High-temperature-resistant flame-retardant rubber and plastic plate as well as preparation method and application thereof

Abstract

The invention relates to the technical field of high-temperature-resistant rubber and plastic materials, in particular to a high-temperature-resistant flame-retardant rubber and plastic plate as well as a preparation method and application thereof. The high-temperature-resistant flame-retardant rubber and plastic plate sequentially comprises a first flame-retardant layer, a supporting layer and a second flame-retardant layer from top to bottom, wherein the main raw materials of the first flame-retardant layer comprise Fe2O3-SiO2 modified silicone rubber and flame-retardant coated glass fibers; the main raw materials of the supporting layer comprise waste rubber and plastic plate particles and chopped basalt fibers; the main raw materials of the second flame-retardant layer comprise graphene-ZnO modified fluororubber, ethylene propylene diene monomer, mica powder and flame-retardant coated glass fibers. According to the high-temperature-resistant flame-retardant rubber and plastic plate, the synergistic effect of all the raw material components is utilized, and the auxiliaries are supplemented, so that the high-temperature-resistant flame-retardant rubber and plastic plate has good mechanical properties, high temperature resistance and flame retardance, and the problems that in the prior art, rubber and plastic materials are limited in high temperature resistance and flame retardance, poor in mechanical properties and unfriendly to the environment are effectively solved.

Description

Technical Field

[0001] The invention relates to the technical field of high temperature resistant rubber and plastic materials, and in particular to a high temperature resistant flame retardant rubber and plastic sheet material and a preparation method and application thereof. Background Art

[0002] With the rapid development of modern industry, the demand for operations in high-temperature environments is increasing. Ordinary rubber and plastic materials often experience performance degradation under high-temperature conditions and cannot meet actual application requirements. In many high-temperature and flammable environment application scenarios, such as aerospace, automobile engine compartments, and the interior of electronic and electrical equipment, high-temperature resistant rubber and plastic materials have received extensive attention and in-depth research because they can maintain stable physical and chemical properties for a long time at high temperatures. This type of material not only has good rubber elasticity and plastic processing performance, but also has excellent flame retardant effects to prevent the occurrence of fire accidents. The continuous improvement of its performance and innovative applications are of great significance to promoting technological progress in related industries.

[0003] However, the existing high-temperature resistant flame-retardant rubber and plastic materials still have certain temperature limitations. When the temperature exceeds its tolerance range, the performance of the material will decline and the flame retardant effect will deteriorate. Compared with materials such as metals, rubber and plastic materials have lower mechanical strength and poorer mechanical properties, and are easily damaged by external forces. In some application environments that need to withstand greater pressure or impact, additional protective measures may be required. In this regard, the prior art has also proposed methods such as modifying rubber and plastic materials. It has been reported that organic modification of rubber or plastic components can further improve the high-temperature resistance of rubber and plastic materials. However, organically modified rubber and plastic materials will inevitably release toxic gases in high-temperature environments, which is not environmentally friendly. In addition, organic modification has very limited effect on the improvement of the high-temperature resistance of rubber and plastic, and it is difficult to meet the application requirements at higher temperatures.

[0004] Based on this, developing a rubber-plastic material with good high temperature resistance and flame retardant properties has great practical significance for the development of rubber-plastic materials. Summary of the invention

[0005] In view of the problems in the prior art that rubber and plastic materials have limited high temperature flame retardant properties, poor mechanical properties and are not environmentally friendly, the present invention provides a high temperature flame retardant rubber and plastic sheet material and its preparation method and application. The high temperature resistant rubber and plastic sheet material comprises a first flame retardant layer, a support layer and a second flame retardant layer from top to bottom, wherein the raw materials of the first flame retardant layer include Fe2O3-SiO2 modified silicone rubber, flame retardant coated glass fiber, antioxidant, activator and vulcanization aid; the raw materials of the support layer include waste rubber and plastic sheet material particles, chopped basalt fiber and adhesive; the raw materials of the second flame retardant layer include graphene-ZnO modified fluororubber, EPDM rubber, mica powder, flame retardant coated glass fiber, antioxidant, activator and vulcanization aid. The present invention utilizes the synergistic effect of the raw materials of each component to successfully prepare a rubber and plastic sheet material with excellent mechanical properties, good high temperature resistance and flame retardant properties, which is environmentally friendly and can effectively alleviate the processing pressure of solid waste materials.

[0006] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions: The first aspect of the present invention provides a high temperature resistant flame retardant rubber-plastic sheet material, which comprises a first flame retardant layer, a support layer and a second flame retardant layer from top to bottom; wherein the raw materials of the first flame retardant layer comprise the following raw material components in parts by weight: 35-60 parts of Fe2O3-SiO2 modified silicone rubber, 5-15 parts of flame retardant coated glass fiber, 1-5 parts of antioxidant, 1-3 parts of activator and 1-3 parts of vulcanization aid; The support layer comprises the following raw material components in parts by weight: 50-60 parts of waste rubber and plastic sheet particles, 20-30 parts of chopped basalt fibers and 5-15 parts of adhesive; The second flame retardant layer comprises the following raw material components in parts by weight: 35-55 parts of graphene-ZnO modified fluororubber, 10-25 parts of EPDM rubber, 10-20 parts of mica powder, 5-15 parts of flame retardant coated glass fiber, 1-5 parts of antioxidant, 1-3 parts of activator and 1-3 parts of vulcanization aid.

[0007] The present invention designs a layered high temperature resistant flame retardant rubber-plastic sheet, the upper surface and the lower bottom surface of which are both flame retardant rubber materials, and the supporting layer is a mixture of waste rubber-plastic sheet and rigid fiber. Among them, the first flame retardant layer (upper surface) is mainly made of Fe2O3-SiO2 modified silicone rubber and flame retardant coated glass fiber. Silicon dioxide modification of silicone rubber can further increase the content of silicon oxygen bonds in silicone rubber. Due to the high bond energy of silicon oxygen bonds, the silicone rubber molecular chain is not easy to break at high temperature. At the same time, organic groups can be connected to silicon atoms, which can adjust the flexibility of silicone rubber to a certain extent, so that it maintains good elasticity in a wide temperature range. Iron oxide can react with free radicals generated by the break of silicone rubber at high temperature, prevent the chain reaction of free radicals, and then destroy the chain degradation reaction of the main chain of silicone rubber caused by free radicals, reduce the high temperature damage of silicone rubber, and improve its heat resistance. At the same time, iron oxide can also absorb part of the heat and slow down the damage rate of silicone rubber caused by temperature rise. Glass fiber itself has high strength and high modulus. After being coated with flame retardant, it can not only improve the tensile strength, bending strength and impact strength of the material, but also form a barrier layer to isolate oxygen and heat, so that the rubber-plastic sheet has good mechanical properties and flame retardant properties.

[0008] The support layer uses waste rubber and plastic sheets and chopped basalt fibers as the main raw materials, which not only effectively alleviates the processing pressure of waste rubber and plastic sheets and realizes the recycling of solid waste materials, but also can be used as fillers for the support layer and filled in the basalt fiber skeleton. Basalt fiber has excellent mechanical properties and the advantages of high strength and high modulus. As the support layer skeleton, it has good rigidity and deformation resistance to maintain the stability of the structure. In addition, basalt fiber has high temperature resistance and can still maintain stable chemical properties in high temperature environments, and is not prone to thermal deformation or embrittlement.

[0009] The second flame retardant layer (bottom surface) designed by the present invention is mainly made of graphene-ZnO modified fluororubber, EPDM rubber, mica powder and flame retardant coated glass fiber. Among them, the addition of graphene can effectively improve the tensile strength and wear resistance of fluororubber, so that it can withstand greater external force and friction; and the lamellar structure of graphene can form a grid structure inside the fluororubber, which can effectively block the penetration of gas molecules, and the molecular structure of the fluororubber modified by graphene is more stable and has better anti-aging performance; the addition of zinc oxide can absorb the free radicals generated by fluororubber at high temperature, slow down the thermal degradation reaction of fluororubber molecules, improve the thermal stability of fluororubber, and reduce the aging and cracking of fluororubber in high temperature environment; and the addition of zinc oxide can also accelerate the vulcanization speed and improve production efficiency. Mica powder has a layered structure. When used as a filler, its layered structure can play a barrier role in the rubber matrix, reduce the transfer speed of gas and heat, and reduce the heat absorbed by rubber in a high temperature environment.

[0010] In summary, the present invention uses Fe2O3-SiO2 modified silicone rubber flame retardant coated glass fiber, waste rubber and plastic sheet particles, chopped basalt fiber, graphene-ZnO modified fluororubber, EPDM rubber and mica powder as main raw materials, supplemented by antioxidants, adhesives, activators and vulcanization aids to prepare a layered rubber and plastic sheet with excellent mechanical properties and good high-temperature flame retardant properties. It effectively solves the problems of limited high-temperature flame retardant properties, poor mechanical properties and environmental unfriendliness of rubber and plastic materials in the prior art, and provides a new design idea for the development of high-temperature resistant rubber and plastic materials.

[0011] Preferably, the thickness of the first flame retardant layer is 10 mm-20 mm.

[0012] Preferably, the thickness of the support layer is 20 mm-30 mm.

[0013] Preferably, the thickness of the second flame retardant layer is 15 mm-25 mm.

[0014] Preferably, the preparation method of the Fe2O3-SiO2 modified silicone rubber comprises the following steps: S1, dispersing nano silicon dioxide and nano iron oxide in a silane coupling agent, and performing ultrasonic treatment to obtain a mixture; S2. Kneading the raw silicone rubber at 90° C.-110° C. to obtain kneaded rubber; uniformly mixing the kneaded rubber with the mixture, kneading at 80° C.-95° C., adding a vulcanizing agent for vulcanization, and obtaining Fe2O3-SiO2 modified silicone rubber.

[0015] Further preferably, in S1, the mass ratio of the nano-silicon dioxide to the nano-iron oxide is 1:0.3-1:0.4.

[0016] Further preferably, in S1, the silane coupling agent is KH570 or KH550.

[0017] Further preferably, in S1, the mass ratio of the nano-silica to the silane coupling agent is 1:3-1:5.

[0018] Further preferably, in S1, the temperature of the ultrasonic treatment is 40°C-50°C, and the time of the ultrasonic treatment is 30min-40min.

[0019] Further preferably, in S2, the mass ratio of the silicone rubber raw rubber to the mixture is 5:1-5:2.

[0020] Further preferably, in S2, the banburying time is 5 min-10 min.

[0021] More preferably, in S2, the mixing time is 8 min-12 min.

[0022] Further preferably, in S2, the vulcanizing agent is dicumyl peroxide.

[0023] Further preferably, in S2, the amount of the vulcanizing agent added is 5%-10% of the mass of the silicone rubber raw rubber.

[0024] Further preferably, in S2, the vulcanization temperature is 180°C-190°C, and the vulcanization time is 20h-24h.

[0025] Preferably, the method for preparing the flame retardant coated glass fiber comprises the following steps: Step a, mixing glass fiber and silane coupling agent and dispersing them in an alcohol solvent, ultrasonicating, filtering, and obtaining pretreated glass fiber; Step b, uniformly mixing the flame retardant and the epoxy resin to obtain a flame retardant slurry; Step c: immersing the pretreated glass fiber in the flame retardant slurry and drying the slurry to obtain the flame retardant coated glass fiber.

[0026] Further preferably, in step a, the length of the glass fiber is 0.5 mm-1 mm.

[0027] Further preferably, in step a, the mass ratio of the glass fiber to the silane coupling agent is 1:0.4-1:0.6.

[0028] Further preferably, in step a, the alcohol solvent is anhydrous ethanol.

[0029] Further preferably, in step a, the mass volume ratio of the silane coupling agent to the alcohol solvent is 1 g:5 mL-1 g:8 mL.

[0030] Further preferably, in step a, the ultrasonic time is 1h-2h.

[0031] Further preferably, in step b, the flame retardant is ammonium polyphosphate flame retardant or diethyl aluminum phosphinate flame retardant.

[0032] Further preferably, in step b, the mass volume ratio of the flame retardant to the epoxy resin is 1g:3mL-1g:4mL.

[0033] Further preferably, in step b, the mass ratio of the pretreated glass fiber to the flame retardant slurry is 1:1.5-1:2.

[0034] Further preferably, in step c, the immersion time is 1 h-3 h.

[0035] Further preferably, in step c, the drying temperature is 80° C.-90° C., the vacuum degree is 0.6 MPa-0.7 MPa; and the drying time is 3 h-5 h.

[0036] Preferably, the preparation method of the graphene-ZnO modified fluororubber comprises the following steps: kneading the raw fluororubber at 60°C-75°C to obtain kneaded fluororubber; adding graphene powder and nano ZnO to the kneaded fluororubber, kneading at 70°C-85°C, adding a vulcanizing agent for vulcanization, and obtaining graphene-ZnO modified fluororubber.

[0037] More preferably, the banburying time is 8 min-10 min.

[0038] Further preferably, the mass ratio of the fluororubber raw rubber, the graphene powder and the nano ZnO is 1:0.2:0.1-1:0.3:0.1.

[0039] More preferably, the mixing time is 4 min-6 min.

[0040] Further preferably, the added amount of the vulcanizing agent is 5%-8% of the mass of the fluororubber raw rubber.

[0041] More preferably, the vulcanization temperature is 170° C.-220° C., and the vulcanization time is 16 h-24 h.

[0042] Preferably, the antioxidant is antioxidant MB.

[0043] Preferably, the activator is stearic acid.

[0044] Preferably, the vulcanization aid is sulfur and ethylene thiourea in a mass ratio of 1:1.

[0045] Preferably, the adhesive is hexamethoxymethylmelamine.

[0046] Preferably, the length of the chopped basalt fibers is 5 mm to 15 mm.

[0047] The second aspect of the present invention provides a method for preparing the high temperature resistant flame retardant rubber-plastic sheet material, comprising the following steps: Step 1: Fe2O3-SiO2 modified silicone rubber, flame retardant coated glass fiber, antioxidant and activator are weighed according to the designed ratio, mixed evenly, kneaded at 85°C-95°C, and then vulcanized at 160°C-180°C, extruded and formed to obtain the first flame retardant layer board; Step 2: weigh the waste rubber and plastic sheet particles, chopped basalt fibers and adhesive according to the designed ratio, mix them evenly, knead them at 100° C.-110° C., and extrude them to obtain a support layer sheet; Step 3: weigh graphene-ZnO modified fluororubber, EPDM rubber, mica powder, flame retardant coated glass fiber, antioxidant and activator according to the designed ratio, mix them evenly, knead them at 80°C-90°C, add vulcanization aids, vulcanize them at 150°C-180°C, and extrude them to obtain a second flame retardant layer plate; Step 4: stack the second flame retardant layer board, the support layer board and the first flame retardant layer board in order from bottom to top, and use hot melt fiber to bond the second flame retardant layer board, the support layer board and the first flame retardant layer board to obtain a high temperature resistant flame retardant rubber-plastic board.

[0048] Preferably, in step 1, the mixing temperature is 8 min-10 min.

[0049] Preferably, in step 1, the vulcanization time is 12h-16h.

[0050] Preferably, in step 2, the mixing time is 15 min-20 min.

[0051] Preferably, in step three, the mixing time is 8 min-12 min.

[0052] Preferably, in step three, the specific operation of the vulcanization is: after adding the vulcanization accelerator, the temperature is raised to 150°C-160°C for a first-stage vulcanization for 2h-4h; and then the temperature is raised to 170°C-180°C for a second-stage vulcanization for 12h-14h.

[0053] Preferably, in step 4, the hot-melt fiber is polyolefin multifilament fiber SWP.

[0054] A third aspect of the present invention provides an application of the high temperature resistant flame retardant rubber-plastic sheet material or the high temperature resistant flame retardant rubber-plastic sheet material prepared by the preparation method of the high temperature resistant flame retardant rubber-plastic sheet material in the field of flame retardant materials.

[0055] In summary, the present invention designs a layered high temperature resistant flame retardant rubber-plastic sheet material, and utilizes the synergistic effect of the raw material components between the layers to obtain a rubber-plastic product with excellent mechanical properties, high temperature resistance and good flame retardant properties. The preparation method of the high temperature resistant flame retardant rubber-plastic sheet material is simple, and the raw materials are mostly inorganically modified and are environmentally friendly. The technical solution of the present invention effectively solves the problems of limited high temperature resistant flame retardant properties, poor mechanical properties and environmental unfriendliness of rubber-plastic materials in the prior art, and provides a new idea for the development of high temperature resistant rubber-plastic materials. DETAILED DESCRIPTION

[0056] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. 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.

[0057] Example 1 This embodiment provides a high temperature resistant flame retardant rubber-plastic sheet and a preparation method thereof, which specifically includes the following contents: The high temperature resistant flame retardant rubber-plastic sheet comprises a first flame retardant layer, a support layer and a second flame retardant layer from top to bottom; the raw materials of the first flame retardant layer comprise the following raw material components by weight: 55 parts of Fe2O3-SiO2 modified silicone rubber, 10 parts of flame retardant coated glass fiber, 3 parts of antioxidant MB, 2 parts of stearic acid and 2 parts of vulcanization aid; The support layer comprises the following raw material components in parts by weight: 55 parts of waste rubber and plastic sheet particles, 25 parts of chopped basalt fibers and 10 parts of hexamethoxymethyl melamine; The second flame retardant layer includes the following raw material components in parts by mass: 45 parts of graphene-ZnO modified fluororubber, 20 parts of EPDM rubber, 15 parts of mica powder, 10 parts of flame retardant coated glass fiber, 3 parts of antioxidant MB, 2 parts of stearic acid and 2 parts of vulcanization aid.

[0058] The method for preparing the high temperature resistant flame retardant rubber-plastic sheet comprises the following steps: Step 1: Fe2O3-SiO2 modified silicone rubber, flame retardant coated glass fiber, antioxidant and activator are weighed according to the designed ratio, mixed evenly, kneaded at 90°C for 10 minutes, and then vulcanized at 175°C for 14 hours, extruded to obtain a first flame retardant layer plate with a thickness of 15 mm; Step 2: Weigh the waste rubber and plastic sheet particles, 10 mm long chopped basalt fibers and hexamethoxymethyl melamine according to the designed ratio, mix them evenly, knead them at 105° C. for 18 min, and extrude them to obtain a support layer sheet with a thickness of 25 mm; Step 3: According to the designed ratio, weigh the graphene-ZnO modified fluororubber, EPDM rubber, mica powder, flame retardant coated glass fiber, antioxidant and activator, mix them evenly, mix them at 85°C for 10 minutes, add the vulcanization aid, first heat to 155°C for a first stage vulcanization for 3 hours, then heat to 175°C for a second stage vulcanization for 14 hours, extrude and mold, and obtain a second flame retardant layer plate with a thickness of 20 mm; Step 4: stack the second flame retardant layer sheet, the support layer sheet and the first flame retardant layer sheet in order from bottom to top, and bond the second flame retardant layer sheet, the support layer sheet and the first flame retardant layer sheet with polyolefin multifilament fiber SWP to obtain a high temperature resistant flame retardant rubber-plastic sheet.

[0059] The preparation method of the Fe2O3-SiO2 modified silicone rubber comprises the following steps: S1. Disperse 100 g of nano-silicon dioxide and 35 g of nano-iron oxide in 400 g of silane coupling agent KH570, and perform ultrasonic treatment at 45° C. for 35 min to obtain a modified mixture; S2. Knead 2.5 kg of raw silicone rubber at 105° C. for 6 min to obtain kneaded rubber; mix the kneaded rubber and the modified mixture evenly, knead at 90° C. for 10 min, add 150 g of diisopropylbenzene peroxide for vulcanization, and vulcanize at 185° C. for 24 h to obtain Fe2O3-SiO2 modified silicone rubber.

[0060] The method for preparing the flame retardant coated glass fiber comprises the following steps: Step a, 200 g of glass fiber with a length of 0.8 mm and 100 g of silane coupling agent KH570 were mixed and dispersed in 600 mL of anhydrous ethanol, ultrasonicated for 1.5 h, and filtered to obtain pretreated glass fiber; Step b, uniformly mixing 100 g of ammonium polyphosphate flame retardant and 350 g of epoxy resin to obtain a flame retardant slurry; Step c, immersing the pretreated glass fiber in the flame retardant slurry, filtering after immersion for 2 hours, and drying at a vacuum degree of 0.7 MPa and 85° C. for 4 hours to obtain the flame retardant coated glass fiber.

[0061] The preparation method of the graphene-ZnO modified fluororubber comprises the following steps: kneading 2kg of fluororubber raw rubber at 70°C for 9 minutes to obtain kneaded fluororubber; adding 450g of graphene powder and 200g of nano ZnO to the kneaded fluororubber, kneading for 5min at 80°C, adding 130g of diisopropylbenzene peroxide, and vulcanizing at 190°C for 20h to obtain graphene-ZnO modified fluororubber.

[0062] The vulcanization aid is sulfur and ethylene thiourea in a mass ratio of 1:1.

[0063] Example 2 This embodiment provides a high temperature resistant flame retardant rubber-plastic sheet and a preparation method thereof, which specifically includes the following contents: The high temperature resistant flame retardant rubber-plastic sheet comprises a first flame retardant layer, a support layer and a second flame retardant layer from top to bottom; the raw materials of the first flame retardant layer comprise the following raw material components in parts by weight: 60 parts of Fe2O3-SiO2 modified silicone rubber, 12 parts of flame retardant coated glass fiber, 5 parts of antioxidant MB, 3 parts of stearic acid and 3 parts of vulcanization aid; The support layer comprises the following raw material components in parts by weight: 50 parts of waste rubber and plastic sheet particles, 30 parts of chopped basalt fibers and 15 parts of hexamethoxymethyl melamine; The second flame retardant layer includes the following raw material components in parts by mass: 55 parts of graphene-ZnO modified fluororubber, 15 parts of EPDM rubber, 20 parts of mica powder, 15 parts of flame retardant coated glass fiber, 3 parts of antioxidant MB, 3 parts of stearic acid and 3 parts of vulcanization aid.

[0064] The method for preparing the high temperature resistant flame retardant rubber-plastic sheet comprises the following steps: Step 1: Fe2O3-SiO2 modified silicone rubber, flame retardant coated glass fiber, antioxidant and activator are weighed according to the designed ratio, mixed evenly, kneaded at 85°C for 9 minutes, and then vulcanized at 170°C for 14 hours, extruded to obtain a first flame retardant layer plate with a thickness of 20 mm; Step 2: Weigh the waste rubber and plastic sheet particles, 10 mm long chopped basalt fibers and hexamethoxymethyl melamine according to the designed ratio, mix them evenly, knead them at 105° C. for 15 min, and extrude them to obtain a support layer sheet with a thickness of 30 mm; Step 3: According to the designed ratio, weigh the graphene-ZnO modified fluororubber, EPDM rubber, mica powder, flame retardant coated glass fiber, antioxidant and activator, mix them evenly, mix them at 85°C for 10 minutes, add the vulcanization aid, first heat to 155°C for a first stage vulcanization for 3 hours, then heat to 175°C for a second stage vulcanization for 14 hours, extrude and mold, and obtain a second flame retardant layer plate with a thickness of 15 mm; Step 4: stack the second flame retardant layer sheet, the support layer sheet and the first flame retardant layer sheet in order from bottom to top, and bond the second flame retardant layer sheet, the support layer sheet and the first flame retardant layer sheet with polyolefin multifilament fiber SWP to obtain a high temperature resistant flame retardant rubber-plastic sheet.

[0065] The preparation method of the Fe2O3-SiO2 modified silicone rubber comprises the following steps: S1. Disperse 100 g of nano-silicon dioxide and 35 g of nano-iron oxide in 400 g of silane coupling agent KH570, and perform ultrasonic treatment at 45° C. for 35 min to obtain a modified mixture; S2. Knead 2.5 kg of raw silicone rubber at 105° C. for 6 min to obtain kneaded rubber; mix the kneaded rubber and the modified mixture evenly, knead at 90° C. for 10 min, add 150 g of diisopropylbenzene peroxide for vulcanization, and vulcanize at 190° C. for 23 h to obtain Fe2O3-SiO2 modified silicone rubber.

[0066] The method for preparing the flame retardant coated glass fiber comprises the following steps: Step a, 200 g of glass fiber with a length of 0.8 mm and 100 g of silane coupling agent KH570 were mixed and dispersed in 600 mL of anhydrous ethanol, ultrasonicated for 1.5 h, and filtered to obtain pretreated glass fiber; Step b, uniformly mixing 100 g of ammonium polyphosphate flame retardant and 300 g of epoxy resin to obtain a flame retardant slurry; Step c, immersing the pretreated glass fiber in the flame retardant slurry, filtering after immersion for 2 hours, and drying at a vacuum degree of 0.7 MPa and 85° C. for 4 hours to obtain the flame retardant coated glass fiber.

[0067] The preparation method of the graphene-ZnO modified fluororubber comprises the following steps: kneading 2kg of fluororubber raw rubber at 70°C for 9 minutes to obtain kneaded fluororubber; adding 450g of graphene powder and 200g of nano ZnO to the kneaded fluororubber, kneading for 5min at 80°C, adding 130g of diisopropylbenzene peroxide, and vulcanizing at 190°C for 20h to obtain graphene-ZnO modified fluororubber.

[0068] The vulcanization aid is sulfur and ethylene thiourea in a mass ratio of 1:1.

[0069] Example 3 This embodiment provides a high temperature resistant flame retardant rubber-plastic sheet and a preparation method thereof, which specifically includes the following contents: The high temperature resistant flame retardant rubber-plastic sheet comprises a first flame retardant layer, a support layer and a second flame retardant layer from top to bottom; the raw materials of the first flame retardant layer comprise the following raw material components in parts by weight: 40 parts of Fe2O3-SiO2 modified silicone rubber, 15 parts of flame retardant coated glass fiber, 5 parts of antioxidant MB, 1 part of stearic acid and 3 parts of vulcanization aid; The support layer comprises the following raw material components in parts by weight: 60 parts of waste rubber and plastic sheet particles, 20 parts of chopped basalt fibers and 5 parts of hexamethoxymethyl melamine; The second flame retardant layer includes the following raw material components in parts by mass: 35 parts of graphene-ZnO modified fluororubber, 25 parts of EPDM rubber, 12 parts of mica powder, 15 parts of flame retardant coated glass fiber, 3 parts of antioxidant MB, 3 parts of stearic acid and 2 parts of vulcanization aid.

[0070] The method for preparing the high temperature resistant flame retardant rubber-plastic sheet comprises the following steps: Step 1: Fe2O3-SiO2 modified silicone rubber, flame retardant coated glass fiber, antioxidant and activator are weighed according to the designed ratio, mixed evenly, kneaded at 90°C for 10 minutes, and then vulcanized at 175°C for 14 hours, extruded to obtain a first flame retardant layer plate with a thickness of 10 mm; Step 2: Weigh the waste rubber and plastic sheet particles, 10 mm long chopped basalt fibers and hexamethoxymethyl melamine according to the designed ratio, mix them evenly, knead them at 105° C. for 18 min, and extrude them to obtain a support layer sheet with a thickness of 23 mm; Step 3: According to the designed ratio, weigh the graphene-ZnO modified fluororubber, EPDM rubber, mica powder, flame retardant coated glass fiber, antioxidant and activator, mix them evenly, mix them at 85°C for 10 minutes, add the vulcanization aid, first heat to 155°C for a first stage vulcanization for 3 hours, then heat to 175°C for a second stage vulcanization for 14 hours, extrude and mold, and obtain a second flame retardant layer plate with a thickness of 18 mm; Step 4: stack the second flame retardant layer sheet, the support layer sheet and the first flame retardant layer sheet in order from bottom to top, and bond the second flame retardant layer sheet, the support layer sheet and the first flame retardant layer sheet with polyolefin multifilament fiber SWP to obtain a high temperature resistant flame retardant rubber-plastic sheet.

[0071] The preparation method of the Fe2O3-SiO2 modified silicone rubber comprises the following steps: S1. Disperse 100 g of nano-silicon dioxide and 35 g of nano-iron oxide in 400 g of silane coupling agent KH550, and perform ultrasonic treatment at 45° C. for 35 min to obtain a modified mixture; S2. Knead 2.5 kg of raw silicone rubber at 105° C. for 6 min to obtain kneaded rubber; mix the kneaded rubber and the modified mixture evenly, knead at 90° C. for 10 min, add 150 g of diisopropylbenzene peroxide for vulcanization, and vulcanize at 180° C. for 24 h to obtain Fe2O3-SiO2 modified silicone rubber.

[0072] The method for preparing the flame retardant coated glass fiber comprises the following steps: Step a, 200 g of glass fiber with a length of 0.8 mm and 100 g of silane coupling agent KH550 were mixed and dispersed in 600 mL of anhydrous ethanol, ultrasonicated for 1.5 h, and filtered to obtain pretreated glass fiber; Step b, uniformly mixing 100 g of ammonium polyphosphate flame retardant and 300 g of epoxy resin to obtain a flame retardant slurry; Step c, immersing the pretreated glass fiber in the flame retardant slurry, filtering after immersion for 2 hours, and drying at a vacuum degree of 0.7 MPa and 85° C. for 4 hours to obtain the flame retardant coated glass fiber.

[0073] The preparation method of the graphene-ZnO modified fluororubber comprises the following steps: kneading 2kg of fluororubber raw rubber at 70°C for 9 minutes to obtain kneaded fluororubber; adding 450g of graphene powder and 200g of nano ZnO to the kneaded fluororubber, kneading for 5 minutes at 80°C, adding 135g of diisopropylbenzene peroxide, and vulcanizing at 190°C for 20 hours to obtain graphene-ZnO modified fluororubber.

[0074] The vulcanization aid is sulfur and ethylene thiourea in a mass ratio of 1:1.

[0075] Comparative Example 1 This comparative example provides a high temperature resistant flame retardant rubber-plastic sheet, which differs from Example 1 in that the Fe2O3-SiO2 modified silicone rubber in the first flame retardant layer is replaced with an equal amount of SiO2 modified silicone rubber, and other components and processes remain unchanged and will not be described again here.

[0076] Comparative Example 2 This comparative example provides a high temperature resistant flame retardant rubber-plastic sheet, which differs from Example 1 in that the flame retardant coated glass fibers in the first flame retardant layer and the second flame retardant layer are replaced with an equal amount of glass fibers, and other components and processes remain unchanged and will not be described in detail here.

[0077] Comparative Example 3 This comparative example provides a high temperature resistant flame retardant rubber-plastic sheet, which differs from Example 1 in that the graphene-ZnO modified fluororubber in the second flame retardant layer is replaced with an equal amount of graphene modified fluororubber, and other components and processes remain unchanged and will not be described again here.

[0078] Comparative Example 4 This comparative example provides a high temperature resistant flame retardant rubber-plastic sheet, which differs from Example 1 in that the mica powder in the second flame retardant layer is replaced with an equal amount of graphite powder, and other components and processes remain unchanged, which will not be described again.

[0079] In order to further demonstrate the technical effect of the present invention, the present invention conducted the following tests on the high temperature resistant flame retardant rubber-plastic sheets obtained in Examples 1-3 and Comparative Examples 1-4: (1) referring to GB / T528-2009, the tensile strength, tear strength and elongation of each high temperature resistant flame retardant rubber-plastic sheet were tested at room temperature (25°C) and high temperature (250°C, placed for 72 hours); (2) referring to UL94 standard to test the flame retardant grade; the test results are shown in Tables 1-3.

[0080] Table 1 Mechanical properties test results of various high temperature resistant flame retardant rubber and plastic sheets at room temperature

[0081] Table 2 Mechanical properties test results of various high temperature resistant flame retardant rubber and plastic sheets at high temperature

[0082] Table 3 Mechanical properties test results of various high temperature resistant flame retardant rubber and plastic sheets at room temperature

[0083] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modification, equivalent substitution or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A high temperature resistant flame retardant rubber-plastic sheet, characterized by: The high temperature resistant flame retardant rubber-plastic sheet material comprises a first flame retardant layer, a support layer and a second flame retardant layer from top to bottom; wherein the raw materials of the first flame retardant layer comprise the following raw material components in parts by weight: 35-60 parts of Fe2O3-SiO2 modified silicone rubber, 5-15 parts of flame retardant coated glass fiber, 1-5 parts of antioxidant, 1-3 parts of activator and 1-3 parts of vulcanization aid; The support layer comprises the following raw material components in parts by weight: 50-60 parts of waste rubber and plastic sheet particles, 20-30 parts of chopped basalt fibers and 5-15 parts of adhesive; The second flame retardant layer comprises the following raw material components in parts by weight: 35-55 parts of graphene-ZnO modified fluororubber, 10-25 parts of EPDM rubber, 10-20 parts of mica powder, 5-15 parts of flame retardant coated glass fiber, 1-5 parts of antioxidant, 1-3 parts of activator and 1-3 parts of vulcanization aid.

2. The high temperature resistant flame retardant rubber-plastic sheet material according to claim 1, characterized in that: The thickness of the first flame retardant layer is 10 mm to 20 mm; and / or The thickness of the support layer is 20 mm to 30 mm; and / or The thickness of the second flame retardant layer is 15 mm-25 mm.

3. The high temperature resistant flame retardant rubber-plastic sheet material according to claim 1, characterized in that: The preparation method of the Fe2O3-SiO2 modified silicone rubber comprises the following steps: S1, dispersing nano silicon dioxide and nano iron oxide in a silane coupling agent, and performing ultrasonic treatment to obtain a mixture; S2. Kneading the raw silicone rubber at 90° C.-110° C. to obtain kneaded rubber; uniformly mixing the kneaded rubber with the mixture, kneading at 80° C.-95° C., adding a vulcanizing agent for vulcanization, and obtaining Fe2O3-SiO2 modified silicone rubber.

4. The high temperature resistant flame retardant rubber-plastic sheet material according to claim 3, characterized in that: In S1, the mass ratio of the nano-silicon dioxide to the nano-iron oxide is 1:0.3-1:0.4; and / or In S1, the silane coupling agent is KH570 or KH550; and / or In S1, the mass ratio of the nano-silicon dioxide to the silane coupling agent is 1:3-1:5; and / or In S1, the temperature of the ultrasonic treatment is 40-50°C, and the time of the ultrasonic treatment is 30min-40min; and / or In S2, the mass ratio of the silicone rubber to the mixture is 5:1-5:2; and / or In S2, the mixing time is 5 min-10 min; and / or In S2, the mixing time is 8 min-12 min; and / or In S2, the vulcanizing agent is dicumyl peroxide; and / or In S2, the amount of the vulcanizing agent added is 5%-10% of the mass of the raw silicone rubber.

5. The high temperature resistant flame retardant rubber-plastic sheet material according to claim 1, characterized in that: The method for preparing the flame retardant coated glass fiber comprises the following steps: Step a, mixing glass fiber and silane coupling agent and dispersing them in an alcohol solvent, ultrasonicating, filtering, and obtaining pretreated glass fiber; Step b, uniformly mixing the flame retardant and the epoxy resin to obtain a flame retardant slurry; Step c: immersing the pretreated glass fiber in the flame retardant slurry and drying the slurry to obtain the flame retardant coated glass fiber.

6. The high temperature resistant flame retardant rubber-plastic sheet material according to claim 5, characterized in that: In step a, the length of the glass fiber is 0.5 mm-1 mm; and / or In step a, the mass ratio of the glass fiber to the silane coupling agent is 1:0.4-1:0.6; and / or In step a, the mass volume ratio of the silane coupling agent to the alcohol solvent is 1g:5mL-1g:8mL; and / or In step a, the ultrasonic time is 1h-2h; and / or In step b, the flame retardant is ammonium polyphosphate flame retardant or diethyl aluminum phosphinate flame retardant; and / or In step b, the mass volume ratio of the flame retardant to the epoxy resin is 1g:3mL-1g:4mL; and / or In step b, the mass ratio of the pretreated glass fiber to the flame retardant slurry is 1:1.5-1:2; and / or In step b, the immersion time is 1h-3h.

7. The high temperature resistant flame retardant rubber-plastic sheet material according to claim 1, characterized in that: The preparation method of the graphene-ZnO modified fluororubber comprises the following steps: kneading the raw fluororubber at 60°C-75°C to obtain kneaded fluororubber; adding graphene powder and nano ZnO to the kneaded fluororubber, kneading at 70°C-85°C, adding a vulcanizing agent for vulcanization, and obtaining the graphene-ZnO modified fluororubber.

8. The high temperature resistant flame retardant rubber-plastic sheet material according to claim 7, characterized in that: The mixing time is 8min-10min; and / or The mass ratio of the fluororubber raw rubber, the graphene powder and the nano ZnO is 1:0.2:0.1-1:0.3:0.1; and / or The mixing time is 4 min to 6 min; and / or The amount of the vulcanizing agent added is 5%-8% of the mass of the fluororubber raw rubber; and / or The vulcanization temperature is 170° C.-220° C., and the vulcanization time is 16 h-24 h.

9. A method for preparing a high temperature resistant flame retardant rubber-plastic sheet material according to any one of claims 1 to 8, characterized in that: The steps include: Step 1: Fe2O3-SiO2 modified silicone rubber, flame retardant coated glass fiber, antioxidant and activator are weighed according to the designed ratio, mixed evenly, kneaded at 85°C-95°C, and then vulcanized at 160°C-180°C, extruded and formed to obtain the first flame retardant layer board; Step 2: weigh the waste rubber and plastic sheet particles, chopped basalt fibers and adhesive according to the designed ratio, mix them evenly, knead them at 100° C.-110° C., and extrude them to obtain a support layer sheet; Step 3: weigh graphene-ZnO modified fluororubber, EPDM rubber, mica powder, flame retardant coated glass fiber, antioxidant and activator according to the designed ratio, mix them evenly, knead them at 80°C-90°C, add vulcanization aids, vulcanize them at 150°C-180°C, and extrude them to obtain a second flame retardant layer plate; Step 4: stack the second flame retardant layer board, the support layer board and the first flame retardant layer board in order from bottom to top, and use hot melt fiber to bond the second flame retardant layer board, the support layer board and the first flame retardant layer board to obtain a high temperature resistant flame retardant rubber-plastic board.

10. Use of the high temperature resistant flame retardant rubber-plastic sheet material according to any one of claims 1 to 8 or the high temperature resistant flame retardant rubber-plastic sheet material prepared by the preparation method of the high temperature resistant flame retardant rubber-plastic sheet material according to claim 9 in the field of flame retardant materials.

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