Highly abrasion-resistant composite rubber material and method for producing the same

Abstract

The application relates to the technical field of rubber materials, and particularly discloses a high-wear-resistance composite rubber material and a preparation method thereof. The high-wear-resistance composite rubber material comprises the following components in parts by weight: 30-55 parts of natural rubber, 30-55 parts of high-cis polybutadiene composite rubber, 15-30 parts of solution-polymerized styrene-butadiene rubber, 5-7 parts of polydicyclopentadiene resin, 2-4 parts of liquid polyisoprene rubber, 0.5-1.5 parts of modified graphene oxide, 30-40 parts of carbon black, 10-15 parts of wear-resistant filler, 4-6 parts of zinc oxide, 1-3 parts of stearic acid, 2-3 parts of sulfur, 0.8-1.6 parts of a coupling agent, 0.5-2.5 parts of an antioxidant and 0.5-2.5 parts of an accelerator. The application adopts a natural rubber / high-cis polybutadiene composite rubber / solution-polymerized styrene-butadiene rubber blending system, uses polydicyclopentadiene resin and liquid polyisoprene rubber as plasticizers, has high crosslinking density and good compatibility, and achieves the purpose of improving the wear resistance of the rubber material.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of rubber materials, in particular to a high wear-resistant composite rubber material and a preparation method thereof. BACKGROUND

[0002] With the continuous expansion of the application field of rubber, people have put forward higher requirements for the functionality of rubber, for example, the rubber material applied to the tire interlayer pad rubber layer not only needs good mechanical properties, but also should have the characteristics of low heat generation, high thermal conductivity, friction resistance and low sliding resistance. Natural rubber (NR) is a natural high molecular compound with cis-1, 4-polyisoprene as the main component, which has the characteristics of large elasticity, high modulus of elongation, excellent tear resistance and electrical insulation, and is widely used in daily life, medical health, transportation, industry, agriculture and other fields. However, the wear resistance of natural rubber is generally poor, which cannot meet the use requirements in strong friction occasions.

[0003] In order to improve the wear resistance of natural rubber, one method is to add fillers such as calcium carbonate, carbon black, white carbon black and montmorillonite to the rubber, which can significantly improve the mechanical properties, thermal properties and electrical properties of the composite material. However, the problem is that the rubber molecular chain is generally a non-polar polydiene material, which has poor compatibility with most polar fillers. It is difficult to uniformly disperse the fillers in the rubber matrix by external mechanical shearing, and it is easy to form large size agglomerates or migrate to produce blooming phenomenon, which seriously affects the processing and performance of the rubber material. In addition, blending with high polymer with excellent wear resistance is also one of the methods to improve the wear resistance of natural rubber. However, the rubber used must have certain compatibility, otherwise it is difficult to form molecular level blending, resulting in separation of the composite rubber material during processing or use of the product. Therefore, how to improve the compatibility of fillers and rubber matrix, as well as the compatibility between various rubber materials, is the key to improving the performance of rubber materials. SUMMARY

[0004] In view of this, the present application provides a high wear-resistant composite rubber material and a preparation method thereof, which adopts a natural rubber / high cis-polybutadiene composite rubber / solution polymerized styrene-butadiene rubber blending system, selects polydicyclopentadiene resin and liquid polyisoprene rubber as plasticizers, and is matched with modified graphene oxide, hard carbon black and wear-resistant fillers, so as to achieve high crosslinking density, good compatibility and the purpose of improving the wear resistance of rubber materials.

[0005] In order to achieve the above-mentioned application purposes, the embodiments of the present application adopt the following technical solutions:

[0006] In a first aspect, the present application provides a high wear-resistant composite rubber material, comprising the following components in parts by weight: 30-55 parts of natural rubber, 30-55 parts of high-cis polybutadiene composite rubber, 15-30 parts of solution styrene-butadiene rubber, 5-7 parts of polydicyclopentadiene resin, 2-4 parts of liquid polyisoprene rubber, 0.5-1.5 parts of modified graphene oxide, 30-40 parts of carbon black, 10-15 parts of wear-resistant filler, 4-6 parts of zinc oxide, 1-3 parts of stearic acid, 2-3 parts of sulfur, 0.8-1.6 parts of coupling agent, 0.5-2.5 parts of antioxidant, and 0.5-2.5 parts of accelerator; wherein the total of the parts by weight of the natural rubber, the high-cis polybutadiene composite rubber, and the solution styrene-butadiene rubber is 100 parts.

[0007] Compared with the prior art, the high wear-resistant composite rubber material provided by the present application has the following advantages:

[0008] The present application uses natural rubber as the main rubber, and uses solution styrene-butadiene rubber and high-cis polybutadiene composite rubber, wherein the natural rubber has a flexible molecular chain, a large crosslinking density, a small intermolecular force, and a large number of C-C single bonds that can rotate internally; the solution styrene-butadiene rubber has excellent wear resistance, and the conjugation effect of the benzene ring can improve the affinity of the filler and the rubber molecular chain, help the interface bonding of the filler and the rubber, reduce the accumulation of hard carbon particles that are not easy to disperse in the rubber material, and avoid the formation of stress concentration points; the high-cis polybutadiene composite rubber has good cold resistance, wear resistance, and elasticity, and generates less heat under dynamic load. The present application blends the three in a specific ratio, which helps the directional arrangement of the molecular chain segments, reduces the internal friction between the macromolecular chains, enhances the crosslinking density between the rubbers, forms a uniform three-dimensional network structure, has a high blending degree, and greatly improves the comprehensive performance of the rubber material.

[0009] The application can improve the dispersion effect of carbon black and other wear-resistant fillers, reduce the friction and slip between the fillers and the rubber molecular chains, increase the crosslinking density of the blended rubber, and make the rubber have good physical properties and chemical stability, so as to improve the wear resistance of the rubber material.

[0010] The application introduces modified graphene oxide, carbon black and other wear-resistant fillers in the formula and uses the reinforcing composite rubber, which can give the composite rubber excellent strength and wear resistance, and the specific filler amount range makes the filler network degree low and the overall dispersion uniform, and the filler is not easy to agglomerate.

[0011] Optionally, the high-cis polybutadiene composite rubber is a mixture of high-cis 1,4-polybutadiene and 1,2-syndiotactic polybutadiene; wherein the content of the 1,2-syndiotactic polybutadiene is 1.5wt%-2.5wt%. The specific content of the 1,2-syndiotactic polybutadiene has high reinforcing performance for the high-cis 1,4-polybutadiene, and the formed high-cis polybutadiene composite rubber can improve the hardness and modulus of the blended rubber.

[0012] Optionally, the content of styrene in the solution polymerized styrene-butadiene rubber is 35wt%-40wt%, and the content of vinyl is 40wt%-60wt%.

[0013] The preferred content of styrene and vinyl in the solution polymerized styrene-butadiene rubber makes the difference between the solubility parameters of the solution polymerized styrene-butadiene rubber and the natural rubber / high-cis polybutadiene composite rubber reduced, and also makes the interaction enthalpy change between the isoprene in the natural rubber molecular chain and the butadiene in the solution polymerized styrene-butadiene rubber molecular chain reduced, which is beneficial to improve the micro-compatibility of the three, so as to improve the strength and wear resistance of the rubber material.

[0014] Optionally, the liquid polyisoprene rubber structure unit has a molar ratio of 70% to 90% of cis-1,4-structure and a molar ratio of 20% to 30% of 3,4-structure, a molecular weight of 20,000 g / mol to 40,000 g / mol, and a molecular weight distribution of 1.2 to 1.3.

[0015] Optionally, the modified graphene oxide is prepared by reacting a rubber accelerator with graphene oxide, and the preparation steps are as follows:

[0016] s1, adding graphene oxide into water, ultrasonic stripping to obtain a water dispersion of graphene oxide;

[0017] s2, dissolving a rubber accelerator in an organic solvent or water to form a rubber accelerator solution;

[0018] s3, mixing the rubber accelerator solution with the water dispersion of graphene oxide, stirring and reacting at 60°C to 80°C for 3h to 5h, and then performing suction filtration, washing, centrifugation, and drying on the mixed solution after reaction to obtain the modified graphene oxide.

[0019] Further optionally, the rubber accelerator is composed of N-tert-butyl-2-benzothiazole sulfenamide and di-o-methyl phenyl guanidine with a mass ratio of 2 to 3:1, and the mass ratio of the rubber accelerator to graphene oxide is 1 to 2:1.

[0020] The preferred modified graphene oxide can participate in the vulcanization of rubber by grafting specific rubber accelerator molecular segments, shorten the vulcanization time, and improve the vulcanization efficiency; and its dispersion state in rubber is uniform, and a good interfacial bond is formed between the rubber and the modified graphene oxide, which can significantly improve the vulcanization performance, mechanical properties, and dynamic viscoelastic properties of the rubber composite material; at the same time, the sheet structure of the modified graphene oxide can reduce the agglomeration of carbon black and other wear-resistant fillers, and improve the dispersibility of the fillers.

[0021] Optionally, the carbon black is at least one of carbon black N110, carbon black N220, carbon black N234, or carbon black N330.

[0022] Optionally, the wear-resistant filler is at least one of carbon fiber powder, carbon nanotube, nano-silicon dioxide, zinc oxide whisker, fly ash, or kaolin.

[0023] Optionally, the coupling agent is at least one of a silane coupling agent, a titanate coupling agent, or an aluminate coupling agent.

[0024] Further optionally, the coupling agent is a mixture of γ-glycidyl ether propyl trimethoxysilane and 3-aminopropyl trimethoxysilane with a mass ratio of 0.9 to 1.1:0.9 to 1.1.

[0025] The preferred coupling agent has active functional groups such as epoxy, amino and methoxy, which can form chemical bonds and physical adsorption with the surface of the filler, improve the wettability and dispersibility of the filler in the polymer, and also can couple with the rubber molecules to form stable hydrogen bonds, improve the crosslinking density of the blending system, effectively improve the compatibility, and greatly improve the tensile resistance, elasticity and wear resistance of the rubber material.

[0026] Optionally, the antioxidant can use conventional antioxidants in the art, preferably at least one of quinoline, p-phenylenediamine or naphthylamine antioxidant, such as antioxidant 4020, antioxidant D, antioxidant BLE, antioxidant H or antioxidant RD, etc.

[0027] Optionally, the accelerator can use conventional accelerators in the art, preferably at least one of thiazole, sulfenamide, thiuram, thiourea, aldehyde amine, dithio carbamate, guanidine or xanthate accelerator, such as accelerator D, accelerator NS, accelerator CZ, accelerator ZDC, accelerator NOBS or accelerator DM, etc.

[0028] In a second aspect, the application also provides a preparation method of the high wear-resistant composite rubber material, comprising the following steps:

[0029] Step one, according to the design ratio, the components are weighed, the natural rubber, high cis-polybutadiene composite rubber and solution-polymerized styrene-butadiene rubber are mixed and plasticized to obtain a mixed rubber;

[0030] Step two, the mixed rubber, polydicyclopentadiene resin, liquid polyisoprene rubber, modified graphene oxide, carbon black, zinc oxide, stearic acid, wear-resistant filler, accelerator, coupling agent and antioxidant are mixed to perform the first time of mixing in an internal mixer to obtain a first-stage mixed rubber;

[0031] Step three, the first-stage mixed rubber and sulfur are mixed to perform the second time of mixing in an internal mixer, and then the mixed material is discharged to a two-roll mill to make a triangle bag, roll, thin pass 3-5 times, sheet out, and cool to obtain a second-stage mixed rubber;

[0032] Step four, the second-stage mixed rubber is hot rolled, rolled and calendered to obtain a semi-finished rubber sheet;

[0033] Step five, the semi-finished rubber sheet is vulcanized to obtain the high wear-resistant composite rubber material.

[0034] Compared with the prior art, the preparation method of the high wear-resistant composite rubber material provided by the application has the following advantages:

[0035] The application adopts natural rubber / high cis-polybutadiene composite rubber / solution styrene-butadiene rubber blending system, selects polydicyclopentadiene resin and liquid polyisoprene rubber as plasticizer, and is matched with modified graphene oxide, hard carbon black and wear-resistant filler, adopts two-stage mixing process, so that the rubber material has good mechanical properties, high tensile strength and tear resistance, good wear resistance, simple operation, no complex process, and is conducive to industrialization promotion.

[0036] Optionally, in step one, the plasticating condition is that the plasticating time is 3-8 minutes, and the plasticating temperature is 70-80 DEG C.

[0037] Optionally, in step two, the first time mixing condition is that the mixing time is 10-20 minutes, the initial temperature is 70-80 DEG C, the discharge temperature is 115-125 DEG C, and the rotating speed is 30-40 rpm.

[0038] Optionally, in step three, the second time mixing condition is that the mixing time is 1.5-3 minutes, the initial temperature is 50-60 DEG C, the discharge temperature is <100 DEG C, and the rotating speed is 30-40 rpm.

[0039] Optionally, in step three, the roll temperature of the open mill is 50-70 DEG C, the thin pass roll gap is 0.5-1.0 mm, and the sheeting roll gap is 6-8 mm.

[0040] Optionally, in step four, the temperature of the heat mixing is 60-70 DEG C.

[0041] Optionally, in step four, the calendering condition is that the calendering temperature is 55-65 DEG C, the calendering speed is 6-12 m / min, and the rubber sheet thickness is 1.5-3.5 mm.

[0042] Optionally, in step five, the vulcanizing condition is that the vulcanizing pressure is 2-4 MPa, the vulcanizing temperature is 130-150 DEG C, and the vulcanizing time is 10-20 minutes. DETAILED DESCRIPTION

[0043] In order to make the purpose, technical scheme and advantages of the application more clear and obvious, the application is further described in detail below in combination with examples. It should be understood that the specific examples described here are only used to explain the application, and are not used to limit the application.

[0044] Example 1

[0045] The embodiment of the present application provides a kind of high wear-resistant composite rubber material, including following weight fraction of each component: natural rubber 45 parts, high cis-polybutadiene composite rubber 40 parts, solution polybutene rubber 15 parts, polydicyclopentadiene resin 6 parts, liquid polyisoprene rubber 3 parts, modified graphene oxide 1 part, 40 parts carbon black N330, nano silicon dioxide 10 parts, zinc oxide 5 parts, stearic acid 2 parts, sulfur 3 parts, coupling agent (the mass ratio of γ-glycidyl ether oxypropyl trimethoxysilane and 3-aminopropyl trimethoxysilane is 1:1) 1.2 parts, 2 parts antioxidant 4020 and 2 parts accelerator CZ.

[0046] Wherein, modified graphene oxide is prepared by the following steps: 200mg of graphene oxide is dispersed in 400ml of water, and ultrasonic stripping is carried out to obtain a water dispersion of graphene oxide. 150mg of N-tert-butyl-2-benzothiazole sulfenamide and 70mg of di-o-methyl benzoguanidine are dissolved in 30ml of anhydrous ethanol, mixed with the above water dispersion of graphene oxide, stirred and reacted at 70 DEG C for 4h, and the reaction product is filtered, washed with ethanol, centrifuged and dried to obtain modified graphene oxide.

[0047] The preparation method of the high wear-resistant composite rubber material includes the following steps:

[0048] Step one, according to the above ratio, each component is weighed, and the natural rubber, high cis-polybutadiene composite rubber and solution polybutene rubber are mixed and plasticated on an open mill at 75 DEG C for 6min to obtain a mixed rubber;

[0049] Step two, the mixed rubber, polydicyclopentadiene resin, liquid polyisoprene rubber, modified graphene oxide, carbon black, zinc oxide, stearic acid, wear-resistant filler, accelerator, coupling agent and antioxidant are put into an internal mixer and mixed for 15min, the initial temperature is controlled at 75 DEG C, the discharge temperature is 120 DEG C, and the rotating speed is 35rpm to obtain a first-stage mixed rubber;

[0050] Step three, the first-stage mixed rubber and sulfur are mixed in the internal mixer for 2min, the initial temperature is controlled at 55 DEG C, the discharge temperature is 90 DEG C, and the rotating speed is 35rpm. Then the mixed material is discharged to an open mill, and a triangular bag is punched, a roll is wound, and thin passes are made for 4 times. The roll temperature is controlled at 60 DEG C, the thin pass roll distance is 0.8mm, the sheet roll distance is 7mm, and then the room temperature is cooled to obtain a second-stage mixed rubber;

[0051] Step four, the second-stage mixed rubber is wound after hot rolling in the open mill, and then is put into a two-roll calender to be formed, the hot rolling temperature is controlled at 65 DEG C, the calendering temperature is 60 DEG C, the calendering speed is 10m / min, and the rubber sheet thickness is 2.5mm to obtain a semi-finished rubber sheet;

[0052] Step five, the semi-finished product film is loaded into a mold for vulcanization, the vulcanization pressure is controlled to be 3 MPa, the vulcanization temperature is 140 DEG C, and the vulcanization time is 15 min, and a high wear-resistant composite rubber plate is obtained.

[0053] Example 2

[0054] The embodiment of the present application provides a kind of high wear-resistant composite rubber material, including following weight fraction of each component: natural rubber 40 parts, high cis-polybutadiene composite rubber 30 parts, solution polybutadiene rubber 30 parts, polydicyclopentadiene resin 5 parts, liquid polyisoprene rubber 2 parts, modified graphene oxide 0.5 parts, 35 parts carbon black N220, carbon fiber powder 10 parts, zinc oxide 4 parts, stearic acid 1 part, sulfur 1.5 parts, coupling agent (the mass ratio of γ-glycidyl ether oxypropyl trimethoxysilane and 3-aminopropyl trimethoxysilane is 0.9:1.1) 0.8 parts, 1.5 parts antioxidant D and 1.5 parts accelerator NS.

[0055] Wherein, modified graphene oxide is prepared by the following steps: 200mg of graphene oxide is dispersed in 400ml of water, ultrasonic stripping, and the water dispersion of graphene oxide is obtained.70mg of N-tert-butyl-2-benzothiazole sulfenamide and 30mg of di-o-methyl benzene guanidine are dissolved in 20ml of anhydrous ethanol, mixed with the above water dispersion of graphene oxide, stirred at 60 DEG C for 3h, and the reaction product is filtered, washed with ethanol, centrifuged and dried to obtain modified graphene oxide.

[0056] The preparation method of the high wear-resistant composite rubber material includes the following steps:

[0057] Step one, according to the above ratio, each component is weighed, and the natural rubber, high cis-polybutadiene composite rubber and solution polybutadiene rubber are mixed and plasticated on an open mill at 70 DEG C for 3 min to obtain a compound;

[0058] Step two, the above compound, polydicyclopentadiene resin, liquid polyisoprene rubber, modified graphene oxide, carbon black, zinc oxide, stearic acid, wear-resistant filler, accelerator, coupling agent and antioxidant are put into an internal mixer and mixed for 10 min, the initial temperature is controlled to be 70 DEG C, the discharge temperature is 115 DEG C, and the rotating speed is 30 rpm to obtain a first-stage mixed rubber;

[0059] Step three, the above first-stage mixed rubber and sulfur are mixed in the internal mixer for 1.5 min, the initial temperature is controlled to be 50 DEG C, the discharge temperature is 70 DEG C, and the rotating speed is 30 rpm. Then the mixed material is discharged to an open mill, and a triangular bag is punched, rolled, thin-passed for 3 times, wrapped around a roller, the roller temperature is controlled to be 50 DEG C, the thin-passing roller distance is 0.5 mm, and the sheet discharging roller distance is 6 mm, and then cooled at room temperature to obtain a second-stage mixed rubber;

[0060] Step four, the two-section mixing rubber is rolled after hot mixing on an open mill, and then is put into a two-roll calender to be calendered into a shape, the hot mixing temperature is controlled to be 60 DEG C, the calendering temperature is controlled to be 55 DEG C, the calendering speed is controlled to be 6 m / min, and the thickness of the rubber sheet is controlled to be 1.5 mm, so that a semi-finished rubber sheet is obtained;

[0061] Step five, the semi-finished rubber sheet is loaded into a mold to be vulcanized, the vulcanization pressure is controlled to be 2 MPa, the vulcanization temperature is controlled to be 135 DEG C, and the vulcanization time is controlled to be 16 min, so that a high wear-resistant composite rubber plate is obtained.

[0062] Example 3

[0063] The embodiment of the present application provides a high wear-resistant composite rubber material, which comprises the following components in parts by weight: 30 parts of natural rubber, 50 parts of high cis-polybutadiene composite rubber, 20 parts of solution-polymerized styrene-butadiene rubber, 7 parts of polydicyclopentadiene resin, 4 parts of liquid polyisoprene rubber, 1.5 parts of modified graphene oxide, 30 parts of carbon black N110, 15 parts of nano-silicon dioxide, 6 parts of zinc oxide, 1.5 parts of stearic acid, 3 parts of sulfur, 1.6 parts of coupling agent (mass ratio of gamma-glycidoxypropyltrimethoxysilane and 3-aminopropyltrimethoxysilane is 1.1:0.9), 2.3 parts of antioxidant H and 2.5 parts of accelerator DM.

[0064] The modified graphene oxide is prepared by the following steps: 200 mg of graphene oxide is dispersed in 400 ml of water, and is ultrasonically exfoliated to obtain a water dispersion of graphene oxide. 300 mg of N-tert-butyl-2-benzothiazolesulfenamide and 100 mg of di-o-methylphenyl guanidine are dissolved in 30 ml of anhydrous ethanol, and are mixed with the water dispersion of graphene oxide, and are stirred at 80 DEG C for 5 h. The reaction product is filtered, washed with ethanol, centrifuged, and dried to obtain the modified graphene oxide.

[0065] The preparation method of the high wear-resistant composite rubber material comprises the following steps:

[0066] Step one, the components are weighed according to the above-mentioned proportion, and the natural rubber, the high cis-polybutadiene composite rubber and the solution-polymerized styrene-butadiene rubber are mixed and plasticated on an open mill at 80 DEG C for 8 min to obtain a mixed rubber;

[0067] Step two, the mixed rubber, the polydicyclopentadiene resin, the liquid polyisoprene rubber, the modified graphene oxide, the carbon black, the zinc oxide, the stearic acid, the wear-resistant filler, the accelerator, the coupling agent and the antioxidant are put into a mixer to be mixed for 20 min, the initial temperature is controlled to be 80 DEG C, the discharge temperature is controlled to be 125 DEG C, and the rotating speed is controlled to be 40 rpm, so that a one-section mixing rubber is obtained;

[0068] Step three, mixing the above-mentioned first-stage mixed rubber and sulfur in an internal mixer, mixing for 3 min, controlling the initial temperature to be 60 DEG C, the discharge temperature to be 90 DEG C, and the rotating speed to be 35 rpm. Then discharging the mixed material to an open mill, packing into a triangle bag, rolling, thin passing 5 times, packing roller, controlling the roller temperature to be 70 DEG C, the thin passing roller distance to be 1.0 mm, and the sheet discharging roller distance to be 8 mm, and then cooling at room temperature to obtain the second-stage mixed rubber;

[0069] Step four, rolling the above-mentioned second-stage mixed rubber after hot mixing in an open mill, and then feeding into a two-roller calender to form, controlling the hot mixing temperature to be 70 DEG C, the calendering temperature to be 65 DEG C, the calendering speed to be 12 m / min, and the rubber sheet thickness to be 3.5 mm, to obtain a semi-finished rubber sheet;

[0070] Step five, vulcanizing the above-mentioned semi-finished rubber sheet in a mold, controlling the vulcanization pressure to be 4 MPa, the vulcanization temperature to be 130 DEG C, and the vulcanization time to be 20 min, to obtain a high wear-resistant composite rubber plate.

[0071] In order to better illustrate the technical scheme of the present application, the following comparative examples and the embodiments of the present application are further compared.

[0072] Comparative Example 1

[0073] The present comparative example provides a high wear-resistant composite rubber material, which is different from Example 1 in that the high-cis polybutadiene composite rubber is replaced by an equal amount of butadiene rubber.

[0074] Comparative Example 2

[0075] The present comparative example provides a high wear-resistant composite rubber material, which is different from Example 1 in that the modified graphene oxide is replaced by an equal amount of unmodified graphene oxide.

[0076] Comparative Example 3

[0077] The present comparative example provides a high wear-resistant composite rubber material, which is different from Example 1 in that the liquid isoprene rubber is replaced by an equal amount of paraffin oil.

[0078] In order to better illustrate the properties of the rubber material provided in the embodiments of the present application, the following standard is used to test the performance of the rubber materials prepared in Examples 1-3 and Comparative Examples 1-3:

[0079] Hardness: GB / T531.1-2008 Shore hardness meter method;

[0080] Tensile strength and elongation: GB / T528-2009 Determination of tensile stress-strain properties of vulcanized rubber or thermoplastic rubber;

[0081] Compression set: GB / T1683-2018 Determination method of constant deformation compression set of vulcanized rubber;

[0082] Akron abrasion: GB / T 1689-2014 Determination of abrasion resistance of vulcanized rubber.

[0083] The detection results are shown in Table 1.

[0084] Table 1 Performance test results

[0085]

[0086] As can be seen from Table 1, by adopting the natural rubber / high-cis polybutadiene composite rubber / solution polybutadiene rubber blending system, selecting polydicyclopentadiene resin and liquid polyisoprene rubber as plasticizers, and matching with modified graphene oxide, hard carbon black and wear-resistant filler, the rubber material can be significantly improved in wear resistance due to high crosslinking density and good compatibility.

[0087] The above only describes the preferred embodiments of the present application and is not intended to limit the present application, and any modification, equivalent replacement or improvement made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A high abrasion resistant composite rubber material, characterized by, The components include the following components by weight: natural rubber 30-55 parts, high cis-polybutadiene composite rubber 30-55 parts, solution styrene-butadiene rubber 15-30 parts, polydicyclopentadiene resin 5-7 parts, liquid polyisoprene rubber 2-4 parts, modified graphene oxide 0.5-1.5 parts, carbon black 30-40 parts, wear-resistant filler 10-15 parts, zinc oxide 4-6 parts, stearic acid 1-3 parts, sulfur 2-3 parts, coupling agent 0.8-1.6 parts, antioxidant 0.5-2.5 parts, and accelerator 0.5-2.5 parts; wherein the total weight of the natural rubber, high cis-polybutadiene composite rubber and solution styrene-butadiene rubber is 100 parts; The modified graphene oxide is prepared by reacting a rubber accelerator with graphene oxide, and the preparation steps are as follows: s1, adding graphene oxide to water, ultrasonic stripping, obtaining a water dispersion of graphene oxide; s2, dissolving the rubber accelerator in an organic solvent or water to form a rubber accelerator solution; s3, mixing the rubber accelerator solution and the water dispersion of graphene oxide, stirring and reacting at 60-80°C for 3-5h to obtain the modified graphene oxide.

2. The high abrasion resistant composite rubber material of claim 1, wherein, The high cis-polybutadiene composite rubber is a mixture of high cis-1,4-polybutadiene and 1,2-syndiotactic polybutadiene. The content of the 1,2-syndiotactic polybutadiene is 1.5wt%-2.5wt%.

3. The high abrasion resistant composite rubber material of claim 1, wherein, The content of styrene in the solution styrene-butadiene rubber is 35wt%-40wt%, and the content of vinyl is 40wt%-60wt%.

4. The high abrasion resistant composite rubber material of claim 1, wherein, The molar ratio of cis-1,4-structure in the structural unit of the liquid polyisoprene rubber is 70%-90%, and the molar ratio of 3,4-structure is 20%-30%, the molecular weight is 20000g / mol-40000g / mol, and the molecular weight distribution is 1.2-1.

3.

5. The high abrasion resistant composite rubber material of claim 1, wherein, The rubber accelerator is composed of N-tert-butyl-2-benzothiazole sulfenamide and di-o-methyl phenyl guanidine with a mass ratio of 2-3:1, and the mass ratio of the rubber accelerator to graphene oxide is 1-2:

1.

6. The high abrasion resistant composite rubber material of claim 1, wherein, The carbon black is at least one of carbon black N110, carbon black N220, carbon black N234 or carbon black N330; And / or the wear-resistant filler is at least one of carbon fiber powder, carbon nanotube, nano-silicon dioxide, zinc oxide whisker, fly ash or kaolin; And / or the coupling agent is at least one of silane coupling agent, titanate coupling agent or aluminate coupling agent.

7. The high abrasion resistant composite rubber material of claim 6, wherein, The coupling agent is a mixture of γ-glycidyl ether propyl trimethoxysilane and 3-aminopropyl trimethoxysilane with a mass ratio of 0.9-1.1:0.9-1.

1.

8. A method of producing the high abrasion resistant composite rubber material according to any one of claims 1 to 7, characterized in that, The steps include: Step one, according to the designed ratio, weigh each component, mix the natural rubber, high cis-polybutadiene composite rubber and solution styrene-butadiene rubber, and plasticize to obtain a mixed rubber; Step two, mix the mixed rubber, polydicyclopentadiene resin, liquid polyisoprene rubber, modified graphene oxide, carbon black, zinc oxide, stearic acid, wear-resistant filler, accelerator, coupling agent and antioxidant to perform the first time of closed mixing to obtain a first-stage mixed rubber; Step three, mixing the one-stage rubber compound and sulfur, carrying out second time closed mixing, then discharging the mixed material to the open mill to make triangle bag, rolling, thin passing 3~5 times, sheeting, cooling, obtaining the two-stage rubber compound; Step four, hot rolling the two-stage rubber compound to obtain semi-finished rubber sheet; Step five, vulcanizing the semi-finished rubber sheet to obtain the high wear-resistant composite rubber material.

9. The method for preparing the high wear-resistant composite rubber material as described in claim 8, characterized in that, In step one, the plasticating conditions are as follows: plasticating time is 3min~8min, initial temperature is 50℃~60℃, discharging temperature is 135℃~145℃, and rotating speed is 30rpm~50rpm; and / or In step two, the first time closed mixing conditions are as follows: mixing time is 10min~20min, initial temperature is 70℃~80℃, discharging temperature is 115℃~125℃, and rotating speed is 30rpm~40rpm; and / or In step three, the second time closed mixing conditions are as follows: mixing time is 1.5min~3min, initial temperature is 50℃~60℃, discharging temperature is <100℃, and rotating speed is 30rpm~40rpm; and / or In step three, the roller temperature of the open mill is 50℃~70℃, the thin passing roller distance is 0.5mm~1.0mm, and the sheeting roller distance is 6mm~8mm; and / or In step four, the hot rolling temperature is 60℃~70℃; and / or In step four, the calendering conditions are as follows: calendering temperature is 55℃~65℃, calendering speed is 6m / min~12m / min, and rubber sheet thickness is 1.5mm~3.5mm; and / or In step five, the vulcanizing conditions are as follows: vulcanizing pressure is 2MPa~4MPa, vulcanizing temperature is 130℃~150℃, and vulcanizing time is 10min~20min.

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