High-reduction-resistance and high-wear-resistance biomass tire reclaimed rubber and preparation method thereof

Abstract

The invention provides high-reduction-resistance and high-wear-resistance biomass tire reclaimed rubber and a preparation method thereof, and relates to the technical field of rubber recovery, the high-reduction-resistance and high-wear-resistance biomass tire reclaimed rubber is prepared from the following raw materials by weight: 80-100 phr of waste tire reclaimed rubber powder, 5-10 phr of a lignin enhancer, 20-30 phr of white carbon black, 2-3 phr of a silane coupling agent, 1-5 phr of an anti-reducing agent, 5-15 phr of a processing aid, and 5-10 phr of a wear-resistant reinforcing agent. According to the rubber material prepared by the invention, the lignin reinforcing agent, the white carbon black, the silane coupling agent, the carbon nanotube-carbon black reinforcing agent, the HVA-2 and the Perkalink 900 combined anti-reducing agent are used for replacing most carbon black filler, so that the environmental pollution is favorably reduced, and the carbon emission is less; in the preparation method provided by the technical scheme provided by the invention, high-speed blending and INP technologies are used, so that the reduction resistance and wear resistance of the regenerated rubber are effectively improved.

Description

Technical Field

[0001] The present invention relates to the technical field of rubber recycling, in particular to a biomass tire reclaimed rubber. Background Art

[0002] Currently, the world produces tens of millions of tons of waste rubber (such as tire rubber) every year. If these waste rubbers are not effectively treated in time, they will have a huge impact on the environmental ecology. According to relevant reports, my country produces a huge amount of waste rubber tires every year. At present, most rubber will be recycled. The patent document CN115490939 mentions a tire recycling technology that uses a lignin-based strengthener, but its anti-reduction performance is insufficient.

[0003] At present, although rubber recycling technology has made certain progress, it still has many limitations. The use of lignin-based regeneration methods only increases partial mechanical strength. Patent document CN115490939 improves the anti-reduction type, but uses traditional reinforcing agents.

[0004] The recycled rubber produced by the existing recycled rubber processing technology using waste tires has defects: the recycled rubber produced has low wear resistance, low reduction resistance, or does not use biomass-based green materials. Therefore, it is very important to propose a biomass tire recycled rubber with high reduction resistance and high wear resistance made from waste tires and a preparation method thereof. Summary of the Invention

[0005] In order to overcome the defects of the reclaimed rubber produced in the prior art that has resistance to reduction but insufficient wear resistance, or high wear resistance but insufficient resistance to reduction, one object of the present invention is to provide a highly reduction-resistant and wear-resistant biomass tire reclaimed rubber to solve the problems raised in the above background technology.

[0006] Another object of the present invention is to provide a method for preparing tire reclaimed rubber with modified wear resistance and reduction resistance based on biomass tire reclaimed rubber.

[0007] To achieve the above objectives, the present invention provides a highly reduction-resistant and wear-resistant biomass tire reclaimed rubber, which specifically comprises the following components and parts by weight:

[0008] 80-100 phr of recycled tire rubber powder, 5-10 phr of lignin sulfonate, 20-30 phr of white carbon black, 2-3 phr of silane coupling agent, 1-5 phr of anti-reducing agent, 5-15 phr of processing aid, and 5-10 phr of wear-resistant reinforcing agent. The biomass-based lignin reinforcing agent, lignin sulfonate, white carbon black, and silane coupling agent, modify the rubber compound's wear resistance and synergistically enhance its anti-reducing properties. The anti-reducing agent modifies the compound's anti-reducing properties, while the wear-resistant reinforcing agent synergistically enhances its wear resistance.

[0009] Preferably, sodium lignin sulfonate is used as the lignin sulfonate, and the effective content of sodium lignin sulfonate is 60%-70%. This concentration range can improve the dispersibility and thermal stability of the reclaimed rubber. The effective content of white carbon black is 95%-99%, and white carbon black in this content range has high strength and high dispersibility.

[0010] Preferably, the silane coupling agent is any one of γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, or Si-69; and the ratio of white carbon black to the silane coupling agent is 9 to 11:1. This combination can improve the physical properties of the product, reduce dependence on carbon black, and form an ionic network polymerization with lignin sulfate and regenerated rubber.

[0011] Preferably, the anti-reducing agent is one or both of maleimides (such as HVA-2) or Perkalink 900. The anti-reducing agent has high-temperature stability, increases vulcanization efficiency, and has dynamic properties. It works synergistically with the lignin group to capture free radicals generated by the rubber under heat, light or mechanical stress, generates stable products, and blocks the free radical chain reaction. In addition, the anti-reducing agent can also form a protective layer on the rubber surface to reduce the attack of oxidants on the unsaturated rubber.

[0012] Preferably, the wear-resistant reinforcing agent is a carbon nanotube-carbon black reinforcing agent, the aspect ratio of the carbon nanotubes in the selected wear-resistant reinforcing agent is greater than 200, and the selected carbon black is one or more of N220, N234, N110, and N134; the reinforcing agent is physically filled to form a network reinforcement structure, and the carbon nanotubes and carbon black form a multi-scale network structure in the rubber matrix. The carbon nanotubes and rubber molecules are entangled and overlapped to form a three-dimensional network, and the carbon black is filled. This network structure interacts with the polymer chain through physical adsorption, restricts the movement of the chain segments, and improves the strength; at the material interface, the carbon nanotubes and carbon black form covalent bonds or hydrogen bonds with the rubber matrix, significantly improving the interfacial bonding strength.

[0013] The technical solution of the present invention also requires the addition of processing aids, and the selected processing aids are 8-17 phr of softener and 0.5-5 phr of activator.

[0014] Preferably, the softener is selected from epoxidized soybean oil, dibutyl sebacate, acetylated tributyl citrate, glycerol, and polyethylene glycol. This softener can optimize the uniformity of the vulcanization network, indirectly improving wear resistance and reduction resistance. Epoxidized soybean oil is a green plasticizer containing epoxy groups, which can improve the thermal stability and heat resistance of the material.

[0015] Preferably, the activator selected is a combination of desulfurizer 480 and accelerator M, and the combination ratio is 1 to 4:1; the composition has a synergistic effect in the vulcanized rubber desulfurization system, and is mainly used to adjust the sulfur bond breaking rate, improve the desulfurization efficiency, and take into account environmental protection needs; dicaprolactam disulfide decomposes into active sulfur and caprolactam at 120-160°C, reducing the activation energy of sulfur bond breaking in the vulcanized rubber, and 2-mercaptobenzothiazole activates the chain scission reaction of the carbon-sulfur bond through the mercapto group, thereby accelerating regeneration desulfurization.

[0016] On the other hand, the present invention provides a method for preparing the above-mentioned high-reduction-resistance and high-wear-resistant biomass tire reclaimed rubber, wherein the preparation method comprises:

[0017] S1. Pretreatment: The waste tires are crushed, screened, washed, and dried to obtain recycled rubber powder with a particle size of 0.12-0.18 mm. This step removes metal impurities in the waste rubber. The recycled rubber powder within this particle size range has a large specific surface area, making it easier to disperse evenly during the preparation process and reducing agglomeration. The rubber powder within this particle size range can enhance interfacial bonding and improve the wear resistance of the material. The rubber powder within this particle size range is easier to fill, thereby ensuring the quality of the recycled rubber.

[0018] S2, mixing, feeding the pretreated reclaimed rubber powder, sodium lignin sulfonate, wear-resistant reinforcing agent, softener, anti-reducing agent and other matching components into a high-speed mixing tank for high-speed blending, and then feeding it into a low-speed mixing tank for continuous stirring in preparation for continuous vulcanization;

[0019] S3, desulfurization regeneration, the solid material mixed evenly in the low-speed stirring tank is sent to the extrusion desulfurizer for desulfurization regeneration;

[0020] S4, mixing process, the desulfurized rubber material is sent to the refiner for kneading and refining;

[0021] S5, extrusion process, the rubber material after kneading and refining is fed into an extruder to extrude into sheets, thus obtaining high-anti-reduction and high-wear-resistant biomass tire reclaimed rubber;

[0022] Preferably, the temperature in the high-speed stirring tank in step S2 is 80-120°C, the blending time is 5-15min, the high-speed blending speed is 100-900rpm, and the low-speed stirring speed is 5-80rpm; the desulfurization temperature of the desulfurizer in step S3 is 170-270°C. The use of high-speed blending can form an ion network polymer in the mixture, and the technology type used is INP technology. INP technology is a technology that forms an interpenetrating network by cross-linking two or more polymers, which can significantly improve the aging resistance and mechanical properties of the material.

[0023] Compared with the prior art, the present invention has the following beneficial effects: the recycled rubber material prepared by the present invention uses the biomass material sodium lignin sulfonate, which is renewable, low-cost, and multi-functional. When blended in the present process, it can disperse the rubber powder, improve the desulfurization effect, and comply with the national carbon reduction policy; white carbon black and silane coupling agent are used to replace N330 carbon black, and white carbon black and silane coupling agent can synergistically enhance the wear resistance and anti-reduction of rubber. At the same time, this method is also an application of green chemistry; carbon nanotube-carbon black reinforcing agent is added to reinforce the wear-resistant material, further improving the wear resistance of the product.

[0024] Ionic network polymer technology is used to mix rubber powder, sodium lignin sulfonate, white carbon black, silane coupling agent and anti-reducing agent at high speed to form an ionic network polymer: the sulfonate group of sodium lignin sulfonate combines with the cation (ammonium salt) in the rubber powder or silane coupling agent to form an ionic bond, forming a dynamic reversible network; maleimides react with the thiol or amino group in the rubber powder to combine to form stable covalent cross-linking points; the phenolic hydroxyl group of lignin and the surface hydroxyl group of silica form hydrogen bonds with the polar groups (hydroxyl, carboxyl, etc.) of the rubber powder. The three bonding mechanisms improve the mechanical strength and stability of the resulting reclaimed rubber, ensuring the high wear resistance and high reduction resistance of the resulting reclaimed rubber. DETAILED DESCRIPTION

[0025] In the present invention, unless otherwise specified, all equipment and raw materials can be purchased from the market or are commonly used in the industry. The methods in the following embodiments, unless otherwise specified, are regarded as conventional methods in the art.

[0026] In the present invention, unless otherwise specified, the numerical range "ab" is an abbreviation for any combination of real numbers between a and b, where a and b are real numbers. For example, "30-60" indicates that all real numbers between "30-60" are listed in the present invention, and "30-60" is merely an abbreviation for these numerical combinations.

[0027] In the present invention, unless otherwise specified, all embodiments and comparative examples mentioned in the present invention can be combined with each other to form a new technical solution.

[0028] In order to make the purpose, technical solutions and advantages of the present invention more clear, the present invention is further described in detail below in conjunction with embodiments. The embodiments described below are some embodiments of the present invention, rather than all embodiments, and are only used to illustrate the present invention and should not be regarded as limiting the scope of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative work are within the scope of protection of the present invention.

[0029] The silane coupling agent used in the following examples and comparative examples is γ-aminopropyltriethoxysilane.

[0030] Example 1: High processing performance reclaimed rubber: Prepare the raw materials: recycled rubber powder 85 phr, sodium lignin sulfonate 5 phr, white carbon black 22 phr, silane coupling agent 2.0 phr, HVA-23 phr, carbon nanotube-carbon black reinforcing agent 8 phr, epoxy soybean oil 9 phr, and a combination of desulfurizer 480 and accelerator M 1 phr (the ratio of desulfurizer 480 to accelerator M is 1:1).

[0031] The preparation method of reclaimed rubber is as follows: This embodiment also provides a preparation method for preparing the above-mentioned high-reduction-resistance and high-wear-resistant biomass tire reclaimed rubber, and the specific preparation method includes the following steps:

[0032] S1, pretreatment, placing the waste tires into a tire crusher, crushing, then screening, washing and drying to obtain tire recycled rubber powder with a particle size of 0.18mm; S2, mixing process, adding rubber powder, sodium lignin sulfonate, white carbon black, silane coupling agent, carbon nanotube-carbon black reinforcing agent, epoxy soybean oil, HVA-2 reagent and activator into a high-speed stirring tank, maintaining the speed at 700 rpm, and uniformly mixing at a temperature of 100° C. for 5 minutes to obtain a solid material; S3, desulfurization process, the mixed solid material is sent to the extrusion desulfurizer for desulfurization regeneration; the desulfurization temperature is set at 200℃; S4, mixing process, sending the above rubber material into the extruder for refining; S5, extrusion process, feeding the kneaded and refined rubber material into an extruder for extrusion into sheets, thereby obtaining high-reduction-resistance and high-wear-resistant biomass tire reclaimed rubber.

[0033] Example 2: Formula of high mechanical properties reclaimed rubber: Prepare the raw materials: recycled rubber powder 95phr, sodium lignin sulfonate 8phr, white carbon black 24phr, silane coupling agent 2.4phr, HVA-24phr, Perkalink 90000.5phr, carbon nanotube-carbon black reinforcing agent 8phr, epoxy soybean oil 8.5phr, desulfurizer 480 and accelerator M combination agent 1phr (the ratio of desulfurizer 480 and accelerator M is 3:1).

[0034] The technical features of this formula: high filler content (white carbon black + carbon nanotubes-carbon black reinforcement) synergistic with HVA-2, suitable for high wear-resistant products.

[0035] The preparation method of this embodiment is the same as that of Example 1.

[0036] Example 3: Environmentally friendly and low-cost formula: Prepare raw materials: recycled rubber powder 90 phr, sodium lignin sulfonate 7 phr, white carbon black 23 phr, silane coupling agent 2.2 phr, HVA-22.5 phr, Perkalink 9001 phr, carbon nanotube-carbon black reinforcement 6 phr, epoxy soybean oil 9.5 phr, and a combination of desulfurizer 480 and accelerator M 0.5 phr (the ratio of desulfurizer 480 to accelerator M is 1:1).

[0037] The technical features of this formula are: high proportion of recycled rubber powder to reduce raw material costs; and the use of epoxidized soybean oil to replace petroleum-based plasticizers.

[0038] The preparation method of this embodiment is the same as that of Example 1.

[0039] The above three embodiments each have their own focus. In Example 1, Perkalink 900 is not added, and the anti-reducing agent selected is a single HVA-2 anti-reducing agent, and the waste recycled rubber powder, sodium lignin sulfonate, white carbon black, silane coupling agent, and HVA-2 are all at the lowest content; in Example 2, the recycled rubber powder, sodium lignin sulfonate, white carbon black, silane coupling agent, and anti-reducing agent are all at the highest content; and in Example 3, the content of each component is moderate.

[0040] Comparative Example 1: Sodium lignin sulfonate-free raw materials were prepared: recycled rubber powder 95 phr, white carbon black 24 phr, silane coupling agent 2.4 phr, HVA-24 phr, Perkalink 9000 0.5 phr, carbon nanotube-carbon black reinforcing agent 8 phr, epoxidized soybean oil 8.5 phr, and a combination of desulfurizer 480 and accelerator M 1 phr (the ratio of desulfurizer 480 to accelerator M is 3:1).

[0041] The lack of lignin in this comparative formula may weaken the interfacial bonding between the filler and rubber, exacerbating wear; the presence of anti-reduction groups in the lignin base will also weaken the anti-reduction ability.

[0042] The preparation method of this comparative example is the same as that of Example 1.

[0043] Comparative Example 2: Prepare raw materials without silane coupling agent: recycled rubber powder 95 phr, sodium lignin sulfonate 8 phr, white carbon black 24 phr, HVA-24 phr, Perkalink 9000.5 phr, carbon nanotube-carbon black reinforcement 8 phr, epoxidized soybean oil 8.5 phr, a combination of desulfurizer 480 and accelerator M 1 phr (the ratio of desulfurizer 480 to accelerator M is 3:1).

[0044] The comparative formula lacks a silane coupling agent, so the dispersion of the filler will deteriorate, and local hard lumps may form, which will aggravate friction loss; the surface of silica is rich in silanol groups, which are highly polar and have poor compatibility with the hydrocarbon structure of rubber, resulting in a decrease in mechanical properties such as tensile strength and tear strength; the interface between silica and rubber will generate a large amount of heat due to sliding friction, resulting in increased dynamic heat generation.

[0045] The preparation method of this comparative example is the same as that of Example 1.

[0046] Comparative Example 3: High graphite filling (replacing carbon black) Prepare the raw materials: recycled rubber powder 95 phr, sodium lignin sulfonate 8 phr, white carbon black 24 phr, silane coupling agent 2.4 phr, HVA-24 phr, Perkalink 9000 0.5 phr, graphite filler 10 phr, epoxy soybean oil 8.5 phr, a combination of desulfurizer 480 and accelerator M 1 phr (the ratio of desulfurizer 480 and accelerator M is 3:1).

[0047] In this comparative technical formula, carbon black is replaced with graphite. The lubricity of graphite is too strong, which reduces surface friction but lacks reinforcement. At the same time, the thermal conductivity of graphite is directional, which is not conducive to the diffusion of heat in the vertical direction.

[0048] The preparation method of this comparative example is the same as that of Example 1.

[0049] Comparative Example 4: Non-epoxidized soybean oil (all paraffin oil plasticized) Prepare the raw materials: recycled rubber powder 95phr, sodium lignin sulfonate 8phr, white carbon black 24phr, silane coupling agent 2.4phr, HVA-24phr, Perkalink 90000.5phr, carbon nanotube-carbon black reinforcing agent 8phr, epoxy soybean oil 8.5phr, desulfurizer 480 and accelerator M combination agent 1phr (the ratio of desulfurizer 480 and accelerator M is 3:1).

[0050] In the comparative technical formula, paraffin oil replaces the epoxy-free soybean oil. Paraffin oil reduces the flexibility of the rubber, hardens the material, and increases frictional heat generation. Paraffin oil is highly volatile, and the resulting rubber may have poor stability.

[0051] The preparation method of this comparative example is the same as that of Example 1.

[0052] Comparative Example 5: High Lignin Strengthener (Replacing Activator) Prepare raw materials: recycled rubber powder 95phr, sodium lignin sulfonate 20phr, white carbon black 24phr, silane coupling agent 2.4phr, HVA-24phr, Perkalink 90000.5phr, carbon nanotube-carbon black reinforcement 8phr, epoxy soybean oil 8.5phr.

[0053] The comparative technical solution: lignin replaces antioxidants, which accelerates oxidative degradation and reduces anti-aging ability; excessive lignin will lead to poor dispersion of rubber and may increase friction resistance.

[0054] Table 1 Raw materials and contents used in Examples 1-3 Raw materials (phr) Example 1 Example 2 Example 3 Recycled rubber powder 85 95 90 Sodium lignin sulfonate 5 8 7 Silica 22 24 23 Silane coupling agent 2 2.4 2.2 HVA-2 3 4 3.5 Perkalink900 0 0.5 1 Carbon nanotube-carbon black reinforcement 8 8 6 Epoxidized soybean oil 9 8.5 9.5 Desulfurizer 480 0.5 0.75 0.25 Accelerator M 0.5 0.25 0.25

[0055] Table 2 Raw materials and contents used in Comparative Examples 1-5

[0056] The test was verified by performing Akron wear test (wear resistance) and hot air aging test (reversion rate).

[0057] Table 3 Test results of wear resistance and reversion rate of Examples 1-3.

[0058] As can be seen from Table 3, Example 2 has the best performance, with the best wear resistance and the highest reversion rate. This is because Example 2 contains white carbon black, graphite, carbon black, and a silane coupling agent, which work synergistically to improve the product's wear resistance. HVA-2 and the antioxidant work together to delay aging, preventing most vulcanization reversion and improving reduction resistance.

[0059] Table 4 Test results of comparative examples 1-5

[0060] Comparing Table 4 with Table 3, and Comparative Example 1 with Example 2, we can see that the absence of sodium lignin sulfonate, the lignin strengthener, by enhancing interfacial bonding, reduces filler shedding, and an appropriate amount of lignin can improve the dispersibility of the system, thereby significantly improving the wear resistance of the product. Lignin contains phenolic hydroxyl groups, which can capture free radicals, which can prevent rubber aging to a certain extent and improve the anti-reduction performance to a certain extent. Therefore, the wear resistance of Comparative Example 1 decreased by 110%, and the reversion rate decreased by 15%. This proves that sodium lignin sulfonate has a significant effect in this technology.

[0061] Comparing Comparative Example 2 with Example 1, the absence of a silane coupling agent reduces the surface polarity of the filler, preventing the formation of localized hard lumps in the rubber compound. The silane coupling agent also improves dispersibility, synergistically enhancing dispersibility with sodium lignin sulfonate and reducing frictional resistance. Compared to Example 1, the wear resistance of Comparative Example 2 decreased by 16%, while the reduction resistance remained almost unchanged.

[0062] Comparative Example 3, compared with Example 2, uses only graphite filler and no carbon nanotube-carbon black reinforcement. N330 carbon black is an important reinforcing wear-resistant material. Graphite has excessive lubricity, which reduces the surface friction coefficient of the material. However, without the reinforcement of carbon black, the wear resistance will gradually decrease after use. Carbon black can form a reinforcing network, while graphite cannot form an effective reinforcing network. With graphite alone, the structure will be destroyed after long-term friction. At the same time, graphite's thermal conductivity is directional, which is not conducive to the diffusion of heat in the vertical direction, resulting in a decrease in the reversion rate. The wear resistance of Comparative Example 3 does not decrease much, but after long-term use, the wear resistance will drop sharply; the initial wear resistance performance remains almost unchanged, and the reversion rate decreases by 18%.

[0063] Comparative Example 4, in contrast to Example 2, uses paraffin oil instead of epoxidized soybean oil. Paraffin oil has poor compatibility with rubber and easily disperses at the interface between the rubber molecules and the reinforcing material, further weakening the reinforcing effect between the reinforcing material and the rubber, and also reducing the product's wear resistance and reduction resistance. Epoxidized soybean oil is an environmentally sustainable resource, highly safe, and non-toxic. It has excellent stability, and its epoxy groups have antioxidant properties, which can delay product aging and extend its service life. Epoxidized soybean oil also has excellent processing properties, low volatility, and high thermal stability. Epoxidized soybean oil can also reduce material hardness while maintaining or improving tensile strength and impact resistance. The experimental results show that the wear resistance of Comparative Example 4 decreased by 18%, and the reversion rate decreased by 12%.

[0064] Comparing Comparative Example 5 with Example 2, sodium lignin sulfonate was used in place of the activator. Lignin was unable to replace the antioxidant's role in the anti-aging system, significantly reducing the reversion rate. Excessive lignin actually reduced the rubber's dispersibility, increased friction, and decreased wear resistance. In Comparative Example 5, wear resistance decreased by 22%, and reversion rate decreased by 25%.

[0065] By comparison of the above embodiments and comparative examples, the advantages of the present invention are that an appropriate amount of lignin increases the dispersibility of rubber powder, and graphite, carbon black, white carbon black and silane coupling agent form a cross-linked network, which greatly enhances the wear resistance of the reclaimed rubber, reduces the use of carbon black, reduces carbon consumption, and has an environmentally friendly effect; lignin, HVA-2 and Perkalink 900 increase the cross-linking density, delay thermal oxidative aging, and the system enhances the thermal stability of the material, which also indirectly improves the wear resistance. Lignin and carbon nanotube-carbon black-white carbon black-silane coupling agent cross-linking system form a synergistic system, further improving wear resistance; at the same time, HVA-2 and Perkalink 900 inhibit vulcanization reversion, and the lignin structure contains phenolic hydroxyl groups that capture free radicals, blocking the chain process of rubber oxidation reaction, improving the anti-aging performance of the reclaimed rubber, and extending its service life.

[0066] Comparative Example 6 The raw material formula of this comparative example is consistent with that of Example 2;

[0067] Preparation method:

[0068] S1, pretreatment, placing the waste tires into a tire crusher, crushing them, and then screening, washing, and drying them to obtain tire recycled rubber powder with a particle size of 0.18mm; S2, mixing process, adding rubber powder, sodium lignin sulfonate, white carbon black, silane coupling agent, carbon nanotube-carbon black reinforcing agent, epoxy soybean oil and activator into a low-speed mixer, uniformly mixing at a blending speed of 80 rpm and a temperature of 100° C. for 5 minutes; then continuing continuous stirring to prepare for vulcanization at a speed of 80 rpm; S3, desulfurization process, the solid materials mixed evenly in the low-speed stirring tank are sent to the extrusion desulfurizer for desulfurization and regeneration, and the desulfurization temperature is controlled at 200℃; S4, mixing process, the desulfurized rubber material is sent to the refiner for kneading and refining; S5. The kneaded and refined rubber material is fed into an extruder to extrude into sheets, thereby obtaining biomass tire reclaimed rubber.

[0069] Comparative Example 7 The raw material formula of this comparative example is consistent with that of Example 2

[0070] Preparation method:

[0071] S1, pretreatment, placing the waste tires into a tire crusher, crushing them, and then screening, washing, and drying them to obtain tire recycled rubber powder with a particle size of 0.18mm; S2, mixing process, adding rubber powder, sodium lignin sulfonate, white carbon black, silane coupling agent, carbon nanotube-carbon black reinforcing agent, epoxy soybean oil and activator into a low-speed mixer, uniformly mixing at a blending speed of 800 rpm and a temperature of 100° C. for 5 minutes; then continuing continuous stirring to prepare for vulcanization at a speed of 80 rpm; S3, desulfurization process, the solid materials mixed evenly in the low-speed stirring tank are sent to the extrusion desulfurizer for desulfurization and regeneration, and the desulfurization temperature is controlled at 200℃; S4, mixing process, the desulfurized rubber material is sent to the refiner for kneading and refining; S5. The kneaded and refined rubber material is fed into an extruder to extrude into sheets, thereby obtaining biomass tire reclaimed rubber.

[0072] Table 5 Test results of Example 2 and Comparative Examples 6-7

[0073] By comparing Example 2, Comparative Example 6 and Comparative Example 7, the following conclusions can be drawn: Example 2 adopts high-speed blending and INP technology, which has the following advantages: appropriate high-speed blending can ensure uniform dispersion of the filler, and high-speed shear force can quickly and evenly disperse the filler (carbon nanotube-carbon black reinforcement, white carbon black, silane coupling agent), reduce the agglomeration of filler and rubber powder, avoid early wear and loss, and the silane coupling agent and filler are efficiently combined to form a stable interface structure, thereby improving the reinforcement effect; high-speed blending can reduce energy consumption and time costs. Compared with traditional mixing, high-speed mixing and mixing shortens the time, reduces process heat accumulation, and avoids material thermal oxidation degradation loss. A moderate speed is conducive to improving product performance, but too high a speed will reduce the product's anti-reduction performance.

[0074] The INP technology used in the present invention has the following advantages over traditional technology. It can efficiently construct a cross-linked network, a network structure of white carbon black, silane coupling agent, and carbon nanotube-carbon black, enhance the wear resistance of the material, and improve the stability of the material. High-speed blending ensures that the filler is evenly dispersed and reduces friction stress concentration; INP technology enhances the surface hardness and self-lubrication of the material through cross-linking; the network ion polymer formed by INP technology is a type of polymer material with a cross-linked structure. It contains ionizable ion groups on the main chain and side chain. Sodium lignin sulfonate forms ion clusters with fillers through sulfate groups, which improves the anti-reduction type. However, if the high-speed blending speed is too fast, the system temperature rise will increase, resulting in partial raw material loss and affecting the anti-reduction performance. Excessive speed makes the system more dispersible and the wear resistance increases. Compared with Example 2, the wear resistance of Comparative Example 6 is reduced by 25%, and the reversion rate is reduced by 8%. Compared with Example 2, the wear resistance of Comparative Example 7 is improved by 16%, and the anti-reduction type is reduced by 3%.

[0075] As can be seen from the above-described embodiments and comparative examples, compared with the prior art, the preparation method of the present invention utilizes high-speed blending and INP technology so that the formula materials are evenly mixed, and a cross-linked structure with a higher density is formed in the obtained product, including CS and SS cross-linking bonds; an ion network polymer can also be formed, and the structure is a dense structure that can isolate part of the reducing agent from contact, and ionic crosslinking is relatively stable to chemical reducing agents. The present invention blends the raw materials at a high speed to form a variety of synergistic mechanisms, and the lignin structure and the anti-reducing agent HVA-2 and Perkalink900 work together to resist reduction ability; the copolymerization structure formed by white carbon black, silane coupling agent, and carbon nanotube-carbon black gives this product a high wear-resistant performance, and can also work together to play a certain anti-reduction ability. By experimental results, it is shown that the high anti-reduction high wear-resistant biomass tire reclaimed rubber provided by the present invention has anti-wear and anti-reversion capabilities, and also has the aging resistance of traditional rubber.

[0076] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the various embodiments of the present invention.

Claims

1. A high-reduction-resistance and high-wear-resistant biomass tire reclaimed rubber, characterized in that: The tire reclaimed rubber comprises, by weight, 80-100 phr of waste tire reclaimed rubber powder, 5-10 phr of lignin sulfonate, 20-30 phr of white carbon black, 2-3 phr of silane coupling agent, 1-5 phr of anti-reducing agent, 5-15 phr of processing aid, and 5-10 phr of wear-resistant reinforcing agent.

2. The high-reduction-resistance and high-wear-resistant biomass tire reclaimed rubber according to claim 1, characterized in that: The lignin sulfonate is sodium lignin sulfonate, and the effective content of sodium lignin sulfonate is 60%-70%; the effective content of white carbon black is 95%-99%.

3. The high-reduction-resistance and high-wear-resistant biomass tire reclaimed rubber according to claim 1 or 2, characterized in that: The silane coupling agent is any one of γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane or Si-69; the ratio of white carbon black to the silane coupling agent is 9 to 11:

1.

4. The high-reduction-resistance and high-wear-resistant biomass tire reclaimed rubber according to claim 1, characterized in that: The anti-reducing agent is selected from one or both of maleimides and Perkalink 900.

5. The high-reduction-resistance and high-wear-resistant biomass tire reclaimed rubber according to claim 1, characterized in that: The wear-resistant reinforcing agent is a carbon nanotube-carbon black reinforcing agent. The aspect ratio of the carbon nanotubes in the wear-resistant reinforcing agent is greater than 200, and the carbon black is one or more of N220, N234, N110, and N134.

6. The high-reduction-resistance and high-wear-resistant biomass tire reclaimed rubber according to claim 1, characterized in that: The processing aids include 8-17 phr of softener and 0.5-5 phr of activator.

7. The high-reduction-resistance and high-wear-resistant biomass tire reclaimed rubber according to claim 6, characterized in that: The softener is selected from one or more of epoxy soybean oil, dibutyl sebacate, acetylated tributyl citrate, glycerol, and polyethylene glycol.

8. The high-reduction-resistance and high-wear-resistant biomass tire reclaimed rubber according to claim 6, characterized in that: The activator is a combination of desulfurizer 480 and accelerator M, with a combination ratio of 1 to 4:

1.

9. A method for preparing highly reduction-resistant and wear-resistant biomass tire reclaimed rubber, characterized in that: The tire reclaimed rubber according to any one of claims 1 to 8, wherein the method comprises the following steps: S1, placing waste tires into a tire crusher for crushing, screening, washing and drying; S2, feeding the pretreated reclaimed rubber powder, sodium lignin sulfonate, wear-resistant reinforcing agent, softener, anti-reducing agent and other matching components into a high-speed stirring tank for stirring, and then feeding them into a low-speed stirring tube for continuous stirring to obtain a solid material; S3, sending the above solid material into an extrusion desulfurizer for desulfurization and regeneration to obtain a rubber compound; S4, feeding the rubber material into a refiner for kneading and refining; S5, sending the kneaded and refined rubber material into an extruder to extrude into sheets.

10. The method for preparing high-reduction-resistance and high-wear-resistant biomass tire reclaimed rubber according to claim 9, characterized in that: In step S2, the temperature in the high-speed stirring tank is 80-120°C, the blending time is 5-15 minutes, the high-speed blending speed is 100-900 rpm, and the low-speed stirring speed is 5-80 rpm; in step S3, the desulfurization temperature of the desulfurizer is 170-270°C.

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