disperser and stir for 10 min at 60℃ and 800 r / min. S2. Add the hyperbranched polymer, reactive nano-mica sheets, and phosphorus-nitrogen flame-retardant core-shell microspheres in sequence. Increase the stirring speed to 1500 r / min and continue stirring and mixing at 70℃ for 30 min to obtain a uniform resin premix. S3. Cool the resin premix obtained in S2 to 50°C, add curing agent and accelerator, stir at low speed of 400r / min for 5min, then transfer to vacuum degassing machine, degas at -0.098 MPa and 50°C for 20min. S4. Pour the completely degassed mixture into a mold preheated to 60°C, and place it in a vacuum oven for a second degassed at -0.095MPa for 10 minutes. S5. Place the mold in an oven for programmed curing: first, heat to 80℃ at 1℃ / min and hold for 2 hours; then heat to 120℃ at 2℃ / min and hold for 2 hours; finally, heat to 150℃ at 2℃ / min and hold for 1 hour; after curing, allow it to cool naturally to below 60℃ before demolding to obtain the flame-retardant and wear-resistant epoxy resin cable material.

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