A kind of impact-resistant and high-temperature-resistant material and its application in cable protection tube

Abstract

The invention discloses an impact-resistant and high-temperature resistant material and application thereof in a cable protection tube, belonging to the technical field of cable protection tube materials, and used to solve the problem that the flame retardant property and wear resistance of the cable protection tube need to be further improved; wherein the impact-resistant and high-temperature resistant material is obtained by mixing polypropylene, nano silicon dioxide containing unsaturated double bonds, initiator, polyetherimide, rubber elastomer, antioxidant, antioxidant and lubricant, stirring, heating reaction, cooling to room temperature after the reaction ends, and granulating; wherein the nano silicon dioxide containing unsaturated double bonds is obtained by reacting modified nano graphene oxide and chlorosilane modified nano silicon dioxide; the impact-resistant and high-temperature resistant material prepared by the invention has good impact resistance, wear resistance and flame retardant property; the cable protection tube prepared by the material is not easy to break, especially when working in underground environment.

Description

Technical Field

[0001] The invention relates to the technical field of cable protection tube materials, and in particular to an impact-resistant and high-temperature-resistant material and application thereof in a cable protection tube. Background Art

[0002] Power cable protection tubes include glass fiber reinforced plastic cable conduits, MPP power cable conduits, CPVC power cable conduits and plastic-coated steel tubes. Power cable protection tubes are mainly installed in areas where communication cables and power lines intersect to prevent short circuit accidents caused by power line breaks and communication cables and wire ropes from being electrified, so as to protect the cables. Power cables have moved from overhead to underground. Most of the power cable protection tubes on the market are relatively simple in function when used, and most of them can only protect power cables. During use, cables are affected by the external environment and generate heat. Power accidents may occur, which poses certain safety hazards, especially near the underground environment of certain oil depots. With the development of urban construction in my country, the demand for wires and cables will also grow rapidly.

[0003] Chinese patent CN116376210B discloses an easy-to-dissipate heat MPP power cable protection tube and its production process, wherein the production process comprises: heating modified polypropylene, a regulator, modified boron nitride, tetrabutylammonium bromide, and dimethyl sulfoxide to react to obtain a mixed raw material; extruding through a screw extruder to obtain a power cable protection tube. The power cable protection tube obtained by the invention has excellent thermal conductivity and insulation properties, but the flame retardant and wear resistance properties need to be further improved to expand the scope of application. Summary of the invention

[0004] In order to solve the above technical problems, the present invention provides an impact-resistant and high-temperature resistant material and its application in a cable protection tube, which solves the problem that the flame retardant and wear-resistant properties of the cable protection tube need to be further improved.

[0005] In order to achieve the above object, the present invention provides a method for preparing an impact-resistant and high-temperature-resistant material, comprising the following steps:

[0006] The polypropylene, nano-silicon dioxide containing unsaturated double bonds, initiator, polyetherimide, rubber elastomer, antioxidant, antioxidant and lubricant are mixed, stirred, heated for reaction, cooled to room temperature after the reaction is finished, and granulated to obtain an impact-resistant and high-temperature-resistant material;

[0007] The preparation method of nano silicon dioxide containing unsaturated double bonds comprises the following steps:

[0008] The modified nano-graphene oxide, the chlorosilane-modified nano-silica and acetone are stirred and mixed, heated, reacted, filtered and dried after the reaction is completed to obtain nano-silica containing unsaturated double bonds;

[0009] The preparation method of modified nano graphene oxide comprises the following steps:

[0010] Step (1) dissolving γ-glycidyloxypropyltrimethoxysilane in an ethanol aqueous solution to obtain a silane-modified solution, dispersing nano-graphene oxide in the silane-modified solution, reacting, filtering, washing with ethanol, and drying to obtain epoxy-modified nano-graphene oxide;

[0011] Step (2) adding epoxy-modified nano-graphene oxide and 2-vinylbenzimidazole into anhydrous ethanol, stirring, heating, reacting, filtering, washing, and drying after the reaction is completed to obtain 2-vinylbenzimidazole-grafted epoxy-modified nano-graphene oxide;

[0012] Step (3) adding diphenyl phosphate and 2-vinylbenzimidazole grafted epoxy-modified nano-graphene oxide to N,N-dimethylformamide, stirring, adding p-toluenesulfonic acid, heating, reacting, filtering, washing, and drying to obtain modified nano-graphene oxide;

[0013] The preparation method of chlorosilane-modified nano-silica comprises the following steps:

[0014] The nano-silica, toluene and 3-chloropropylmethyldimethoxysilane are mixed evenly, heated, reacted, filtered, washed and dried after the reaction is completed to obtain chlorosilane-modified nano-silica.

[0015] Preferably, the mass ratio of polypropylene, nano-silica containing unsaturated double bonds, initiator, polyetherimide, rubber elastomer, antioxidant, antioxidant and lubricant is (80-100):(8-12):(0.2-0.4):(8-10):(3-5):(0.1-0.5):(0.4-0.8):(1-3).

[0016] Preferably, the antioxidant is N,N'-di(β-naphthyl)-p-phenylenediamine.

[0017] Preferably, the antioxidant is any one of antioxidant 1010, antioxidant 168, antioxidant 1098, or a mixture thereof.

[0018] Preferably, the lubricant is any one of polyethylene wax, polypropylene wax and stearic acid.

[0019] Preferably, the initiator is a peroxidic initiator.

[0020] Preferably, the rubber elastic body is any one of EPDM rubber, EPDM rubber and nitrile rubber.

[0021] Preferably, the mass ratio of modified nano-graphene oxide, chlorosilane-modified nano-silica and acetone is (300-500):(60-80):(2500-4500); the reaction conditions are 25-35° C. for 4-6 hours; and drying in an oven at 60-80° C. for 10-12 hours.

[0022] Preferably, the mass ratio of nano-graphene oxide, γ-glycidyloxypropyltrimethoxysilane and ethanol aqueous solution is (80-100):200:(4000-6000); the reaction conditions are 55-75° C. for 70-130 min; and the drying conditions are 55-75° C. for 1-3 h.

[0023] Preferably, the mass ratio of epoxy-modified nano-graphene oxide, 2-vinylbenzimidazole and anhydrous ethanol is (200-240):(150-180):(600-900); the reaction conditions are 30-50° C. for 5-7 hours; and the drying conditions are 50-60° C. for 2-4 hours.

[0024] Preferably, the mass ratio of diphenyl phosphate, 2-vinylbenzimidazole grafted epoxy-modified nano-graphene oxide, N,N-dimethylformamide and p-toluenesulfonic acid is (280-320):(300-500):(1000-2000):(16-22); the reaction conditions are 80-100° C. for 16-18 hours.

[0025] Preferably, the mass ratio of nano-silica, toluene and 3-chloropropylmethyldimethoxysilane is (80-100):(1500-2500):(60-80); the reaction conditions are 75-85° C. for 14-16 hours; and the drying conditions are 80-100° C. for 6-8 hours.

[0026] Preferably, the impact-resistant and high-temperature resistant material is prepared by the method for preparing the impact-resistant and high-temperature resistant material.

[0027] Preferably, the impact-resistant and high-temperature-resistant material is used in a cable protection tube.

[0028] Preferably, the manufacturing process of the cable protection tube in the application comprises the following steps:

[0029] Polypropylene, nano-silica containing unsaturated double bonds, initiator, polyetherimide, rubber elastomer, antioxidant, antioxidant and lubricant are mixed, then transferred to a twin-screw extruder, extruded and granulated at 170-200°C, and then added to the hopper of a pipe extruder and extruded to obtain a cable protection pipe.

[0030] Compared with the prior art, the present invention has the following beneficial effects:

[0031] 1. In the present invention, polypropylene is a matrix material and a thermoplastic synthetic resin, which is not only low in price and high in production capacity, but also has good wear resistance and chemical resistance, but polypropylene at low temperatures has the problem of poor impact resistance. The introduced graphene oxide is a wear-resistant and heat-resistant inorganic material, and after modification, the dispersibility is better; the epoxy in the epoxy-modified nano graphene oxide reacts with the imine group in 2-vinylbenzimidazole to obtain 2-vinylbenzimidazole-grafted epoxy-modified nano graphene oxide containing hydroxyl, unsaturated bond and tertiary amine group; the hydroxyl in the 2-vinylbenzimidazole-grafted epoxy-modified nano graphene oxide reacts with the hydroxyl in diphenyl phosphate to generate modified nano graphene oxide; the tertiary amine in the modified nano graphene oxide reacts with the chlorine group in the chlorosilane-modified nano silicon dioxide to generate a quaternary ammonium salt-type substance, i.e., nano silicon dioxide containing unsaturated double bonds. Nano-silica containing unsaturated double bonds can react chemically with polypropylene under the action of an initiator and be grafted onto the chain of polypropylene, thereby enhancing the interfacial bonding between polypropylene and filler and giving polypropylene more properties; the added polyetherimide has good flexibility and the rubber elastomer also has good toughness, which can effectively reduce the brittleness of the material, increase the ductility and crack resistance of the material, and the impact-resistant and high-temperature resistant material obtained after mixing has excellent comprehensive properties including impact resistance, wear resistance and flame retardancy, which increases its scope of application, especially in cable protection tubes.

[0032] 2. In the present invention, graphene oxide has certain flame retardant properties, which can promote the formation of a dense carbon layer in the matrix during the combustion process, block heat from entering the matrix, and inhibit the escape of small molecules. After modification, the graphene oxide can be evenly dispersed in the matrix, which improves compatibility and is conducive to flame retardancy. The introduced 2-vinylbenzimidazole can absorb ultraviolet rays and improve the aging resistance under ultraviolet light; it can also produce acidic substances such as phosphoric acid and phosphorous acid, promote the dehydration and carbonization of the matrix during the combustion process, and be grafted to the surface of graphene oxide, which can accelerate the formation of a carbon layer on the surface of the matrix. At the same time, the PO· free radicals generated can quench the combustion chain reaction and prevent the combustion reaction from proceeding. The nitrogen element contained in the combustion process will also produce non-combustible gas, dilute the concentration of oxygen in the combustion system, and is conducive to flame retardancy. In the present invention, the two are used together to synergistically increase the flame retardant properties of the matrix.

[0033] 3. The impact-resistant and high-temperature-resistant material provided by the present invention has the advantage of low cost, and especially its application in cable protection pipes reduces the cost of urban construction. At the same time, in the present invention, the introduced rubber elastomer can improve the ductility and impact resistance of polypropylene, especially under low temperature conditions, avoid brittle fracture of polypropylene materials, increase its low-temperature resistance, and improve impact resistance. Graphene oxide has a low friction coefficient and can provide a lubrication effect during friction, thereby reducing wear; while silicon dioxide has a high hardness and can be added to the matrix as particles to improve the wear resistance of the material, but compared with graphene oxide, its main function is to improve wear resistance by increasing hardness and reducing plastic deformation; the use of both can further improve the wear resistance of polypropylene materials, which is beneficial for it to maintain good performance in harsh environments and expand its scope of application. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 This is a process flow chart for preparing the impact-resistant and high-temperature-resistant material of the present invention;

[0035] Figure 2 The figure is a process flow chart of the preparation of nano silicon dioxide containing unsaturated double bonds in the present invention;

[0036] Figure 3 The schematic diagram of the reaction for preparing 2-vinylbenzimidazole grafted epoxy-modified nano graphene oxide in the present invention;

[0037] Figure 4 It is a schematic diagram of the reaction for preparing modified nano graphene oxide in the present invention. DETAILED DESCRIPTION

[0038] The technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all of the embodiments. 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.

[0039] Example 1

[0040] This embodiment provides a method for preparing an impact-resistant and high-temperature-resistant material, comprising the following steps:

[0041] Polypropylene, nano-silicon dioxide containing unsaturated double bonds, dibenzoyl peroxide, polyetherimide, nitrile rubber, N,N'-di(β-naphthyl)-p-phenylenediamine, antioxidant 1010 and stearic acid are mixed, stirred at a speed of 60 r / min for 12 minutes, reacted at a temperature of 170° C. for 30 minutes, cooled to room temperature after the reaction, and granulated to obtain an impact-resistant and high-temperature resistant material;

[0042] The mass ratio of polypropylene, nano-silicon dioxide containing unsaturated double bonds, dibenzoyl peroxide, polyetherimide, nitrile rubber, N,N'-di(β-naphthyl)-p-phenylenediamine, antioxidant 1010 and stearic acid is 80:8:0.2:8:3:0.1:0.4:1;

[0043] The preparation method of nano silicon dioxide containing unsaturated double bonds comprises the following steps:

[0044] The modified nano-graphene oxide, chlorosilane-modified nano-silica and acetone were mixed in a mass ratio of 300:60:2500, reacted at 25°C for 6 hours, filtered, and dried in an oven at 60°C for 12 hours to obtain nano-silica containing unsaturated double bonds;

[0045] The preparation method of modified nano graphene oxide comprises the following steps:

[0046] Step (1) dissolving γ-glycidyloxypropyltrimethoxysilane in a 30% ethanol aqueous solution to obtain a silane-modified solution, dispersing nano-graphene oxide in the silane-modified solution, reacting at a temperature of 55° C. for 130 min, filtering, washing with ethanol, and drying at a temperature of 55° C. for 3 h to obtain epoxy-modified nano-graphene oxide;

[0047] The mass ratio of nano-graphene oxide, γ-glycidyloxypropyltrimethoxysilane and ethanol aqueous solution is 80:200:4000;

[0048] Step (2) mixing epoxy-modified nano-graphene oxide, 2-vinylbenzimidazole and anhydrous ethanol in a mass ratio of 200:150:600, reacting at 30° C. for 7 h, filtering after the reaction, washing with deionized water, and drying at 50° C. for 4 h to obtain 2-vinylbenzimidazole-grafted epoxy-modified nano-graphene oxide;

[0049] Step (3) diphenyl phosphate, 2-vinylbenzimidazole grafted epoxy-modified nano-graphene oxide, N,N-dimethylformamide and p-toluenesulfonic acid are mixed in a mass ratio of 280:300:1000:16, reacted at 80° C. for 18 h, filtered, washed, and dried at 50° C. for 4.5 h to obtain modified nano-graphene oxide;

[0050] The preparation method of chlorosilane-modified nano-silica comprises the following steps:

[0051] Nano-silica, toluene and 3-chloropropylmethyldimethoxysilane were mixed in a mass ratio of 80:1500:60, reacted at 75°C for 16 hours, filtered, washed, and dried at 80°C for 8 hours to obtain chlorosilane-modified nano-silica.

[0052] Example 2

[0053] This embodiment provides a method for preparing an impact-resistant and high-temperature-resistant material, comprising the following steps:

[0054] Polypropylene, nano-silicon dioxide containing unsaturated double bonds, dibenzoyl peroxide, polyetherimide, nitrile rubber, N,N'-di(β-naphthyl)-p-phenylenediamine, antioxidant 1010 and stearic acid were mixed, stirred at a speed of 70 r / min for 11 minutes, reacted at a temperature of 177° C. for 45 minutes, and after the reaction was completed, cooled to room temperature, and granulated to obtain an impact-resistant and high-temperature-resistant material;

[0055] The mass ratio of polypropylene, nano-silicon dioxide containing unsaturated double bonds, dibenzoyl peroxide, polyetherimide, nitrile rubber, N,N'-di(β-naphthyl)-p-phenylenediamine, antioxidant 1010 and stearic acid is 85:9:0.25:8.5:3.5:0.2:0.5:1.5;

[0056] The preparation method of nano silicon dioxide containing unsaturated double bonds comprises the following steps:

[0057] The modified nano-graphene oxide, chlorosilane-modified nano-silica and acetone were mixed in a mass ratio of 350:65:3000, reacted at 27°C for 5.5h, filtered, and dried in an oven at 65°C for 11.5h to obtain nano-silica containing unsaturated double bonds;

[0058] The preparation method of modified nano graphene oxide comprises the following steps:

[0059] Step (1) dissolving γ-glycidyloxypropyltrimethoxysilane in a 30% ethanol aqueous solution to obtain a silane-modified solution, dispersing nano-graphene oxide in the silane-modified solution, reacting at 60° C. for 115 min, filtering, washing with ethanol, and drying at 60° C. for 2.5 h to obtain epoxy-modified nano-graphene oxide;

[0060] The mass ratio of nano-graphene oxide, γ-glycidyloxypropyltrimethoxysilane and ethanol aqueous solution is 85:200:4500;

[0061] Step (2) mixing epoxy-modified nano-graphene oxide, 2-vinylbenzimidazole and anhydrous ethanol in a mass ratio of 210:157:675, reacting at 35° C. for 6.5 h, filtering, washing with deionized water, and drying at 52° C. for 3.5 h to obtain 2-vinylbenzimidazole-grafted epoxy-modified nano-graphene oxide;

[0062] Step (3) diphenyl phosphate, 2-vinylbenzimidazole grafted epoxy-modified nano-graphene oxide, N,N-dimethylformamide and p-toluenesulfonic acid are mixed in a mass ratio of 290:350:1250:17.5, reacted at 85° C. for 17.5 h, filtered, washed, and dried at 55° C. for 4 h to obtain modified nano-graphene oxide;

[0063] The preparation method of chlorosilane-modified nano-silica comprises the following steps:

[0064] Nano-silica, toluene and 3-chloropropylmethyldimethoxysilane were mixed in a mass ratio of 85:1750:65, reacted at 77°C for 15.5 hours, filtered, washed, and dried at 85°C for 7.5 hours to obtain chlorosilane-modified nano-silica.

[0065] Example 3

[0066] This embodiment provides a method for preparing an impact-resistant and high-temperature-resistant material, comprising the following steps:

[0067] Polypropylene, nano-silicon dioxide containing unsaturated double bonds, dibenzoyl peroxide, polyetherimide, nitrile rubber, N,N'-di(β-naphthyl)-p-phenylenediamine, antioxidant 1010 and stearic acid are mixed, stirred at a speed of 80 r / min for 10 minutes, reacted at a temperature of 185° C. for 40 minutes, cooled to room temperature after the reaction is completed, and granulated to obtain an impact-resistant and high-temperature-resistant material;

[0068] The mass ratio of polypropylene, nano-silicon dioxide containing unsaturated double bonds, dibenzoyl peroxide, polyetherimide, nitrile rubber, N,N'-di(β-naphthyl)-p-phenylenediamine, antioxidant 1010 and stearic acid is 90:10:0.3:9:4:0.3:0.6:2;

[0069] The preparation method of nano silicon dioxide containing unsaturated double bonds comprises the following steps:

[0070] The modified nano-graphene oxide, chlorosilane-modified nano-silica and acetone were mixed in a mass ratio of 400:70:3500, reacted at 30°C for 5 hours, filtered, and dried in an oven at 70°C for 11 hours to obtain nano-silica containing unsaturated double bonds;

[0071] The preparation method of modified nano graphene oxide comprises the following steps:

[0072] Step (1) dissolving γ-glycidyloxypropyltrimethoxysilane in a 30% ethanol aqueous solution to obtain a silane-modified solution, dispersing nano-graphene oxide in the silane-modified solution, reacting at 65° C. for 100 min, filtering, washing with ethanol, and drying at 65° C. for 2 h to obtain epoxy-modified nano-graphene oxide;

[0073] The mass ratio of nano-graphene oxide, γ-glycidyloxypropyltrimethoxysilane and ethanol aqueous solution is 90:200:5000;

[0074] Step (2) mixing epoxy-modified nano-graphene oxide, 2-vinylbenzimidazole and anhydrous ethanol in a mass ratio of 220:165:750, reacting at 40° C. for 6 h, filtering after the reaction, washing with deionized water, and drying at 55° C. for 3 h to obtain 2-vinylbenzimidazole-grafted epoxy-modified nano-graphene oxide;

[0075] Step (3) diphenyl phosphate, 2-vinylbenzimidazole grafted epoxy-modified nano-graphene oxide, N,N-dimethylformamide and p-toluenesulfonic acid are mixed in a mass ratio of 300:400:1500:19, reacted at 90° C. for 17 h, filtered, washed, and dried at 60° C. for 3.5 h to obtain modified nano-graphene oxide;

[0076] The preparation method of chlorosilane-modified nano-silica comprises the following steps:

[0077] Nano-silica, toluene and 3-chloropropylmethyldimethoxysilane were mixed in a mass ratio of 90:2000:70, reacted at 80°C for 15 hours, filtered, washed, and dried at 90°C for 7 hours to obtain chlorosilane-modified nano-silica.

[0078] Example 4

[0079] This embodiment provides a method for preparing an impact-resistant and high-temperature-resistant material, comprising the following steps:

[0080] Polypropylene, nano-silicon dioxide containing unsaturated double bonds, dibenzoyl peroxide, polyetherimide, nitrile rubber, N,N'-di(β-naphthyl)-p-phenylenediamine, antioxidant 1010 and stearic acid were mixed, stirred at a speed of 90 r / min for 9 minutes, reacted at a temperature of 192° C. for 35 minutes, and after the reaction was completed, cooled to room temperature, and granulated to obtain an impact-resistant and high-temperature resistant material;

[0081] The mass ratio of polypropylene, nano-silicon dioxide containing unsaturated double bonds, dibenzoyl peroxide, polyetherimide, nitrile rubber, N,N'-di(β-naphthyl)-p-phenylenediamine, antioxidant 1010 and stearic acid is 95:11:0.35:9.5:4.5:0.4:0.7:2.5;

[0082] The preparation method of nano silicon dioxide containing unsaturated double bonds comprises the following steps:

[0083] The modified nano-graphene oxide, chlorosilane-modified nano-silica and acetone were mixed in a mass ratio of 450:75:4000, reacted at 32°C for 4.5 hours, filtered, and dried in an oven at 75°C for 10.5 hours to obtain nano-silica containing unsaturated double bonds;

[0084] The preparation method of modified nano graphene oxide comprises the following steps:

[0085] Step (1) dissolving γ-glycidyloxypropyltrimethoxysilane in a 30% ethanol aqueous solution to obtain a silane-modified solution, dispersing nano-graphene oxide in the silane-modified solution, reacting at 70° C. for 85 min, filtering, washing with ethanol, and drying at 70° C. for 1.5 h to obtain epoxy-modified nano-graphene oxide;

[0086] The mass ratio of nano-graphene oxide, γ-glycidyloxypropyltrimethoxysilane and ethanol aqueous solution is 95:200:5500;

[0087] Step (2) mixing epoxy-modified nano-graphene oxide, 2-vinylbenzimidazole and anhydrous ethanol in a mass ratio of 230:172:825, reacting at 45° C. for 5.5 h, filtering, washing with deionized water, and drying at 57° C. for 2.5 h to obtain 2-vinylbenzimidazole-grafted epoxy-modified nano-graphene oxide;

[0088] Step (3) diphenyl phosphate, 2-vinylbenzimidazole grafted epoxy-modified nano-graphene oxide, N,N-dimethylformamide and p-toluenesulfonic acid are mixed in a mass ratio of 310:450:1750:20.5, reacted at 95° C. for 16.5 h, filtered, washed, and dried at 65° C. for 3 h to obtain modified nano-graphene oxide;

[0089] The preparation method of chlorosilane-modified nano-silica comprises the following steps:

[0090] Nano-silica, toluene and 3-chloropropylmethyldimethoxysilane were mixed in a mass ratio of 95:2250:75, reacted at 82°C for 14.5 hours, filtered, washed, and dried at 95°C for 6.5 hours to obtain chlorosilane-modified nano-silica.

[0091] Example 5

[0092] This embodiment provides a method for preparing an impact-resistant and high-temperature-resistant material, comprising the following steps:

[0093] Polypropylene, nano-silicon dioxide containing unsaturated double bonds, dibenzoyl peroxide, polyetherimide, nitrile rubber, N,N'-di(β-naphthyl)-p-phenylenediamine, antioxidant 1010 and stearic acid are mixed, stirred at a speed of 100 r / min for 8 minutes, reacted at a temperature of 200° C. for 30 minutes, cooled to room temperature after the reaction is completed, and granulated to obtain an impact-resistant and high-temperature resistant material;

[0094] The mass ratio of polypropylene, nano-silicon dioxide containing unsaturated double bonds, dibenzoyl peroxide, polyetherimide, nitrile rubber, N,N'-di(β-naphthyl)-p-phenylenediamine, antioxidant 1010 and stearic acid is 100:12:0.4:10:5:0.5:0.8:3;

[0095] The preparation method of nano silicon dioxide containing unsaturated double bonds comprises the following steps:

[0096] The modified nano-graphene oxide, chlorosilane-modified nano-silica and acetone were mixed in a mass ratio of 500:80:4500, reacted at 35°C for 4 hours, filtered, and dried in an oven at 80°C for 10 hours to obtain nano-silica containing unsaturated double bonds;

[0097] The preparation method of modified nano graphene oxide comprises the following steps:

[0098] Step (1) dissolving γ-glycidyloxypropyltrimethoxysilane in a 30% ethanol aqueous solution to obtain a silane-modified solution, dispersing nano-graphene oxide in the silane-modified solution, reacting at 75° C. for 70 min, filtering, washing with ethanol, and drying at 75° C. for 1 h to obtain epoxy-modified nano-graphene oxide;

[0099] The mass ratio of nano-graphene oxide, γ-glycidyloxypropyltrimethoxysilane and ethanol aqueous solution is 100:200:6000;

[0100] Step (2) mixing epoxy-modified nano-graphene oxide, 2-vinylbenzimidazole and anhydrous ethanol in a mass ratio of 240:180:900, reacting at 50° C. for 5 h, filtering, washing with deionized water, and drying at 60° C. for 2 h to obtain 2-vinylbenzimidazole-grafted epoxy-modified nano-graphene oxide;

[0101] Step (3) diphenyl phosphate, 2-vinylbenzimidazole grafted epoxy-modified nano-graphene oxide, N,N-dimethylformamide and p-toluenesulfonic acid are mixed in a mass ratio of 320:500:2000:22, reacted at 100° C. for 16 h, filtered, washed, and dried at 70° C. for 2.5 h to obtain modified nano-graphene oxide;

[0102] The preparation method of chlorosilane-modified nano-silica comprises the following steps:

[0103] Nano-silica, toluene and 3-chloropropylmethyldimethoxysilane were mixed in a mass ratio of 100:2500:80, reacted at 85°C for 14 hours, filtered, washed, and dried at 100°C for 6 hours to obtain chlorosilane-modified nano-silica.

[0104] Comparative Example 1

[0105] This comparative example provides a method for preparing an impact-resistant and high-temperature-resistant material, comprising the following steps:

[0106] Polypropylene, nano-silica containing unsaturated double bonds, polyetherimide, nitrile rubber, N,N'-di(β-naphthyl)-p-phenylenediamine, antioxidant 1010 and stearic acid were mixed, stirred at a speed of 60 r / min for 12 minutes, reacted at a temperature of 170° C. for 30 minutes, cooled to room temperature after the reaction was completed, and granulated to obtain an impact-resistant and high-temperature resistant material;

[0107] The mass ratio of polypropylene, nano-silica containing unsaturated double bonds, polyetherimide, nitrile rubber, N,N'-di(β-naphthyl)-p-phenylenediamine, antioxidant 1010 and stearic acid is 80.2:8:8:3:0.1:0.4:1;

[0108] The preparation method of nano silicon dioxide containing unsaturated double bonds comprises the following steps:

[0109] The modified nano-graphene oxide, chlorosilane-modified nano-silica and acetone were mixed in a mass ratio of 300:60:2500, reacted at 25°C for 6 hours, filtered, and dried in an oven at 60°C for 12 hours to obtain nano-silica containing unsaturated double bonds;

[0110] The preparation method of modified nano graphene oxide comprises the following steps:

[0111] Step (1) dissolving γ-glycidyloxypropyltrimethoxysilane in a 30% ethanol aqueous solution to obtain a silane-modified solution, dispersing nano-graphene oxide in the silane-modified solution, reacting at a temperature of 55° C. for 130 min, filtering, washing with ethanol, and drying at a temperature of 55° C. for 3 h to obtain epoxy-modified nano-graphene oxide;

[0112] The mass ratio of nano-graphene oxide, γ-glycidyloxypropyltrimethoxysilane and ethanol aqueous solution is 80:200:4000;

[0113] Step (2) mixing epoxy-modified nano-graphene oxide, 2-vinylbenzimidazole and anhydrous ethanol in a mass ratio of 200:150:600, reacting at 30° C. for 7 h, filtering after the reaction, washing with deionized water, and drying at 50° C. for 4 h to obtain 2-vinylbenzimidazole-grafted epoxy-modified nano-graphene oxide;

[0114] Step (3) diphenyl phosphate, 2-vinylbenzimidazole grafted epoxy-modified nano-graphene oxide, N,N-dimethylformamide and p-toluenesulfonic acid are mixed in a mass ratio of 280:300:1000:16, reacted at 80° C. for 18 h, filtered, washed, and dried at 50° C. for 4.5 h to obtain modified nano-graphene oxide;

[0115] The preparation method of chlorosilane-modified nano-silica comprises the following steps:

[0116] Nano-silica, toluene and 3-chloropropylmethyldimethoxysilane were mixed in a mass ratio of 80:1500:60, reacted at 75°C for 16 hours, filtered, washed, and dried at 80°C for 8 hours to obtain chlorosilane-modified nano-silica.

[0117] Comparative Example 2

[0118] This comparative example provides a method for preparing an impact-resistant and high-temperature-resistant material, comprising the following steps:

[0119] Polypropylene, modified nano-graphene oxide, polyetherimide, nitrile rubber, N,N'-di(β-naphthyl)-p-phenylenediamine, antioxidant 1010 and stearic acid were mixed, stirred at a speed of 60 r / min for 12 min, reacted at a temperature of 170° C. for 30 min, cooled to room temperature after the reaction was completed, and granulated to obtain an impact-resistant and high-temperature-resistant material;

[0120] The mass ratio of polypropylene, modified nano-graphene oxide, polyetherimide, nitrile rubber, N,N'-di(β-naphthyl)-p-phenylenediamine, antioxidant 1010 and stearic acid is 80.2:8:8:3:0.1:0.4:1;

[0121] The preparation method of modified nano graphene oxide comprises the following steps:

[0122] Step (1) dissolving γ-glycidyloxypropyltrimethoxysilane in a 30% ethanol aqueous solution to obtain a silane-modified solution, dispersing nano-graphene oxide in the silane-modified solution, reacting at a temperature of 55° C. for 130 min, filtering, washing with ethanol, and drying at a temperature of 55° C. for 3 h to obtain epoxy-modified nano-graphene oxide;

[0123] The mass ratio of nano-graphene oxide, γ-glycidyloxypropyltrimethoxysilane and ethanol aqueous solution is 80:200:4000;

[0124] Step (2) mixing epoxy-modified nano-graphene oxide, 2-vinylbenzimidazole and anhydrous ethanol in a mass ratio of 200:150:600, reacting at 30° C. for 7 h, filtering after the reaction, washing with deionized water, and drying at 50° C. for 4 h to obtain 2-vinylbenzimidazole-grafted epoxy-modified nano-graphene oxide;

[0125] Step (3) diphenyl phosphate, 2-vinylbenzimidazole grafted epoxy modified nano-graphene oxide, N,N-dimethylformamide and p-toluenesulfonic acid are mixed in a mass ratio of 280:300:1000:16, reacted at 80°C for 18h, filtered, washed and dried at 50°C for 4.5h to obtain modified nano-graphene oxide.

[0126] In the embodiments and comparative examples of the present invention, polypropylene is homopolypropylene, which is from Yangzi Petrochemical, model F401, wherein MFR is 2.5±0.5g / 10min; polyetherimide is from Dongguan Kaixili Plastic Raw Materials Co., Ltd.; nitrile rubber is from Beijing Chemical Research Institute of China Petrochemical Corporation, VP-401, which is an ultrafine nitrile rubber powder; graphene oxide is from Beijing Huawei Ruike Chemical Co., Ltd., and graphene oxide is a single-layer graphene oxide with an average thickness of 0.8-1.2nm and a diameter of 0.5-5μm; nano-silicon dioxide is provided by Jiangsu Tianxing New Materials Co., Ltd., model TSP-H10, and a particle size of 20nm; 2-vinylbenzimidazole is from Shanghai Haohong Biomedical Technology Co., Ltd., CAS No.: 14984-26-0.

[0127] The flame retardant properties of the impact-resistant and high-temperature resistant materials prepared in Examples 1-5 and Comparative Examples 1-2 were tested. The limiting oxygen index test was performed with reference to GB / T 2406.2-2009 Oxygen Index Method - Plastic Combustion Performance Test Method. Each group was tested 5 times, and the average value was calculated. The test results are shown in Table 1.

[0128] Table 1

[0129]

[0130] According to the test results in Table 1, it can be seen that the impact-resistant and high-temperature resistant material prepared by the present invention has excellent flame retardant properties, especially the flame retardant properties of the impact-resistant and high-temperature resistant material corresponding to Example 5 are the best. Compared with Example 1, Comparative Example 1 lacks the effect of the initiator, and the nano-silicon dioxide containing unsaturated double bonds cannot be grafted on the polypropylene chain. The dispersibility and compatibility are lower than those of Example 1, which is not conducive to flame retardant properties. Therefore, the flame retardant properties of Comparative Example 1 are lower than those of Example 1; Comparative Example 2 lacks chlorosilane-modified nano-silicon dioxide compared to Comparative Example 1. The chlorine element contained in it has certain flame retardant properties. Once it is lacking, the flame retardant properties are naturally reduced.

[0131] The cable protection tubes prepared by using the impact-resistant and high-temperature-resistant materials prepared in Example 1 and Comparative Examples 1-2 were respectively tested accordingly, wherein the ring stiffness was tested according to GB / T9647-2015 "Test for Ring Stiffness of Thermoplastic Plastic Pipes"; wherein the heat aging performance test method was tested according to GB / T 2951.12-2008 "General Test Methods for Insulation and Sheath Materials of Cables and Optical Cables"; the mass wear was tested according to GB / T3930-2016 "Test Methods for Sliding Friction and Wear of Plastics"; the test results are shown in Table 2;

[0132] Table 2

[0133]

[0134] It can be seen from Table 2 that the cable protection tube made of the impact-resistant and high-temperature resistant material in Example 1 has higher deformation resistance, wear resistance and aging resistance than Comparative Examples 1-2. Graphene oxide and silicon dioxide are both heat-resistant and wear-resistant particles. Adding them to the matrix material can appropriately improve the high temperature resistance and wear resistance. In Comparative Example 1, nano-silica and polypropylene containing unsaturated double bonds are physically mixed, and their dispersibility is lower than that of Example 1. Therefore, the ring stiffness value and tensile performance retention rate value of Example 1 are greater than those of Comparative Example 1, and the wear amount of Example 1 is lower than that of Comparative Example 1; in Comparative Example 2, there is no chlorosilane-modified nano-silica, so the deformation resistance, wear resistance and aging resistance of Comparative Example 1 are better than those of Comparative Example 2.

[0135] Although the embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that all equivalent changes and improvements made within the scope of the present invention should still fall within the scope of the patent coverage of the present invention.

Claims

1. A method for preparing an impact-resistant and high-temperature resistant material, characterized in that: The following steps are involved: The polypropylene, nano-silicon dioxide containing unsaturated double bonds, initiator, polyetherimide, rubber elastomer, antioxidant, antioxidant and lubricant are mixed, stirred, heated for reaction, cooled to room temperature after the reaction is finished, and granulated to obtain an impact-resistant and high-temperature-resistant material; The preparation method of nano silicon dioxide containing unsaturated double bonds comprises the following steps: The modified nano-graphene oxide, the chlorosilane-modified nano-silica and acetone are stirred and mixed, heated, reacted, filtered and dried after the reaction is completed to obtain nano-silica containing unsaturated double bonds; The preparation method of modified nano graphene oxide comprises the following steps: Step (1) dissolving γ-glycidyloxypropyltrimethoxysilane in an ethanol aqueous solution to obtain a silane-modified solution, dispersing nano-graphene oxide in the silane-modified solution, reacting, filtering, washing with ethanol, and drying to obtain epoxy-modified nano-graphene oxide; Step (2) adding epoxy-modified nano-graphene oxide and 2-vinylbenzimidazole into anhydrous ethanol, stirring, heating, reacting, filtering, washing, and drying after the reaction is completed to obtain 2-vinylbenzimidazole-grafted epoxy-modified nano-graphene oxide; Step (3) adding diphenyl phosphate and 2-vinylbenzimidazole grafted epoxy-modified nano-graphene oxide to N,N-dimethylformamide, stirring, adding p-toluenesulfonic acid, heating, reacting, filtering, washing, and drying to obtain modified nano-graphene oxide; The preparation method of chlorosilane-modified nano-silica comprises the following steps: The nano-silica, toluene and 3-chloropropylmethyldimethoxysilane are mixed evenly, heated, reacted, filtered, washed and dried after the reaction is completed to obtain chlorosilane-modified nano-silica.

2. The method for preparing an impact-resistant and high-temperature-resistant material according to claim 1, characterized in that: The mass ratio of polypropylene, nano-silica containing unsaturated double bonds, initiator, polyetherimide, rubber elastomer, antioxidant, antioxidant and lubricant is (80-100):(8-12):(0.2-0.4):(8-10):(3-5):(0.1-0.5):(0.4-0.8):(1-3).

3. The method for preparing an impact-resistant and high-temperature-resistant material according to claim 1, characterized in that: The mass ratio of modified nano-graphene oxide, chlorosilane-modified nano-silica and acetone is (300-500):(60-80):(2500-4500); the reaction conditions are 25-35° C. and the reaction time is 4-6 hours.

4. The method for preparing an impact-resistant and high-temperature-resistant material according to claim 1, characterized in that: The mass ratio of nano-graphene oxide, γ-glycidyloxypropyltrimethoxysilane and ethanol aqueous solution is (80-100):200:(4000-6000); the reaction conditions are 55-75° C. and 70-130 min.

5. The method for preparing an impact-resistant and high-temperature-resistant material according to claim 1, characterized in that: The mass ratio of epoxy-modified nano-graphene oxide, 2-vinylbenzimidazole and anhydrous ethanol is (200-240):(150-180):(600-900); the reaction conditions are 30-50° C. for 5-7 hours.

6. The method for preparing an impact-resistant and high-temperature-resistant material according to claim 1, characterized in that: The mass ratio of diphenyl phosphate, 2-vinylbenzimidazole grafted epoxy-modified nano-graphene oxide, N,N-dimethylformamide and p-toluenesulfonic acid is (280-320):(300-500):(1000-2000):(16-22); the reaction conditions are 80-100° C. for 16-18 hours.

7. The method for preparing an impact-resistant and high-temperature-resistant material according to claim 1, characterized in that: The mass ratio of nano-silica, toluene and 3-chloropropylmethyldimethoxysilane is (80-100):(1500-2500):(60-80); the reaction conditions are 75-85° C. and 14-16 hours.

8. An impact-resistant and high-temperature resistant material prepared by the method for preparing an impact-resistant and high-temperature resistant material according to any one of claims 1 to 7.

9. Use of the impact-resistant and high-temperature-resistant material according to claim 8 in a cable protection tube.

10. The use according to claim 9, characterized in that: The manufacturing process of the cable protection tube in the application includes the following steps: Polypropylene, nano-silica containing unsaturated double bonds, initiator, polyetherimide, rubber elastomer, antioxidant, antioxidant and lubricant are mixed, then transferred to a twin-screw extruder, extruded and granulated at 170-200°C, then added to the hopper of a pipe extruder, extruded and formed to obtain a cable protection tube.

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