Rubber material with anti-infrared function and preparation method thereof

Abstract

The invention belongs to the technical field of rubber materials, and particularly discloses a rubber material with an anti-infrared function and a preparation method thereof. The rubber material is prepared from the following raw materials in parts by weight: 100 to 102 parts of T145, 28 to 32 parts of SSBR, 8 to 10 parts of white carbon black, 4 to 5 parts of silane coupling agent SI-69, 28 to 32 parts of carbon black N660, 4 to 6 parts of titanium dioxide, 9 to 11 parts of ITO, 2 to 3 parts of LaB6, 1 to 1.2 parts of stearic acid, 4 to 6 parts of ZnO, 1.4 to 1.6 parts of carbon nanotubes, 1.4 to 1.6 parts of anti-aging agent 4020, 1.3 to 1.7 parts of anti-aging agent RD, 0.2 to 0.4 part of PVI, 0.7 to 1.1 parts of NS, 0.7 to 1.1 parts of S, 18 to 20 parts of modified nanoscale calcium carbonate, 12 to 15 parts of nylon powder and 8 to 9 parts of aromatic oil. The T145, the SSBR, the white carbon black and the carbon nanotubes are subjected to multi-reinforcement, so that the anti-infrared cable material has relatively high tensile strength, tear strength and wear resistance, and meanwhile, an anti-infrared function is realized.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of rubber materials, in particular to a rubber material with an infrared-proof function and a preparation method thereof. BACKGROUND

[0002] Rubber materials are a kind of high-molecular polymer materials with high elasticity and reversible deformation capacity, and are widely used in many fields such as industry, automobile, medical treatment and daily life. In the field of automobiles, rubber materials are the core base materials for preparing camouflage tires due to their modifiability, high elasticity and weather resistance.

[0003] Camouflage tires are mainly used for military vehicles, and in the actual use process of military vehicles, especially when performing tasks, the tires need to be hidden. In order to be successfully hidden, the tires need to have an infrared-proof function. By adding infrared absorbers or infrared reflective fillers in the rubber material, the heat signal of the target object can be reduced by absorbing or reflecting infrared radiation, so that the target object is more difficult to be detected, thereby improving the concealment and safety.

[0004] When adding infrared absorbers or infrared reflective fillers in the rubber material to realize the infrared-proof function, the fillers are prone to agglomeration and are not uniformly dispersed in the rubber material, which further leads to the occurrence of micro-cracks inside, and further affects the mechanical properties and durability of the tire. SUMMARY

[0005] In order to improve the problem that the infrared fillers are prone to agglomeration and affect the mechanical properties of the tire, the application provides a rubber material with an infrared-proof function and a preparation method thereof.

[0006] The application provides a rubber material with an infrared-proof function, which adopts the following technical scheme: The rubber material with an infrared-proof function comprises the following raw materials in parts by weight: T145 100-102 parts, SSBR 28-32 parts, white carbon black 8-10 parts, silane coupling agent SI-69 4-5 parts, carbon black N660 28-32 parts, titanium dioxide 4-6 parts, ITO 9-11 parts, LaB6 2-3 parts, stearic acid 1-1.2 parts, ZnO 4-6 parts, carbon nanotubes 1.4-1.6 parts, antioxidant 4020 1.4-1.6 parts, antioxidant RD 1.3-1.7 parts, PVI 0.2-0.4 parts, NS 0.7-1.1 parts, S 0.7-1.1 parts, modified nano calcium carbonate 18-20 parts, nylon powder 12-15 parts, and aromatic oil 8-9 parts.

[0007] By adopting the above technical scheme, T145 provides excellent elasticity, strength and low heat generation, improves the mechanical properties and wear resistance of the rubber material. SSBR (solution polymerized butadiene styrene rubber) has good elasticity and wear resistance, cooperates with T145 to improve the aging resistance of the rubber material. The white carbon black and the modified white carbon black in T145 form double reinforcement, further improving the strength, tear resistance and wear resistance of the material. One end of the silane coupling agent SI-69 reacts with the hydroxyl group on the surface of the white carbon black, and the other end reacts with the rubber molecular chain, establishing a firm connection between the white carbon black and the rubber, and improving the dispersibility of the white carbon black. Carbon black N660 provides certain reinforcing effect, adjusts the electrical conductivity and color of the material. Titanium dioxide has high hiding power and stability, and can also effectively reflect and scatter ultraviolet rays, assisting in improving the weather resistance of the material. ITO has extremely strong reflection and absorption ability for infrared rays, and achieves the effect of infrared stealth by reflecting and blocking infrared radiation. LaB6 is good at absorbing near-infrared rays, and is used in combination with ITO to widen the wave band range of infrared shielding, realizing more comprehensive protection effect from near-infrared to medium and far-infrared. Stearic acid plays a lubricating role in mixing, promoting the dispersion of fillers.

[0008] ZnO reacts with stearic acid to improve the efficiency of the vulcanization system, making the vulcanization process more complete and uniform, and is an indispensable component of the sulfur vulcanization system. Carbon nanotubes can form a conductive network to adjust the electromagnetic shielding performance of the material, providing strong reinforcing effect and greatly improving the strength, modulus and wear resistance. Antioxidant 4020 cooperates with antioxidant RD to effectively prevent cracking and aging of rubber caused by oxygen and ozone invasion, and improve the anti-aging performance of the rubber material. PVI can delay the scorching time of the sulfur vulcanization system, improve the safety of the rubber compound during processing, and prevent early vulcanization during mixing, extrusion and storage. NS has the characteristics of rapid vulcanization in the later stage, and has good vulcanization flatness. S reacts with the rubber molecular chain to form a three-dimensional network structure, making the material change from a plastic body to a highly elastic vulcanized rubber. Modified nano calcium carbonate improves the tensile strength and tear strength, and is uniformly dispersed in the rubber matrix, filling the micropores in the rubber matrix and improving the elasticity and aging resistance. Nylon powder has high hardness, high wear resistance and high impact resistance, improving the mechanical properties of the rubber material and prolonging the service life of the rubber product. T145 is used in combination with SSBR, and cooperates with the multiple reinforcement of white carbon black, carbon black and carbon nanotubes, has high tensile strength, tear strength and wear resistance, and realizes the function of preventing infrared.

[0009] Preferably, T145 101.5 parts, SSBR 30 parts, white carbon black 9 parts, silane coupling agent SI-69 4 parts, carbon black N660 30 parts, titanium dioxide 5 parts, ITO 10 parts, LaB6 2 parts, stearic acid 1 part, ZnO 5 parts, carbon nanotube 1.5 parts, antioxidant 4020 1.5 parts, antioxidant RD 1.5 parts, PVI 0.3 parts, NS 0.9 parts, S 0.9 parts, modified nano calcium carbonate 19 parts, nylon powder 14 parts, aromatic oil 8 parts.

[0010] By adopting the above technical scheme, the use amount of each component is further limited, so that each component has relatively optimal comprehensive performance under a specific use amount ratio. ITO, LaB6, and titanium dioxide cooperate to enhance the infrared shielding capability and synergistically enhance the infrared shielding effect. White carbon black, carbon black N660, and carbon nanotube cooperate to enhance the tensile strength, tear strength, and wear resistance. T145 and SSBR serve as the base rubber phase and cooperate with various fillers such as modified nano calcium carbonate and nylon powder to improve the wear resistance, wet skid resistance, and aging resistance of the material. The various components in the present application synergistically cooperate to improve the infrared shielding function, tensile strength, tear strength, and wear resistance of the rubber material.

[0011] Preferably, the preparation method of the modified nano calcium carbonate comprises the following steps: (1) dispersing nano calcium carbonate in ethanol, adding diatomite, polymethyl acrylate, and sodium laurate, stirring for 20-25 min, grinding to obtain a mixture, and calcining the mixture at 320-340℃ for 1-2h to obtain a porous mixture; (2) dispersing modified graphene in deionized water, ultrasonicating for 1-2h, adding the porous mixture of step (1), continuing to ultrasonicate for 2-3h, and filtering to obtain a mixture; (3) dispersing aluminum dihydrogen phosphate and chitosan in an acetic acid solution to obtain a mixed solution, spraying the mixed solution onto the surface of the mixture of step (2), and drying to obtain the modified nano calcium carbonate.

[0012] By adopting the above technical scheme, the nano calcium carbonate has a high specific surface area, the diatomite introduces large pore diameters and through pores, enhances the specific surface area and adsorption capacity of the mixture, and provides mechanical support. At room temperature, the polymethyl acrylate is mixed with the calcium carbonate and diatomite, so that the calcium carbonate and diatomite are tightly bonded, improving the mechanical properties. The sodium laurate improves the dispersibility of the nano calcium carbonate and diatomite in ethanol, prevents them from agglomerating, and makes them more uniformly mixed with other components. After subsequent calcination at 320-340℃, the polymethyl acrylate and sodium laurate decompose, leaving a large number of pores in the system, further expanding the porosity of the porous structure.

[0013] The modified graphene has high specific surface area, excellent mechanical properties and electrical conductivity in deionized water. The modified graphene and the porous mixture are mixed, and the modified graphene can be uniformly wrapped and covered on the surface and inner wall of the pores of the porous mixture, so that the mechanical properties of the material are enhanced, the material is endowed with high specific surface area, porous structure and electrical conductivity, and the thermal stability is improved.

[0014] The aluminum dihydrogen phosphate provides good adhesion, heat resistance, weather resistance and corrosion resistance, the chitosan has good film forming property, biocompatibility and adsorption, the spraying makes the mixed solution uniformly cover the surface of the porous-graphene composite structure, forms an organic-inorganic hybrid composite coating layer, completely wraps the porous mixture and the modified graphene, ensures the stability of the structure, and the obtained modified nanoscale calcium carbonate has a nanoscale calcium carbonate / diatomite porous skeleton, provides support and surface area, has good mechanical properties, and is matched with multiple components in the rubber material subsequently, has excellent reinforcing and mechanical property improvement, and is helpful to uniform dispersion of the components.

[0015] Preferably, the mass ratio of the nanoscale calcium carbonate, the modified graphene and the aluminum dihydrogen phosphate is 1:0.65-0.78:0.12-0.18.

[0016] By adopting the above technical solution, the mass ratio of the nanoscale calcium carbonate, the modified graphene and the aluminum dihydrogen phosphate is further limited within a certain range, and the obtained modified nanoscale calcium carbonate has excellent comprehensive performance. The particle size of the nanoscale calcium carbonate provides a large specific surface area for the adhesion of the modified graphene, prevents the graphene sheet from re-stacking and agglomerating, and is helpful to adsorption and loading. The modified graphene is wrapped and overlapped on the surface of the calcium carbonate particles and in the pores, forms a continuous three-dimensional network structure, and improves the mechanical properties such as tensile strength and toughness of the composite material. The aluminum dihydrogen phosphate has good viscosity, can penetrate into the gaps of the calcium carbonate and the graphene, and firmly sticks the calcium carbonate particles and the graphene sheet together, has excellent heat resistance, weather resistance and chemical corrosion resistance, and maintains the stability of the performance of the composite material. Subsequent application in the rubber material makes the components uniformly dispersed, and improves the comprehensive performance such as the mechanical properties and wear resistance of the rubber material.

[0017] Preferably, the preparation method of the modified graphene comprises the following steps: dispersing graphene in a sulfuric acid solution, heating and refluxing at a temperature of 120-130 DEG C for 4-5 h, washing with water to obtain sulfurized graphene, dispersing the sulfurized graphene into deionized water, adding aluminum oxide whiskers and sodium dodecyl sulfonate, and irradiating under a ultraviolet lamp for 15-17 min to obtain a mixture, and then immersing the mixture in a sodium alginate solution and drying to obtain the modified graphene. The sodium alginate, nanometer nickel, tea polyphenol extract and calcium gluconate are dispersed into deionized water, and stirred at a temperature of 60-65 DEG C for 1-2 h to obtain a sodium alginate solution.

[0018] By adopting the technical scheme, the sulfonic acid group is grafted to the defect or edge position of the graphene, the dispersibility and surface reactivity of the graphene in water are improved, the alumina whisker has extremely high strength and modulus, and a multi-dimensional reinforcing network is constructed by compounding the graphene and the alumina whisker, so that the mechanical properties (such as hardness, strength and wear resistance) of the final composite material are significantly improved. The sodium dodecyl sulfonate helps the sulfurized graphene and the alumina whisker to be better dispersed in water and prevents agglomeration. Under ultraviolet light irradiation, the sulfur-containing groups on the surface of the sulfurized graphene are activated, and the interaction between the sulfur-containing groups and the surface hydroxyl groups of the alumina whisker is enhanced. Moreover, the sodium dodecyl sulfonate is decomposed to generate free radicals, and the free radicals initiate complex radical reactions between the graphene, the alumina whisker and the sodium dodecyl sulfonate molecules, promote crosslinking or strong combination between them, and ensure that the components of the mixture are tightly combined.

[0019] The mixture is immersed in a sodium alginate solution, the sodium alginate solution penetrates into the pores of the sulfurized graphene / alumina whisker composite, and after drying, an organic coating layer is formed to firmly encapsulate the entire composite structure and improve the mechanical properties of the system. In the sodium alginate solution, the sodium alginate has good water solubility, biocompatibility and film-forming property, the nano-nickel is dispersed in the sodium alginate system, the tea polyphenol extract has strong antioxidant property, and the calcium gluconate provides calcium ions to crosslink with the carboxyl negative ions of the sodium alginate, so as to improve the viscosity and stability of the sodium alginate solution and the mechanical strength of the subsequent coating layer.

[0020] The sodium alginate coating layer tightly combines the sulfurized graphene, the alumina whisker, the nano-nickel and the like, so that the final product has excellent mechanical properties, excellent dispersibility and stability, and the subsequent nano-calcium carbonate helps to improve the corresponding properties of the nano-calcium carbonate, and further improves the comprehensive performance of the rubber material.

[0021] Preferably, the preparation method of the nylon powder comprises the following steps: (1) melt nylon resin, silane coupling agent, modified molecular sieve, dibutyltin dilaurate and antioxidant at 220-230℃ for 1-1.2h to obtain a mixed solution, grind and then disperse into deionized water, stir at 60-65℃ for 1-2h, dry, sieve and obtain a powder; (2) disperse the powder into deionized water, add boron fiber, flow agent and superdispersant coating agent, stir at 80-85℃ for 2-3h at a stirring speed of 440-450r / min, and dry to obtain a nylon powder.

[0022] By adopting the technical scheme, the nylon resin has good mechanical properties, heat resistance and processability, the silane coupling agent improves the compatibility and binding force between the inorganic filler (calcium carbonate, modified molecular sieve) and the organic nylon matrix, prevents interface defects, and improves the mechanical properties of the final product. The modified molecular sieve has a porous structure and adsorbability, and the porous structure can reduce the powder density and help the uniform mixing of multiple components. The dibutyltin dilaurate reduces the viscosity of the molten system and improves the flowability, so that the multiple components are uniformly mixed. The antioxidant prevents the nylon from being oxidized and degraded during high-temperature melting and processing, and ensures the material properties.

[0023] The nylon is completely melted, all fillers and additives are preliminarily and uniformly mixed with the nylon melt under strong shear force, and then grinding is easier to obtain small particles, which have high mechanical properties and wear resistance. The boron fiber has extremely high specific strength and specific modulus, is adsorbed on the surface of the particles, and improves the hardness, rigidity and heat resistance of the final product. The flow agent is adsorbed on the surface of the powder particles, reduces the friction and electrostatic force between the particles, and significantly improves the flowability of the powder. The ultra-dispersing coating agent is anchored on one end of the powder particle surface and extends to the medium to form a steric hindrance effect. It can prevent the boron fiber and powder particles from agglomerating during the drying process, and ensure that all components are uniformly distributed and stably exist.

[0024] The final nylon powder has excellent mechanical properties, boron fiber, nylon resin, modified molecular sieve synergistic reinforcement, and interface optimization of the silane coupling agent. The products after powder forming have good tensile strength and impact strength, and subsequent compounding with other resins and fillers to prepare high-performance composite materials.

[0025] Preferably, the mass ratio of the nylon resin, the modified molecular sieve and the boron fiber is 1:0.46-0.52:0.15-0.23.

[0026] By adopting the technical scheme, the mass ratio of the nylon resin, the modified molecular sieve and the boron fiber is further limited in a certain range, and the obtained nylon powder has excellent comprehensive performance. The nylon resin has good flowability after melting, is uniformly mixed with the modified molecular sieve, and provides good toughness, wear resistance and chemical resistance. The modified molecular sieve has regular nanoscale pores and a large specific surface area, and good adsorbability, which, in cooperation with the nylon resin, improves the modulus, hardness and heat distortion temperature of the composite material.

[0027] Boron fiber has very high specific modulus and specific strength, which improves the elastic modulus, tensile strength and heat resistance of the composite material. The boron fiber is loaded on the surface of the nylon particles, which significantly improves the tensile strength, bending strength and impact resistance of the material. The nylon resin provides the basic molding and bonding ability, the modified molecular sieve gives the functional properties (adsorption, heat resistance), the boron fiber strengthens the mechanical properties and structural stability, and the combination of the three prepares a nylon powder with high strength, high stability and functionality (such as adsorption, heat resistance), which is then applied to rubber materials to improve the comprehensive performance of the rubber materials.

[0028] Preferably, the preparation method of the modified molecular sieve comprises the following steps: dispersing the molecular sieve into an aqueous solution of amino silane, stirring for 1-2 h, filtering, crushing, sieving, calcining at a temperature of 220-240℃ for 1-2 h, then dispersing into deionized water, adding aluminum sol, ceramic fiber and metal organic framework (MOFs), stirring at a temperature of 60-65℃ for 2-3 h, and drying to obtain the modified molecular sieve.

[0029] By adopting the above technical solution, the amino silane and the silicon hydroxyl on the surface of the molecular sieve undergo condensation reaction to form stable Si-O-Si covalent bond. Calcining at 220-240℃ promotes the further solidification of the chemical bond between the silane and the surface of the molecular sieve, making the covalent bond more firm. The modified molecular sieve obtained has a surface rich in amino active sites, which provides anchoring points for the next reaction with MOFs and aluminum sol.

[0030] The aluminum sol has hydroxyl groups on the surface of the colloidal particles, which form hydrogen bonds or acid-base interactions with the amino groups on the surface of the molecular sieve, and can also bond ceramic fibers and MOFs to anchor the components on the surface or pores of the molecular sieve, enhancing the structural integrity of the composite system. The ceramic fiber has high strength and heat resistance, and forms a network with the aluminum sol and the molecular sieve, significantly improving the mechanical strength, toughness and wear resistance of the material. The MOFs have a specific surface area much larger than that of the molecular sieve, which can greatly improve the overall adsorption capacity of the composite material. The microporous-mesoporous complementary structure of the molecular sieve and the microporous structure of the molecular sieve can adsorb active molecules such as oxygen and ozone, reducing their contact with rubber molecules and enhancing the anti-aging performance. At the same time, the modified molecular sieve obtained has good mechanical properties and can withstand mechanical impact and high temperature environment.

[0031] In a second aspect, the application also provides a preparation method of the rubber material with infrared-proof function, comprising the following steps: mixing T145 to obtain T145 plasticated rubber, mixing T145 plasticated rubber, SSBR, white carbon black, silane coupling agent SI-69, carbon black N660, titanium dioxide, ITO, stearic acid, carbon nanotube, antioxidant 4020, antioxidant RD, PVI, zinc oxide, modified nano calcium carbonate, nylon powder and aromatic oil to obtain a masterbatch; adding the masterbatch into LaB6, NS and S, and mixing to obtain a final rubber; and returning and vulcanizing the final rubber to obtain the rubber material.

[0032] By using the above technical scheme and the preparation method, the mechanical properties and wear resistance of the rubber material with infrared-proof function can be improved, and the obtained rubber material with infrared-proof function has good durability.

[0033] In summary, the application has the following advantages: 1. In the application, SSBR is combined with T145 to improve the aging resistance of the rubber material, and the white carbon black is combined with the modified white carbon black in T145 to form double reinforcement, thereby further improving the strength, tear resistance and wear resistance of the material.

[0034] 2. In the application, ITO has strong reflection and absorption ability to infrared rays, and achieves the effect of infrared stealth by reflecting and blocking infrared radiation.

[0035] 3. In the application, T145 is combined with SSBR, and the multiple reinforcements of white carbon black, carbon black and carbon nanotube are used, so that the rubber material has high tensile strength, tear strength and wear resistance, and realizes the infrared-proof function. DETAILED DESCRIPTION

[0036] The application will be further described in detail below in combination with examples.

[0037] The raw materials used in the examples and comparative examples can be obtained by market purchase.

[0038] Preparation example of modified nano calcium carbonate The preparation method of the modified nano calcium carbonate comprises the following steps: (1) 5 kg of nano calcium carbonate is dispersed in 25 L of ethanol, 2 kg of diatomite, 1.5 kg of polymethyl acrylate and 0.7 kg of sodium laurate are added, stirred for 22 min, ground, and the mixture is calcined at 330 DEG C for 1.5 h to obtain a porous mixture; (2) The modified graphene is dispersed in 50 L of deionized water, ultrasonic for 1.5 h, and the porous mixture of step (1) is added and ultrasonic for 2.5 h, and then filtered to obtain a mixture; (3) dispersing 0.2 kg of aluminum dihydrogen phosphate and 0.2 kg of chitosan in 10 L of a 3% acetic acid solution to obtain a mixed solution, spraying 0.5 kg of the mixed solution onto the surface of the mixture in step (2), and drying to obtain modified nano-sized calcium carbonate.

[0039] The mass ratio of the nano-sized calcium carbonate, the modified graphene, and the aluminum dihydrogen phosphate is 1:0.65:0.18.

[0040] A method for preparing modified graphene includes the following steps: dispersing 3 kg of graphene in 10 L of a sulfuric acid solution, heating and refluxing at a temperature of 125℃ for 4.5 h, washing with water to obtain sulfurized graphene, dispersing the sulfurized graphene into 35 L of deionized water, adding 1.2 kg of aluminum oxide whiskers and 0.5 kg of sodium dodecyl sulfonate, irradiating under a 365 nm ultraviolet lamp for 15 min, filtering to obtain a mixture, immersing the mixture in a sodium alginate solution, taking out, and drying to obtain modified graphene. Dispersing 2.5 kg of sodium alginate, 0.3 kg of nano-sized nickel, 0.7 kg of tea polyphenol extract, and 0.25 kg of calcium gluconate into 10 L of deionized water, stirring at a temperature of 62℃ for 1.5 h to obtain a sodium alginate solution.

[0041] Preparation Example 1-2 The difference from Preparation Example 1-1 is that no modified graphene is added in step (2).

[0042] Preparation Example 1-3 The difference from Preparation Example 1-1 is that no aluminum dihydrogen phosphate is added in step (3).

[0043] Preparation Example 1-4 The difference from Preparation Example 1-1 is that the mass ratio of the nano-sized calcium carbonate, the modified graphene, and the aluminum dihydrogen phosphate is 1:0.78:0.12.

[0044] Preparation Example 1-5 The difference from Preparation Example 1-1 is that the mass ratio of the nano-sized calcium carbonate, the modified graphene, and the aluminum dihydrogen phosphate is 1:0.12:0.56.

[0045] Preparation Example 1-6 The difference from Preparation Example 1-1 is that no aluminum oxide whisker is added in the preparation process of the modified graphene.

[0046] Preparation Example 1-7 The difference from Preparation Example 1-1 is that no sodium alginate solution is added in the preparation process of the modified graphene.

[0047] Preparation Example of Nylon Powder Preparation Example 2-1 A method for preparing nylon powder includes the following steps: (1) 10 kg of nylon resin (PA6), 1 kg of silane coupling agent KH550, 3 kg of modified molecular sieve, 1 kg of dibutyltin dilaurate, and 0.5 kg of antioxidant 1010 were melted at 230°C for 1 h to obtain a mixed solution, cooled to 70°C, ground, and then dispersed into 30 L of deionized water, stirred at a temperature of 62°C for 1.5 h, dried, and sieved through an 80-mesh sieve to obtain a powder; (2) The powder was dispersed into 35 L of deionized water, 4 kg of boron fiber, 1 kg of flow agent (sodium stearate), and 0.5 kg of super-dispersant coating agent (sodium polyacrylate) were added, stirred at a temperature of 82°C for 2.5 h at a stirring speed of 450 r / min, and dried to obtain a nylon powder.

[0048] The mass ratio of the nylon resin, the modified molecular sieve, and the boron fiber was 1:0.46:0.15.

[0049] The preparation method of the modified molecular sieve included the following steps: 4 kg of molecular sieve was dispersed into 8 L of an aqueous solution of amino silane (silane coupling agent KH550) with a mass fraction of 10%, stirred for 1.5 h, filtered, crushed, sieved through a 30-mesh sieve, calcined at a temperature of 230°C for 1.5 h, then dispersed into 25 L of deionized water, 2 kg of aluminum sol, 2.8 kg of ceramic fiber, and 1 kg of metal organic framework (MOFs) were added, stirred at a temperature of 62°C for 2.5 h, and dried to obtain the modified molecular sieve.

[0050] The metal organic framework (MOFs) was purchased from Suzhou Beikona Nanometer Technology Co., Ltd., and specifically was MOFs material ultra-fine spherical carbon powder, brand: Manli Nanometer.

[0051] Preparation Example 2-2 The difference from Preparation Example 2-1 was that no modified molecular sieve was added in step (1).

[0052] Preparation Example 2-3 The difference from Preparation Example 2-1 was that no boron fiber was added in step (2).

[0053] Preparation Example 2-4 The difference from Preparation Example 2-1 was that the mass ratio of the nylon resin, the modified molecular sieve, and the boron fiber was 1:0.52:0.23.

[0054] Preparation Example 2-5 The difference from Preparation Example 2-1 was that the mass ratio of the nylon resin, the modified molecular sieve, and the boron fiber was 1:0.10:0.36.

[0055] Preparation Example 2-6 The difference from Preparation Example 2-1 was that no ceramic fiber was added in the preparation method of the modified molecular sieve.

[0056] Preparation Example 2-7 The difference from Preparation Example 2-1 is that no aluminum sol is added in the preparation method of the modified molecular sieve. Example

[0057] Example 1 A rubber material with infrared function prevention, comprising the following raw materials by weight: T145 101.5 kg, SSBR (solution polymerized butadiene styrene rubber) 30 kg, white carbon black 9 kg, silane coupling agent SI-69 4 kg, carbon black N660 30 kg, titanium dioxide 5 parts, ITO 10 kg, LaB6 2 kg, stearic acid 1 kg, ZnO 5 kg, carbon nanotube 1.5 kg, antioxidant 4020 1.5 kg, antioxidant RD (antioxidant) 1.5 kg, PVI (N-cyclohexyl thio phthalimide) 0.3 kg, NS (N-tert-butyl-2-benzothiazole sulfenamide) 0.9 kg, S 0.9 kg, modified nano calcium carbonate 19 kg, nylon powder 14 kg, aromatic oil 8 kg. The aromatic oil is purchased from Hansheng V500, an environmentally friendly aromatic oil.

[0058] T145 (wet modified natural rubber compound) is prepared according to Example 4 in the granted patent CN 108070180 B.

[0059] The preparation method of the above rubber material with infrared function prevention, comprising the following steps: T145 is put into the internal mixer for plasticizing, the rotor speed is 50 revolutions, the pressure is 0.6 MPa, the mixing time is 4 min or the discharge at 150℃ (the first one is accurate), and the sheet is passed through the open mill (the roller temperature is 50℃) and is parked for 12 h to obtain T145 plasticized rubber; T145 plasticized rubber, SSBR, white carbon black, silane coupling agent SI-69, carbon black N660, titanium dioxide, ITO, stearic acid, carbon nanotube, antioxidant 4020, antioxidant RD, PVI, zinc oxide, modified nano calcium carbonate, nylon powder, and aromatic oil are put into the internal mixer (the rotor speed is 50 revolutions, and the pressure is 0.6 MPa), and mixing is performed until the temperature reaches 158℃ and the material is discharged, and then the material is passed through the open mill (the roller temperature is 70℃) and is packed into a triangle bag, and the sheet is cooled and parked for 30 h to obtain a masterbatch; the masterbatch is added into the internal mixer, LaB6, NS and S are further added, mixing is performed for 4 min or the material is discharged at 105℃ (the first one is accurate), and after the material is passed through the open mill and packed into a triangle bag, the sheet is cooled and parked for 4 h, the internal mixer is returned to the mixing position, the sheet is taken out, and is parked for 2 h, and then the material is vulcanized at 150℃ to obtain the rubber material.

[0060] The modified nano calcium carbonate is prepared by Preparation Example 1-1, and the nylon powder is prepared by Preparation Example 2-1.

[0061] Example 2 A rubber material with infrared protection function, which is different from example 1 in that it comprises the following raw materials by weight: T145 100 kg, SSBR 28 kg, white carbon black 8 kg, silane coupling agent SI-69 4 kg, carbon black N660 28 kg, titanium dioxide 4 kg, ITO 9 kg, LaB6 2 kg, stearic acid 1 kg, ZnO 6 kg, carbon nanotube 1.4 kg, antioxidant 4020 1.4 kg, antioxidant R 1.3 kg, PVI 0.2 kg, NS 0.7 kg, S 0.7 kg, modified nano calcium carbonate 18 kg, nylon powder 15 kg, aromatic oil 9 kg.

[0062] The preparation method of the above-mentioned rubber material with infrared protection function comprises the following steps: T145 is plasticized in an internal mixer, the rotor speed is 40 revolutions, the pressure is 0.6 MPa, the mixing time is 3 min or the discharge temperature is 145°C (whichever comes first), and the T145 plasticized rubber is obtained by thin passing on an open mill (roller temperature 40°C) and standing for 8 h; T145 plasticized rubber, SSBR, white carbon black, silane coupling agent SI-69, carbon black N660, titanium dioxide, ITO, stearic acid, carbon nanotube, antioxidant 4020, antioxidant R, PVI, zinc oxide, modified nano calcium carbonate, nylon powder and aromatic oil are put into an internal mixer (rotor speed 40 revolutions, pressure 0.6 MPa), and mixing is carried out until the temperature reaches 155°C, and then discharged to an open mill (roller temperature 60°C) for thin passing, triangle bagging, and cooling and standing for 16 h to obtain a masterbatch; the masterbatch is added to the internal mixer, and LaB6, NS and S are added, and mixing is carried out for 3 min or 105°C (whichever comes first), and then cooled and stood for 4 h, and then returned to the mixer for re-mixing, and then discharged and cooled, and then placed for 2 h, and then vulcanized at 150°C to obtain the rubber material.

[0063] Example 3 A rubber material with infrared protection function, which is different from example 1 in that it comprises the following raw materials by weight: T145 102 kg, SSBR 32 kg, white carbon black 10 kg, silane coupling agent SI-69 5 kg, carbon black N660 32 kg, titanium dioxide 6 kg, ITO 11 kg, LaB6 3 kg, stearic acid 1.2 kg, ZnO 4 kg, carbon nanotube 1.6 kg, antioxidant 4020 1.6 kg, antioxidant R 1.7 kg, PVI 0.4 kg, NS 1.1 kg, S 1.1 kg, modified nano calcium carbonate 20 kg, nylon powder 12 kg, aromatic oil 8 kg.

[0064] The preparation method of the rubber material with infrared-proof function comprises the following steps: T145 is put into a plastic mixer, the rotor speed is 60 revolutions, the pressure is 0.7 MPa, the mixing time is 5 minutes or 155 DEG C discharging (the first one is accurate), and the plastic mixer (the roller temperature is 50 DEG C) is used for thin passing and sheeting, and the rubber material is obtained after being placed for 16 hours; the T145 plasticized rubber, SSBR, white carbon black, silane coupling agent SI-69, carbon black N660, titanium dioxide, ITO, stearic acid, carbon nanotubes, antioxidant 4020, antioxidant RD, PVI, zinc oxide, modified nano calcium carbonate, nylon powder and aromatic oil are put into a plastic mixer (the rotor speed is 60 revolutions, the pressure is 0.7 MPa), and mixing is carried out until the temperature reaches 160 DEG C and discharging, and the plastic mixer (the roller temperature is 70 DEG C) is used for thin passing and sheeting, and the rubber material is obtained after being placed for 48 hours; the masterbatch is added into the plastic mixer, LaB6, NS and S are further added, mixing is carried out for 5 minutes or 110 DEG C discharging (the first one is accurate), and the rubber material is obtained after being placed for 4 hours, back to the plastic mixer, sheeting, placing for 2 hours, 150 DEG C vulcanization, and the rubber material with infrared-proof function is obtained.

[0065] Example 4 A rubber material with infrared-proof function, which is different from example 1 in that the modified nano calcium carbonate is prepared by the preparation example 1-2.

[0066] Example 5 A rubber material with infrared-proof function, which is different from example 1 in that the modified nano calcium carbonate is prepared by the preparation example 1-3.

[0067] Example 6 A rubber material with infrared-proof function, which is different from example 1 in that the modified nano calcium carbonate is prepared by the preparation example 1-4.

[0068] Example 7 A rubber material with infrared-proof function, which is different from example 1 in that the modified nano calcium carbonate is prepared by the preparation example 1-5.

[0069] Example 8 A rubber material with infrared-proof function, which is different from example 1 in that the modified nano calcium carbonate is prepared by the preparation example 1-6.

[0070] Example 9 A rubber material with infrared-proof function, which is different from example 1 in that the modified nano calcium carbonate is prepared by the preparation example 1-7.

[0071] Example 10 A rubber material with infrared-proof function, which is different from example 1 in that the nylon powder is prepared by the preparation example 2-2.

[0072] Example 11 A rubber material with infrared protection function, which is different from Example 1 in that the nylon powder is prepared by Preparation Example 2-3.

[0073] Example 12 A rubber material with infrared protection function, which is different from Example 1 in that the nylon powder is prepared by Preparation Example 2-4.

[0074] Example 13 A rubber material with infrared protection function, which is different from Example 1 in that the nylon powder is prepared by Preparation Example 2-5.

[0075] Example 14 A rubber material with infrared protection function, which is different from Example 1 in that the nylon powder is prepared by Preparation Example 2-6.

[0076] Example 15 A rubber material with infrared protection function, which is different from Example 1 in that the nylon powder is prepared by Preparation Example 2-7.

[0077] Comparative Example Comparative Example 1 A rubber material with infrared protection function, which is different from Example 1 in that no nylon powder is added.

[0078] Comparative Example 2 A rubber material with infrared protection function, which is different from Example 1 in that no modified nano-sized calcium carbonate is added.

[0079] Performance test The rubber materials with infrared protection function prepared by Examples 1-15 and Comparative Examples 1-2 are tested for performance; The tensile properties are tested according to GB / T 528-2009, the wear resistance is tested according to GB / T 1689-2014, and the 100% modulus is tested according to GB / T 528-2009 test standard.

[0080] The aging performance is tested according to GB / T 3512-2014 vulcanized rubber or thermoplastic rubber hot air accelerated aging and heat resistance test standard, the aging time is 24h, and the aging temperature is 120℃; the tensile strength of the sample after aging is tested, and the tensile strength change rate after aging is calculated according to the effect value before and after aging; the test results are shown in Table 1.

[0081] Table 1 Test data of examples and comparative examples As can be seen from Table 1, the rubber material with infrared function prepared in Examples 1-3 has good mechanical properties and wear resistance, wherein the tensile strength of Example 1 is 31.2 MPa, the wear volume is 0.059 cm 3 , the absolute value of the tensile strength change rate after aging is 2.1%, and the 100% elongation stress is 5.2 MPa. It can be seen that the rubber material prepared in the application has good comprehensive performance, T145 is used with SSBR, and multiple reinforcements of white carbon black, carbon black and carbon nanotubes are used, which is expected to have high tensile strength, tear strength and wear resistance, and at the same time realize the infrared function.

[0082] The rubber material prepared in Example 1 is tested for infrared resistance, and the radiation rate at a wavelength of 10 μm is measured as 0.38 according to the infrared radiation rate detection method of national standard GJB8700-2015. The application uses ITO (mainly for medium and far infrared), LaB6 (supplement near infrared), and multiple components (constructing conductive reflection network) such as conductive carbon black / carbon nanotube to compound, and then uses processing aid (SI-69) to ensure that all functional components can be uniformly dispersed and form an effective functional layer, so that the obtained rubber material has excellent infrared resistance / stealth potential.

[0083] In the preparation method of modified nano calcium carbonate in Examples 4-5, no modified graphene and aluminum dihydrogen phosphate is added respectively, and the mass ratio of nano calcium carbonate, modified graphene and aluminum dihydrogen phosphate is changed in Examples 6-7. As can be seen from Table 1, the test results of tensile strength, wear volume, absolute value of tensile strength change rate after aging, and 100% elongation stress of Examples 4-5 are obviously poorer than those of Examples 1-3 and Example 6, and the corresponding performance test results of Example 7 are better than those of Examples 4-5, but poorer than those of Examples 1-3 and Example 6. It shows that aluminum dihydrogen phosphate can penetrate into the gap between calcium carbonate particles and graphene sheets, firmly bond them together, has excellent heat resistance, weather resistance and chemical corrosion resistance, maintains the stability of the performance of the composite material, and improves the comprehensive performance of the rubber material such as mechanical properties and wear resistance.

[0084] In the preparation method of modified graphene in Examples 8-9, no aluminum oxide whisker and sodium alginate solution is added respectively. As can be seen from Table 1, the test results of tensile strength, wear volume, absolute value of tensile strength change rate after aging, and 100% elongation stress of Examples 8-9 are obviously poorer than those of Examples 1-3, but better than those of Example 4. It shows that aluminum oxide whisker has extremely high strength and modulus, and when it is compounded with graphene, a multi-dimensional reinforcing network is constructed, which significantly improves the mechanical properties of the final composite material. The sodium alginate solution will penetrate into the pores of the sulfurized graphene / aluminum oxide whisker composite, and after drying, it will form an organic coating layer, which will firmly encapsulate the entire composite structure and improve the mechanical properties of the system.

[0085] The preparation method of the nylon powder of examples 10-11 does not add modified molecular sieve, boron fiber respectively, examples 12-13 change the mass ratio of nylon resin, modified molecular sieve and boron fiber. As can be seen from table 1, the tensile strength, wear volume, absolute value of tensile strength change rate after aging, 100% tensile stress test effect of examples 10-11 are obviously worse than examples 1-3 and examples 12, and the corresponding performance test effect of examples 13 is better than examples 10-11, but worse than examples 1-3 and examples 12. It shows that boron fiber has very high specific strength and specific modulus, is adsorbed on the surface of the particles, and improves the hardness, rigidity and heat resistance of the final product; boron fiber, nylon resin, modified molecular sieve synergistically enhance, and the interface optimization of silane coupling agent, the product after powder forming has good tensile strength and impact strength, and high performance composite material is prepared.

[0086] The preparation method of modified molecular sieve of examples 14-15 does not add ceramic fiber and aluminum sol respectively. As can be seen from table 1, the tensile strength, wear volume, absolute value of tensile strength change rate after aging, 100% tensile stress test effect of examples 14-15 are obviously worse than examples 1-3, but better than examples 10. It shows that ceramic fiber has high strength and heat resistance, forms a network with aluminum sol and molecular sieve, and significantly improves the mechanical strength, toughness and wear resistance of the material; the colloidal particles of aluminum sol have hydroxyl groups on the surface, form hydrogen bonds or acid-base interaction with the amino groups on the surface of molecular sieve, and can bond ceramic fiber and MOFs, enhancing the structural integrity of the composite system.

[0087] Comparative example 1 and comparative example 2 do not add nylon powder and do not add modified nano calcium carbonate respectively. As can be seen from table 1, the tensile strength, wear volume, absolute value of tensile strength change rate after aging, 100% tensile stress test effect of comparative examples 1 and 2 are obviously worse than examples 1-2, which shows that modified nano calcium carbonate improves the tensile strength and tear strength, and is uniformly dispersed in the rubber matrix, filling the micropores in the rubber matrix, improving the elasticity and aging resistance; nylon powder has high hardness, high wear resistance and high impact resistance, which improves the mechanical properties of rubber material, and further prolongs the service life of rubber products.

[0088] The specific embodiments are only an explanation of the present application, which is not a limitation of the present application, and those skilled in the art can make modifications to the embodiments without creative contribution after reading the specification, but as long as it is within the scope of the claims of the present application, it is protected by the patent law.

Claims

1. A rubber material having an infrared shielding function, characterized by comprising a rubber material having a structure in which a plurality of carbon nanotubes are dispersed in a rubber matrix. The raw materials include the following weight parts: T145 100-102 parts, SSBR 28-32 parts, white carbon black 8-10 parts, silane coupling agent SI-69 4-5 parts, carbon black N660 28-32 parts, titanium dioxide 4-6 parts, ITO 9-11 parts, LaB62-3 parts, stearic acid 1-1.2 parts, ZnO 4-6 parts, carbon nanotube 1.4-1.6 parts, antioxidant 4020 1.4-1.6 parts, antioxidant RD 1.3-1.7 parts, PVI 0.2-0.4 parts, NS 0.7-1.1 parts, S 0.7-1.1 parts, modified nano calcium carbonate 18-20 parts, nylon powder 12-15 parts, aromatic oil 8-9 parts.

2. The rubber material having an infrared protection function according to claim 1, wherein, T145 101.5 parts, SSBR 30 parts, white carbon black 9 parts, silane coupling agent SI-69 4 parts, carbon black N660 30 parts, titanium dioxide 5 parts, ITO 10 parts, LaB62 parts, stearic acid 1 part, ZnO 5 parts, carbon nanotube 1.5 parts, antioxidant 4020 1.5 parts, antioxidant RD 1.5 parts, PVI 0.3 parts, NS 0.9 parts, S 0.9 parts, modified nano calcium carbonate 19 parts, nylon powder 14 parts, aromatic oil 8 parts.

3. The rubber material having an infrared protection function according to claim 1, wherein The preparation method of the modified nano calcium carbonate comprises the following steps: (1) dispersing nano calcium carbonate in ethanol, adding diatomite, polymethyl acrylate and sodium laurate, stirring for 20-25 min, grinding, obtaining a mixture, calcining the mixture at 320-340 DEG C for 1-2 h, obtaining a porous mixture; (2) dispersing modified graphene in deionized water, ultrasonicating for 1-2 h, adding the porous mixture of step (1), continuing to ultrasonicate for 2-3 h, filtering, obtaining a mixture; (3) dispersing aluminum dihydrogen phosphate and chitosan in acetic acid solution, obtaining a mixed solution, spraying the mixed solution to the surface of the mixture of step (2), drying, obtaining the modified nano calcium carbonate.

4. The rubber material having an infrared protection function according to claim 3, wherein The mass ratio of the nano calcium carbonate, the modified graphene and the aluminum dihydrogen phosphate is 1:0.65-0.78:0.12-0.

18.

5. The rubber material having an infrared protection function according to claim 3, wherein The preparation method of the modified graphene comprises the following steps: dispersing graphene in sulfuric acid solution, heating and refluxing at a temperature of 120-130 DEG C for 4-5 h, water washing, obtaining sulfurized graphene, dispersing the sulfurized graphene into deionized water, adding aluminum oxide whisker and sodium dodecyl sulfonate, placing under ultraviolet lamp for 15-17 min, filtering, obtaining a mixture, immersing the mixture in sodium alginate solution, drying, obtaining the modified graphene; dispersing sodium alginate, nano nickel, tea polyphenol extract and calcium gluconate into deionized water, stirring at a temperature of 60-65 DEG C for 1-2 h, obtaining a sodium alginate solution.

6. The rubber material having an infrared protection function according to claim 1, wherein The preparation method of the nylon powder comprises the following steps: (1) melt nylon resin, silane coupling agent, modified molecular sieve, dibutyltin dilaurate and antioxidant at 220-230 DEG C for 1-1.2 h to obtain a mixed solution, grind at 65-70 DEG C, then disperse in deionized water, stir at 60-65 DEG C for 1-2 h, dry, sieve to obtain a powder; (2) disperse the powder in deionized water, add boron fiber, flow agent and superdispersion coating agent, stir at 80-85 DEG C for 2-3 h at a stirring speed of 440-450 r / min, dry to obtain a nylon powder.

7. The rubber material having an infrared protection function according to claim 6, wherein The mass ratio of the nylon resin, modified molecular sieve and boron fiber is 1:0.46-0.52:0.15-0.

23.

8. The rubber material having an infrared protection function according to claim 6, wherein The preparation method of the modified molecular sieve comprises the following steps: disperse the molecular sieve in an aqueous solution of aminosilane, stir for 1-2 h, filter, crush, sieve, calcine at 220-240 DEG C for 1-2 h, then disperse in deionized water, add aluminum sol, ceramic fiber and metal organic framework, stir at 60-65 DEG C for 2-3 h, dry to obtain the modified molecular sieve.

9. The method of claim 1, wherein the rubber material having an infrared protection function is prepared by adding the infrared absorbing agent to the rubber material. The method comprises the following steps: T145 is subjected to internal mixing to obtain T145 plasticated rubber, T145 plasticated rubber, SSBR, white carbon black, silane coupling agent SI-69, carbon black N660, titanium dioxide, ITO, stearic acid, carbon nanotube, antioxidant 4020, antioxidant RD, PVI, zinc oxide, modified nano calcium carbonate, nylon powder and aromatic oil are mixed to obtain a masterbatch; the masterbatch is added with LaB6, NS and S, and is subjected to mixing to obtain a final rubber; the final rubber is subjected to return mixing and vulcanization to obtain a rubber material.

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