Rubber product and processing technology thereof
By modifying aluminum borate whiskers and silicon nitride particles to form an interpenetrating structure, combining the porous network junction of MCM-41 and BNNS-PO4, the problem of insufficient coordinated design of reinforcement fillers and flame retardant components in traditional rubber products is solved, and high-strength, environmentally friendly and flame retardant rubber products are achieved.
Patent Information
- Application Number
- CN202510451632.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-11
- Publication Date
- 2025-07-08
AI Technical Summary
Traditional rubber products have insufficient coordinated design of reinforcement fillers and flame retardant components, resulting in high product density and poor environmental protection. When the amount of flame retardant is added, the mechanical properties deteriorate, and the compatibility of recycled materials is poor, making it difficult to use at a high proportion.
The preparation method of homemade composite reinforcement fillers and flame retardant composite materials is adopted to form an interpenetrating structure by modifying aluminum borate whiskers and modified silicon nitride particles, combining the porous network junction of MCM-41 and BNNS-PO4, and combining plasma treatment to improve the interface bonding and cross-linking layer density.
It has achieved high strength, environmental protection and flame retardant rubber products, with improved tensile strength, wear resistance and flame retardant performance reaching UL94 V-0 level, and plasma treatment enhances the density of the crosslinked layer.
Smart Images
Figure CN120271900A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to rubber materials, and particularly to a rubber product with high strength, high flame retardancy and environmental protection characteristics and its processing technology. Background Art
[0002] Traditional rubber products generally have the following defects: (1) relying on carbon black reinforcement, resulting in high product density and poor environmental protection; (2) when the amount of flame retardant added is large, the mechanical properties are easily deteriorated; (3) the compatibility of recycled materials is poor and it is difficult to be incorporated at a high ratio. When the amount of flame retardant (aluminum hydroxide) added reaches 20 parts, the tensile strength decreases by 30%. In the prior art, the co-design of reinforcing fillers and flame retardant components is insufficient, and the processing technology is difficult to balance efficiency and interfacial bonding. Summary of the Invention
[0003] Object of the Invention: The object of the present invention is to provide a rubber product and its processing technology; to solve the problem that the co-design of reinforcing fillers and flame retardant components in traditional rubber products is insufficient, resulting in the performance of rubber products not meeting the requirements.
[0004] Technical Solution: A rubber product, by weight, includes: 50-60 parts of hydrogenated butadiene rubber, 8-12 parts of self-made composite reinforcing filler, 6-12 parts of self-made flame retardant composite material, 6-10 parts of environmental protection recycled material, 3-5 parts of processing aids, and 1-3 parts of accelerator; The preparation method of the self-made composite reinforcing filler is: disperse aluminum borate whiskers in absolute ethanol, ultrasonic treatment for 30 minutes to form a uniform suspension; dropwise add KH550 coupling agent, control the reaction temperature at 60 °C, magnetic stirring for 2 hours; centrifuge, wash 3 times with ethanol to remove unreacted coupling agent; vacuum dry at 80 °C for 6 hours to obtain modified aluminum borate whiskers with epoxy groups grafted on the surface; Add silicon nitride particles to an acidic aqueous solution, ultrasonic disperse for 20 minutes; add KH171 coupling agent, stir and react in a water bath at 70 °C for 3 hours, after suction filtration, wash with deionized water until neutral; dry in an oven at 100 °C for 4 hours to obtain modified silicon nitride particles with vinyl groups grafted on the surface; Mix the modified aluminum borate whiskers and modified silicon nitride at a mass ratio of 2:1 in a high-speed mixer with a rotation speed set at 1500 rpm, premix for 10 minutes; add 0.5% of zinc stearate as a dispersion aid, continue to mix for 15 minutes; through a twin-screw extruder with a temperature set at 120 °C and a rotation speed set at 200 rpm for melt blending, extrude and pelletize, and then crush into 80-mesh powder to obtain the self-made composite reinforcing filler; The preparation method of the self-made flame retardant composite material is: impregnate MCM-41 in an ethanol solution of silane coupling agent KH-550, ultrasonic treatment at 60 °C for 2 h, after the reaction ends, centrifuge, wash 3 times with ethanol, vacuum dry at 50 °C for 6 h to obtain NH2-MCM-41; Boric acid and urea are dissolved in purified water at a ratio of 1:3. h-BN powder is added at 1 g / 100 mL. The system temperature is controlled at 180 °C and reacted for 12 hours. After centrifugation, the filter cake is collected and vacuum dried at 80 °C for 6 hours to obtain BNNS. BNNS is dispersed in a phosphate buffer solution with a pH of 4.0 and stirred at 60 °C for 4 hours. After centrifugation, it is washed with purified water and vacuum dried at 80 °C for 8 h to obtain BNNS-PO4; NH2-MCM-41 and BNNS-PO4 are mixed at a mass ratio of 2:1, and 0.5 wt% calcium stearate is added. The temperature is set at 110 °C and the rotation speed is set at 40 rpm in a mixer for 10 minutes to obtain a self-made flame retardant composite material.
[0005] Preferably, the aspect ratio of aluminum borate whiskers > 50; the pore size of MCM-41 is 5 nm.
[0006] Preferably, the environmentally friendly recycled material is: recycled rubber powder, PLA microspheres, and epoxidized soybean oil mixed at 1:1:1.
[0007] Preferably, the processing aid type is: zinc stearate and antioxidant 4010NA, mixed at 1:1.
[0008] Preferably, the accelerator is: dicumyl peroxide, sulfur, tetrabenzyl thiuram disulfide, and zinc oxide mixed at 1:1:1:1.
[0009] The processing technology of the above rubber products includes the following technological steps: S1. The mixer is preheated to 100 °C, and hydrogenated nitrile rubber and environmentally friendly recycled material are added for plasticizing for 3 minutes; S2. The self-made composite reinforcing filler and the self-made flame retardant composite material are added in two times, with an interval of 2 minutes each time. The mixing temperature is 120 °C and the rotation speed is 60 rpm; S3. Then, environmentally friendly recycled material, processing aid type, and accelerator are added for dynamic pre-vulcanization for 15 minutes. The temperature is set at 140 °C and the pressure is set at 5 MPa; S4. The rubber compound is transferred to a microwave vulcanization device, with a frequency of 2.45 GHz, a power of 10 kW, irradiated for 4 minutes, and a pressure of 5 MPa; S5. The power of an argon plasma device is set at 300 W, and the surface of the vulcanized rubber is bombarded for 3 minutes to form a dense cross-linked layer.
[0010] The above rubber products are applicable to scenarios such as automobiles, aerospace, and industrial seals.
[0011] Beneficial effects: (1)Modification of aluminum borate whiskers: The silane coupling agent KH550 hydrolyzes in ethanol to form Si-OH; Si-OH undergoes dehydration condensation with the hydroxyl groups (-OH) on the surface of the whiskers to form Si-O-Al covalent bonds, and epoxy groups (-O-CH2-CH2-O-) are grafted onto the surface of the aluminum borate whiskers; Modification of silicon nitride particles: KH171 hydrolyzes in acidic water to form Si-OH; Si-OH combines with the hydroxyl groups (-OH) on the surface of silicon nitride to form Si-O-Si bonds, and the vinyl groups (-CH=CH2) of KH171 are grafted onto the surface of the silicon nitride particles; Under the high-temperature (120 °C) shearing conditions of a twin-screw extruder, the epoxy groups on the surface of the aluminum borate whiskers are activated, and the vinyl groups (-CH=CH2) of the silicon nitride particles undergo a nucleophilic addition reaction with the epoxy groups (-O-CH2-CH2-O-) to form C-O-Si covalent bonds. Silicon nitride nanoparticles (particle size 50 nm) are filled in the gaps between the whiskers, and the interfacial bonding is enhanced through mechanical interlocking and van der Waals forces to form a "whisker-particle" interpenetrating structure, improving the tensile strength and wear resistance.
[0012] (2)Modification of MCM-41: The silane coupling agent KH550 hydrolyzes in ethanol to form Si-OH, and the hydrolyzed silanol (Si-OH) condenses with the hydroxyl groups (-OH) on the surface of MCM-41 to form Si-O-Si covalent bonds. After drying, NH2-MCM-41 is obtained; Thermal exfoliation of h-BN: Urea (NH2CONH2) decomposes at high temperature to form NH3 and CO2. The gases are inserted into the interlayer of h-BN to expand the interlayer spacing. Boric acid (H3BO3) reacts with the edges of h-BN to weaken the interlayer van der Waals forces, and finally it is exfoliated into single-layer BNNS; In an acidic buffer solution (pH = 4.0), the surface of BNNS is positively charged (protonated), and phosphate groups (PO4 -3 )are negatively charged and adsorbed on the surface of BNNS through electrostatic interaction; After compounding NH2-MCM-41 and BNNS-PO4, a self-made flame-retardant composite material with a porous network structure is obtained. The nanopores of MCM-41 adsorb combustible gases, the amino groups of MCM-41 react with the flame retardant to catalyze carbonization, the lamellar structure of BNNS blocks the transfer of heat and oxygen, and the phosphate groups of BNNS promote the densification of the carbon layer, synergistically achieving UL94 V-0 level flame retardancy.
[0013] (3)Plasma treatment: When argon plasma bombards the surface, the unsaturated bonds in the rubber molecular chains are activated, generating a large number of free radicals. These free radicals combine with the active groups released by the accelerator during the dynamic vulcanization process to initiate a chain cross-linking reaction, forming a thicker and denser cross-linked layer, improving the wear resistance. Description of the Drawings
[0014] Figure 1 It is a schematic diagram of the formation of a whisker-particle interpenetrating structure by modified aluminum borate whiskers and modified silicon nitride; Figure 2 It is the porous network structure diagram after the compounding of NH2-MCM-41 and BNNS-PO4; Figure 3 (a)is the surface bombardment diagram of vulcanized rubber without using an argon plasma device; Figure 3 (b)is the surface bombardment diagram of vulcanized rubber by an argon plasma device. Specific implementation manners
[0015] To make the technical solution of the present invention clearer, the present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
[0016] Example 1 Formulation: 55 parts of hydrogenated nitrile rubber, 10 parts of self-made composite reinforcing filler, 8 parts of self-made flame retardant composite material, 8 parts of environmentally friendly recycled material, 4 parts of processing aid, and 2 parts of accelerator.
[0017] Preparation steps: (1)Disperse aluminum borate whiskers in absolute ethanol, perform ultrasonic treatment for 30 minutes to form a uniform suspension; dropwise add KH550 coupling agent, control the reaction temperature at 60 °C, and stir magnetically for 2 hours; perform centrifugal separation, and wash 3 times with ethanol to remove the unreacted coupling agent; dry in vacuum at 80 °C for 6 hours to obtain modified aluminum borate whiskers with epoxy groups grafted on the surface; Add silicon nitride particles to an acidic aqueous solution, perform ultrasonic dispersion for 20 minutes; add KH171 coupling agent, stir and react in a water bath at 70 °C for 3 hours, then perform suction filtration, and wash with deionized water until neutral; dry in an oven at 100 °C for 4 hours to obtain modified silicon nitride particles with vinyl groups grafted on the surface.
[0018] Mix the modified aluminum borate whiskers and the modified silicon nitride at a mass ratio of 2:1 in a high-speed mixer with a rotation speed set at 1500 rpm, and premix for 10 minutes; add 0.5% of zinc stearate as a dispersion aid, and continue to mix for 15 minutes; melt and blend through a twin-screw extruder with the temperature set at 120 °C and the rotation speed set at 200 rpm, and after extrusion and pelletization, crush into 80-mesh powder to obtain the self-made composite reinforcing filler; (2)Immerse MCM-41 in an ethanol solution of silane coupling agent KH550, perform ultrasonic treatment at 60 °C for 2 h, after the reaction ends, perform centrifugal separation, and wash 3 times with ethanol. Dry in vacuum at 50 °C for 6 h to obtain NH2-MCM-41; Boric acid and urea were dissolved in purified water at a ratio of 1:3, and h-BN powder was added at 1 g / 100 mL. The reaction was carried out at 180 °C for 12 hours while controlling the system temperature. After centrifugation, the filter cake was collected and vacuum dried at 80 °C for 6 hours to obtain BNNS. BNNS was dispersed in a phosphate buffer solution with a pH of 4.0 and stirred at 60 °C for 4 hours. After centrifugation and washing, it was vacuum dried at 80 °C for 8 h to obtain BNNS-PO4; NH2-MCM-41 and BNNS-PO4 were mixed at a mass ratio of 2:1, and 0.5 wt% calcium stearate was added. The temperature was set at 110 °C and the rotation speed was set at 40 rpm in a mixer for 10 minutes to form a self-made flame retardant composite material with a three-dimensional porous network structure.
[0019] (3)Preheat the mixer to 100 °C, add 65 parts of hydrogenated nitrile rubber and 10 parts of environmentally friendly recycled material, and plasticize for 3 minutes; (4)Add 5 parts of the self-made composite reinforcing filler and 4 parts of the self-made flame retardant composite material to step (3). After an interval of 2 minutes, add another 5 parts of the self-made composite reinforcing filler and 4 parts of the self-made flame retardant composite material. The mixing temperature is 120 °C and the rotation speed is 60 rpm; (5)Continue to add 4 parts of processing aids and 2 parts of accelerators in step (4), and perform dynamic pre-vulcanization for 5 minutes with the temperature set at 140 °C and the pressure set at 5 MPa; (6)Transfer the rubber compound from step (5) to a microwave vulcanization device with a frequency of 2.45 GHz, a power of 10 kW, irradiate for 4 minutes, and the pressure is 5 MPa; (7)Transfer the rubber compound from step (6) to an argon plasma device with a power set at 300 W, bombard the surface of the vulcanized rubber for 3 minutes to obtain a rubber product.
[0020] Example 2 Formulation: 50 parts of hydrogenated nitrile rubber, 8 parts of self-made composite reinforcing filler, 6 parts of self-made flame retardant composite material, 6 parts of environmentally friendly recycled material, 3 parts of processing aids, 1 part of accelerator.
[0021] Preparation steps: (1)Disperse aluminum borate whiskers in absolute ethanol, perform ultrasonic treatment for 30 minutes to form a homogeneous suspension; dropwise add KH550 coupling agent, control the reaction temperature at 60 °C, and stir magnetically for 2 hours; perform centrifugal separation, wash 3 times with ethanol to remove the unreacted coupling agent; vacuum dry at 80 °C for 6 hours to obtain modified aluminum borate whiskers with epoxy groups grafted on the surface; Add silicon nitride particles to an acidic aqueous solution, perform ultrasonic dispersion for 20 minutes; add KH171 coupling agent, stir and react in a water bath at 70 °C for 3 hours, then perform suction filtration, and wash with deionized water until neutral; dry in an oven at 100 °C for 4 hours to obtain modified silicon nitride particles with vinyl groups grafted on the surface.
[0022] Mix the modified aluminum borate whiskers and modified silicon nitride at a mass ratio of 2:1 in a high-speed mixer with a rotation speed of 1500 rpm and premix for 10 minutes; add 0.5% zinc stearate as a dispersion aid and continue mixing for 15 minutes; perform melt blending through a twin-screw extruder with a temperature set at 120 °C and a rotation speed set at 200 rpm, and after extrusion granulation, crush it into 80-mesh powder to obtain a self-made composite reinforcing filler; (2) Immerse MCM-41 in an ethanol solution of silane coupling agent KH550 and perform ultrasonic treatment at 60 °C for 2 h. After the reaction ends, perform centrifugal separation and wash it with ethanol three times. Dry it in vacuum at 50 °C for 6 h to obtain NH2-MCM-41; Dissolve boric acid and urea in purified water at a ratio of 1:3, add h-BN powder at 1 g / 100 mL, and control the system temperature at 180 °C and react for 12 hours. After centrifugation, collect the filter cake and dry it in vacuum at 80 °C for 6 hours to obtain BNNS. Disperse BNNS in a phosphate buffer solution with a pH of 4.0 and stir at 60 °C for 4 hours. Centrifuge and wash, and dry in vacuum at 80 °C for 8 h to obtain BNNS-PO4; Mix NH2-MCM-41 and BNNS-PO4 at a mass ratio of 2:1, add 0.5 wt% calcium stearate, and perform blending in a mixer at a temperature set at 110 °C and a rotation speed set at 40 rpm for 10 minutes to form a self-made flame-retardant composite material with a three-dimensional porous network structure.
[0023] (3) Preheat the mixer to 100 °C, add 50 parts of hydrogenated nitrile rubber and 6 parts of environmentally friendly recycled material and plasticize for 3 minutes; (4) Add 4 parts of the self-made composite reinforcing filler and 3 parts of the self-made flame-retardant composite material in step (3), add 4 parts of the self-made composite reinforcing filler and 3 parts of the self-made flame-retardant composite material after an interval of 2 minutes, with a mixing temperature of 120 °C and a rotation speed of 60 rpm; (5) Continue to add 3 parts of processing aid and 1 part of accelerator in step (4), perform dynamic pre-vulcanization for 5 minutes with a temperature set at 140 °C and a pressure set at 5 MPa; (6) Transfer the rubber compound in step (5) to a microwave vulcanization device with a frequency of 2.45 GHz and a power of 10 kW, and irradiate for 4 minutes with a pressure of 5 MPa; (7) Transfer the rubber compound in step (6) to an argon plasma device with a power set at 300 W and bombard the surface of the vulcanized rubber for 3 minutes to obtain a rubber product.
[0024] Example 3 Formulation: 60 parts of hydrogenated nitrile rubber, 12 parts of self-made composite reinforcing filler, 12 parts of self-made flame-retardant composite material, 10 parts of environmentally friendly recycled material, 5 parts of processing aid, 3 parts of accelerator.
[0025] Preparation steps: (1) Disperse aluminum borate whiskers in absolute ethanol, and perform ultrasonic treatment for 30 minutes to form a uniform suspension; dropwise add KH550 coupling agent, control the reaction temperature at 60 °C, and stir magnetically for 2 hours; perform centrifugal separation, and wash with ethanol 3 times to remove the unreacted coupling agent; dry in vacuum at 80 °C for 6 hours to obtain modified aluminum borate whiskers with epoxy groups grafted on the surface; Add silicon nitride particles to an acidic aqueous solution, and perform ultrasonic dispersion for 20 minutes; add KH171 coupling agent, stir and react in a water bath at 70 °C for 3 hours, after suction filtration, wash with deionized water until neutral; dry in an oven at 100 °C for 4 hours to obtain modified silicon nitride particles with vinyl groups grafted on the surface.
[0026] Set the rotation speed of the high-speed mixer at 1500 rpm for the modified aluminum borate whiskers and the modified silicon nitride according to the mass ratio of 2:1, and premix for 10 minutes; add 0.5% zinc stearate as a dispersion aid, and continue mixing for 15 minutes; through the twin-screw extruder, set the temperature at 120 °C and the rotation speed at 200 rpm for melt blending, and after extrusion granulation, crush it into 80-mesh powder to obtain a self-made composite reinforcing filler; (2) Immerse MCM-41 in an ethanol solution of silane coupling agent KH550, and perform ultrasonic treatment at 60 °C for 2 h. After the reaction ends, perform centrifugal separation and wash with ethanol 3 times. Dry in vacuum at 50 °C for 6 h to obtain NH2-MCM-41; Dissolve boric acid and urea in purified water at a ratio of 1:3, add h-BN powder at 1 g / 100 mL, and control the system temperature at 180 °C for reaction for 12 hours. After centrifugation, collect the filter cake, and dry in vacuum at 80 °C for 6 hours to obtain BNNS. Disperse BNNS in a phosphate buffer solution with a pH of 4.0, and stir at 60 °C for 4 hours. Centrifuge and wash, and dry in vacuum at 80 °C for 8 h to obtain BNNS-PO4; Mix NH2-MCM-41 and BNNS-PO4 according to a mass ratio of 2:1, add 0.5 wt% calcium stearate, and blend in a mixer at a temperature of 110 °C and a rotation speed of 40 rpm for 10 minutes to form a self-made flame-retardant composite material with a three-dimensional porous network structure.
[0027] (3) Preheat the mixer to 100 °C, add 65 parts of hydrogenated nitrile rubber and 10 parts of environmentally friendly recycled material, and plasticize for 3 minutes; (4) Add 6 parts of the self-made composite reinforcing filler and 5 parts of the self-made flame-retardant composite material to step (3), add 6 parts of the self-made composite reinforcing filler and 5 parts of the self-made flame-retardant composite material at an interval of 2 minutes, with a mixing temperature of 120 °C and a rotation speed of 60 rpm; (5) Continue to add 5 parts of processing aids and 3 parts of accelerators in step (4), and perform dynamic pre-vulcanization for 5 minutes, with the temperature set at 140 °C and the pressure set at 5 MPa; (6) Transfer the rubber compound from step (5) to a microwave vulcanization device with a frequency of 2.45 GHz, a power of 10 kW, irradiate for 4 minutes, and a pressure of 5 MPa; (7) Transfer the rubber compound from step (6) to an argon plasma device with a power setting of 300 W, bombard the surface of the vulcanized rubber for 3 minutes to obtain a rubber product.
[0028] Comparative Example 1 Formulation: 55 parts of hydrogenated nitrile rubber, 8 parts of self-made flame retardant composite material, 8 parts of environmentally friendly recycled material, 4 parts of processing aid, 2 parts of accelerator.
[0029] Preparation steps: (1) Immerse MCM-41 in an ethanol solution of silane coupling agent KH550, perform ultrasonic treatment at 60 °C for 2 h. After the reaction ends, perform centrifugal separation and wash 3 times with ethanol. Dry in vacuum at 50 °C for 6 h to obtain NH2-MCM-41; Boric acid and urea are dissolved in purified water at a ratio of 1:3, add h-BN powder at 1 g / 100 mL, control the system temperature at 180 °C and react for 12 hours. After centrifugation, collect the filter cake, dry in vacuum at 80 °C for 6 hours to obtain BNNS. Disperse BNNS in a phosphate buffer solution with a pH of 4.0, stir at 60 °C for 4 hours. Centrifuge and wash, dry in vacuum at 80 °C for 8 h to obtain BNNS-PO4; Mix NH2-MCM-41 and BNNS-PO4 at a mass ratio of 2:1, add 0.5 wt% calcium stearate, set the temperature at 110 °C and the rotation speed at 40 rpm in a mixer and blend for 10 minutes to form a self-made flame retardant composite material with a three-dimensional porous network structure.
[0030] (2) Preheat the mixer to 100 °C, add 65 parts of hydrogenated nitrile rubber and 10 parts of environmentally friendly recycled material and plasticize for 3 minutes; (3) Add 4 parts of the self-made flame retardant composite material to step (2), add another 4 parts of the self-made flame retardant composite material after 2 minutes, with a mixing temperature of 120 °C and a rotation speed of 60 rpm; (4) Continue to add 4 parts of processing aid and 2 parts of accelerator in step (3), perform dynamic pre-vulcanization for 5 minutes with a temperature setting of 140 °C and a pressure setting of 5 MPa; (5) Transfer the rubber compound from step (4) to a microwave vulcanization device with a frequency of 2.45 GHz, a power of 10 kW, irradiate for 4 minutes, and a pressure of 5 MPa; (6) Transfer the rubber compound from step (5) to an argon plasma device with a power setting of 300 W, bombard the surface of the vulcanized rubber for 3 minutes to obtain a rubber product.
[0031] Comparative Example 2 Formula: 55 parts of hydrogenated nitrile rubber, 10 parts of self-made composite reinforcing filler, 8 parts of environmentally friendly recycled material, 4 parts of processing aid, 2 parts of accelerator.
[0032] Preparation steps: (1) Disperse aluminum borate whiskers in absolute ethanol, ultrasonically treat for 30 minutes to form a uniform suspension; dropwise add KH550 coupling agent, control the reaction temperature at 60 °C, and magnetically stir for 2 hours; centrifuge and separate, wash 3 times with ethanol to remove unreacted coupling agent; vacuum dry at 80 °C for 6 hours to obtain modified aluminum borate whiskers with epoxy groups grafted on the surface; Add silicon nitride particles to an acidic aqueous solution, ultrasonically disperse for 20 minutes; add KH171 coupling agent, stir and react in a water bath at 70 °C for 3 hours, after filtration, wash with deionized water until neutral; dry in an oven at 100 °C for 4 hours to obtain modified silicon nitride particles with vinyl groups grafted on the surface.
[0033] Mix the modified aluminum borate whiskers and modified silicon nitride at a mass ratio of 2:1, set the speed of the high-speed mixer at 1500 rpm, and premix for 10 minutes; add 0.5% zinc stearate as a dispersion aid and continue to mix for 15 minutes; melt and blend through a twin-screw extruder with the temperature set at 120 °C and the speed set at 200 rpm, after extrusion and pelletization, crush into 80-mesh powder to obtain the self-made composite reinforcing filler; (2) Preheat the internal mixer to 100 °C, add 65 parts of hydrogenated nitrile rubber and 10 parts of environmentally friendly recycled material, and plastify for 3 minutes; (3) Add 5 parts of the self-made composite reinforcing filler and 4 parts of the self-made flame-retardant composite material in step (2), add another 5 parts of the self-made composite reinforcing filler and 4 parts of the self-made flame-retardant composite material after an interval of 2 minutes, the mixing temperature is 120 °C, and the speed is 60 rpm; (4) Continue to add 4 parts of processing aid and 2 parts of accelerator in step (3), dynamically pre-vulcanize for 5 minutes with the temperature set at 140 °C and the pressure set at 5 MPa; (5) Transfer the rubber compound in step (4) to a microwave vulcanization device, with a frequency of 2.45 GHz, a power of 10 kW, irradiate for 4 minutes, and a pressure of 5 MPa; (6) Transfer the rubber compound in step (5) to an argon plasma device with the power set at 300 W, bombard the surface of the vulcanized rubber for 3 minutes to obtain the rubber product.
[0034] Comparative Example 3 Formula: 55 parts of hydrogenated nitrile rubber, 10 parts of self-made composite reinforcing filler, 8 parts of self-made flame-retardant composite material, 8 parts of environmentally friendly recycled material, 4 parts of processing aid, 2 parts of accelerator.
[0035] Preparation steps: (1) Disperse aluminum borate whiskers in absolute ethanol and ultrasonically treat for 30 minutes to form a uniform suspension; dropwise add KH550 coupling agent, control the reaction temperature at 60 °C, and magnetically stir for 2 hours; centrifuge and separate, wash with ethanol 3 times to remove the unreacted coupling agent; vacuum dry at 80 °C for 6 hours to obtain modified aluminum borate whiskers with epoxy groups grafted on the surface; Add silicon nitride particles to an acidic aqueous solution and ultrasonically disperse for 20 minutes; add KH171 coupling agent, stir and react in a water bath at 70 °C for 3 hours, after suction filtration, wash with deionized water until neutral; dry in an oven at 100 °C for 4 hours to obtain modified silicon nitride particles with vinyl groups grafted on the surface.
[0036] Set the rotation speed of the high-speed mixer at 1500 rpm for the modified aluminum borate whiskers and the modified silicon nitride with a mass ratio of 2:1, and premix for 10 minutes; add 0.5% zinc stearate as a dispersion aid and continue mixing for 15 minutes; melt blend through a twin-screw extruder with the temperature set at 120 °C and the rotation speed set at 200 rpm, and after extrusion and pelletization, crush into 80-mesh powder to obtain a self-made composite reinforcing filler (2) Immerse MCM-41 in an ethanol solution of silane coupling agent KH550 and ultrasonically treat at 60 °C for 2 h. After the reaction, centrifuge and separate, and wash with ethanol 3 times. Vacuum dry at 50 °C for 6 h to obtain NH2-MCM-41; Dissolve boric acid and urea in purified water at a ratio of 1:3, add h-BN powder at 1 g / 100 mL, control the system temperature at 180 °C and react for 12 hours. Centrifuge and collect the filter cake, vacuum dry at 80 °C for 6 hours to obtain BNNS. Disperse BNNS in a phosphate buffer solution with a pH of 4.0 and stir at 60 °C for 4 hours. Centrifuge and wash, vacuum dry at 80 °C for 8 h to obtain BNNS-PO4; Mix NH2-MCM-41 and BNNS-PO4 at a mass ratio of 2:1, add 0.5 wt% calcium stearate, and blend in a mixer at a temperature of 110 °C and a rotation speed of 40 rpm for 10 minutes to form a self-made flame-retardant composite material with a three-dimensional porous network structure.
[0037] (3) Preheat the mixer to 100 °C, add 65 parts of hydrogenated nitrile rubber and 10 parts of environmentally friendly recycled material and plasticize for 3 minutes; (4) Add 5 parts of the self-made composite reinforcing filler and 4 parts of the self-made flame-retardant composite material in step (3), add 5 parts of the self-made composite reinforcing filler and 4 parts of the self-made flame-retardant composite material after an interval of 2 minutes, with a mixing temperature of 120 °C and a rotation speed of 60 rpm; (5) Continue to add 4 parts of processing aids and 2 parts of accelerators in step (4), and dynamically pre-vulcanize for 5 minutes with the temperature set at 140 °C and the pressure set at 5 MPa; (6) Transfer the rubber compound obtained in step (5) to a microwave vulcanization device with a frequency of 2.45 GHz, a power of 10 kW, irradiate for 4 minutes, and apply a pressure of 5 MPa to obtain a rubber product.
[0038] Performance testing method Tensile strength: Testing standard: ASTM D412.
[0039] Limiting oxygen index (LOI): Testing standard: ASTM D2863.
[0040] Smoke density rating (SDR): Testing standard: ASTM E662 (smoke density chamber method).
[0041] Abrasion resistance; Testing standard: GB / T 9867.
[0042] The test results are shown in Table 1.
[0043] Table 1 Performance test results of the examples and comparative examples From Examples 1 to 3 and Comparative Examples 1 to 3, it can be seen that the self-made composite reinforcing filler: the modified aluminum borate whiskers form a "whisker - particle" interpenetrating structure with the modified silicon nitride (particle size 200 nm), as Figure 1 shown, which can improve the tensile strength and abrasion resistance. The self-made flame-retardant composite material: the mesoporous structure of NH2-MCM-41 adsorbs pyrolysis gases, and BNNS-PO4 promotes the densification of the carbon layer. After the two are compounded, a self-made flame-retardant composite material with a porous network structure can be formed, as Figure 2 shown, achieving UL94 V-0 level flame retardancy synergistically; Plasma treatment: as Figure 3 (a) shown, the surface of the vulcanized rubber was not treated with an argon plasma device, and the surface of the colloid was relatively sparse. As Figure 3 (b) shown, after the surface of the vulcanized rubber was treated with an argon plasma device, the thickness of the cross-linked layer on the surface of the colloid increased, which was beneficial to the improvement of abrasion resistance.
[0044] The above-described embodiments only represent several implementation manners of the present invention, and their descriptions are relatively specific and detailed, but should not be construed as limiting the scope of the present invention patent. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can still be made, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the present invention patent should be subject to the appended claims.
Claims
1. A rubber product, characterized in that, Comprising by weight parts: 50 - 60 parts of hydrogenated butadiene rubber, 8 - 12 parts of self-made composite reinforcing filler, 6 - 12 parts of self-made flame retardant composite material, 6 - 10 parts of environmentally friendly recycled material, 3 - 5 parts of processing aid, 1 - 3 parts of accelerator; The preparation method of the self-made composite reinforcing filler is as follows: Disperse aluminum borate whiskers in anhydrous ethanol, perform ultrasonic treatment for 30 minutes to form a uniform suspension; dropwise add KH550 coupling agent, control the reaction temperature at 60 °C, and stir magnetically for 2 hours; perform centrifugal separation, and wash with ethanol 3 times to remove the unreacted coupling agent; dry in vacuum at 80 °C for 6 hours to obtain modified aluminum borate whiskers with epoxy groups grafted on the surface; Add silicon nitride particles to an acidic aqueous solution, and perform ultrasonic dispersion for 20 minutes; add KH171 coupling agent, stir and react in a water bath at 70 °C for 3 hours, after suction filtration, wash with deionized water until neutral; dry in an oven at 100 °C for 4 hours to obtain modified silicon nitride particles with vinyl groups grafted on the surface; Set the rotation speed of the high-speed mixer at 1500 rpm for the modified aluminum borate whiskers and the modified silicon nitride according to the mass ratio of 2:1, and premix for 10 minutes; add 0.5% zinc stearate as a dispersion aid, and continue to mix for 15 minutes; set the temperature of the twin-screw extruder at 120 °C and the rotation speed at 200 rpm for melt blending, and after extrusion and pelletization, crush into 80-mesh powder to obtain the self-made composite reinforcing filler; The preparation method of the self-made flame retardant composite material is as follows: Immerse MCM-41 in an ethanol solution of silane coupling agent KH-550, perform ultrasonic treatment at 60 °C for 2 h, after the reaction ends, perform centrifugal separation, wash with ethanol 3 times, and dry in vacuum at 50 °C for 6 h to obtain NH2-MCM-41; Boric acid and urea are dissolved in purified water according to a ratio of 1:3, add h-BN powder at 1 g / 100 mL, control the system temperature at 180 °C and react for 12 hours, collect the filter cake after centrifugation, and dry in vacuum at 80 °C for 6 hours to obtain BNNS. Disperse BNNS in a phosphate buffer solution with a pH of 4.0, stir at 60 °C for 4 hours, wash with centrifuged purified water, and dry in vacuum at 80 °C for 8 h to obtain BNNS-PO4; Mix NH2-MCM-41 and BNNS-PO4 according to a mass ratio of 2:1, add 0.5 wt% calcium stearate, and blend in a kneader at a temperature of 110 °C and a rotation speed of 40 rpm for 10 minutes to obtain the self-made flame retardant composite material.
2. The rubber product according to claim 1, wherein The aspect ratio of the aluminum borate whiskers > 50; the pore diameter of MCM-41 is 5 nm.
3. The rubber product according to claim 1, characterized in that, The environmentally friendly recycled material is: recycled rubber powder, PLA microspheres, and epoxidized soybean oil mixed in a ratio of 1:1:
1.
4. The rubber product according to claim 1, characterized in that, The type of processing aid is: zinc stearate, antioxidant 4010NA, mixed in a ratio of 1:
1.
5. The rubber product according to claim 1, characterized in that, The accelerator is: dicumyl peroxide, sulfur, tetrabenzylthiuram disulfide, zinc oxide, mixed in a ratio of 1:1:1:
1.
6. A processing technology for the rubber product according to any one of claims 1 to 5, characterized in that, Including the following steps: S1. Preheat the kneader to 100 °C, add hydrogenated nitrile rubber and the environmentally friendly recycled material and plastify for 3 minutes; S2. Add the self-made composite reinforcing filler and the self-made flame retardant composite material in two batches, with an interval of 2 minutes each time, the mixing temperature is 120 °C, and the rotation speed is 60 rpm; S3. Then add environmentally friendly recycled materials, processing aids, and accelerators, and conduct dynamic pre-vulcanization for 15 minutes, with the temperature set at 140 °C and the pressure set at 5 MPa; S4. Transfer the rubber compound to a microwave vulcanization equipment, with a frequency of 2.45 GHz, a power of 10 kW, and irradiate for 4 minutes, with a pressure of 5 MPa; S5. Set the power of the argon plasma equipment to 300 W, bombard the surface of the vulcanized rubber for 3 minutes to form a dense cross-linked layer.