Semi-steel radial tire with low rolling resistance and wet skid resistance and preparation method of semi-steel radial tire

Abstract

The invention discloses a preparation method of a low-rolling-resistance and wet-skid-resistant semi-steel radial tire, belongs to the technical field of tire manufacturing, and is used for solving the problem that tread rubber used by a semi-steel radial tire in the prior art needs to balance rolling resistance and wet-skid resistance at the same time. Wherein the tread rubber comprises modified solution polymerized styrene-butadiene rubber, natural rubber, butadiene rubber, an accelerant, an anti-aging agent, solid silane, white carbon black, zinc oxide, an anti-aging agent composition, wax, stearic acid, carbon black, an accelerant CBS and oil-extended sulfur powder, and the preparation method of the modified solution polymerized styrene-butadiene rubber comprises the following steps: mixing the solution polymerized styrene-butadiene rubber, cyclohexane and 3-chloroperoxybenzoic acid, reacting, adding a catalyst, and stirring to obtain the modified solution polymerized styrene-butadiene rubber. The epoxidized solution polymerized styrene-butadiene rubber is obtained; in a nitrogen atmosphere, uniformly mixing epoxidized solution polymerized styrene-butadiene rubber, maleic anhydride grafted polypropylene, xylene and an initiator, and reacting to obtain modified solution polymerized styrene-butadiene rubber; the low-rolling-resistance and wet-skid-resistant semi-steel radial tire obtained by the invention has good comprehensive performance and conforms to the energy-saving concept.

Description

Technical Field

[0001] The invention relates to the technical field of tire manufacturing, and in particular to a low rolling resistance, anti-slip semi-steel radial tire and a preparation method thereof. Background Art

[0002] On the roads of modern cities, vehicles frequently change their driving status, starting, stopping and turning. Under such complex road conditions, semi-steel radial tires stand out with their unique advantages and become the ideal choice for many vehicles. They have excellent comfort and can effectively buffer the bumps during driving; excellent handling, allowing drivers to easily cope with various road conditions; and excellent anti-slip performance, even in the face of waterlogged roads can be calm. For example, at the traffic lights frequently encountered in the city, frequent starts and stops are a test of tire performance, and semi-steel radial tires can adapt well. On the basis of ensuring the safety of tire driving, the service life of tires and their impact on automobile fuel consumption have received widespread attention. Today, it has been made clear that reducing rolling resistance can significantly reduce fuel consumption, thereby improving the fuel economy of vehicles and allowing vehicles to travel longer distances. Improving anti-slip performance can greatly enhance the safety of tires on slippery roads and reduce the occurrence of traffic accidents. However, these two performance indicators are often contradictory and it is difficult to achieve the best at the same time. People need to seek a more ideal balance between the two. With the popularization of the "green tire" concept in Europe and the successive proposals of my country's energy conservation and emission reduction strategies, people's requirements for automobile tire performance are becoming increasingly stringent.

[0003] Semi-steel radial tires include: carcass cord layer, belt layer, bead wire, tread rubber and sidewall rubber. Among them, the tread rubber is the outermost layer of the tire and is in direct contact with the ground. It plays a key role in the driving process of the tire, such as providing grip to ensure the vehicle's handling and braking performance; it has good anti-skid properties to ensure the safety of the vehicle on slippery roads. Tread rubber is generally made of a mixture of multiple rubbers, the most common of which are natural rubber, styrene-butadiene rubber and cis-butadiene rubber. Natural rubber has excellent elasticity, tensile strength and tear strength; styrene-butadiene rubber has good wear resistance and aging resistance; cis-butadiene rubber can improve the cold resistance and wear resistance of the tire. People also add reinforcing agents such as carbon black and white carbon black to enhance its physical properties. When white carbon black reinforces rubber, it is difficult to disperse evenly in the rubber compound because white carbon black with polar hydroxyl groups on the surface is easy to self-agglomerate.

[0004] Chinese patent CN109337141B discloses a low-resistance tire tread rubber and its preparation method and application, wherein the low-resistance tire tread rubber is prepared by mixing terminal-modified solution-polymerized styrene-butadiene rubber, natural rubber, high-cis polybutadiene composite rubber, zinc oxide, stearic acid, antioxidant, protective wax, softener, white carbon black, dispersant, plasticizer, carbon black, silane coupling agent, sulfur and accelerator in a mass ratio of (20-55):(3-35):(30-80):(2-5):(1-4):(1-5):(2-4):(2-10):(35-65):(1-5):(0.3-1.5:(10-35):(3.5-6.5):(2-7):(3-15), and extruding and tableting through a twin-screw extruder. The rolling resistance of the tread rubber prepared by the invention needs to be further reduced, and the dispersibility of white carbon black needs to be further improved. Chinese patent CN118812930B discloses a wear-resistant tire tread rubber and a preparation method thereof, wherein the wear-resistant tire tread rubber comprises natural rubber, styrene-butadiene rubber, isoprene rubber, modified white carbon black, composite filler, N330 carbon black, stearic acid, calcium oxide, zinc oxide, antioxidant 4020, environmentally friendly aromatic oil TDAE, polyimide, sulfur, accelerator TMTD, accelerator BS, and anti-vulcanization reversion agent HTS; wherein the mass ratio of the above components is (40- 60):(25-35):(15-25):(25-30):(20-25):(15-20):(2-3):(1-2):(1-2):(2.5-3.5):(8-12):(0.1-0.5):(1.2-2):(1-2):(0.5-1):(1-3). In the dynamic performance test of the wear-resistant tire tread rubber prepared by this invention, the highest 0℃·tanδ value is 0.278, and the anti-skid performance represented by it needs to be further improved. Summary of the invention

[0005] In order to solve the above technical problems, the present invention provides a low rolling resistance, anti-skid semi-steel radial tire and a preparation method thereof, which solves the problem in the prior art that the tread rubber used in the semi-steel radial tire needs to balance rolling resistance and anti-skid performance.

[0006] In order to achieve the above object, the present invention provides a method for preparing a low rolling resistance and anti-slip semi-steel radial tire, comprising the following steps:

[0007] S1: Put modified solution polymerized styrene-butadiene rubber, natural rubber, butadiene rubber, accelerator, antioxidant and solid silane into an internal mixer, press the top bolt and mix; raise the bolt, add white carbon black, press the top bolt and mix and adjust; discharge the rubber and cool to obtain MB1;

[0008] S2: MB1, zinc oxide, antioxidant composition, wax, stearic acid, and solid silane are put into an internal mixer, and the top bolt is pressed, and mixing is performed; the bolt is raised, and white carbon black and carbon black are added, and mixing is performed; the bolt is raised, and oil is added, the temperature is increased, the speed is reduced, and mixing is performed; the glue is discharged, and the mixture is cooled to obtain MB2;

[0009] S3: MB2 is put into an internal mixer, the top bolt is pressed, mixing, debonding, and cooling are performed to obtain MB3;

[0010] S4: MB3, accelerator CBS, and oil-extended sulfur powder are put into an internal mixer, a top bolt is pressed, mixing is performed, and the bolt is lifted to discharge the rubber to obtain the tread rubber;

[0011] S5: The tread rubber is extruded through a screw extruder, parked for 24 hours, assembled with carcass cords, belt layers and other components on a molding machine to form a tire blank, and vulcanized in a vulcanizer to obtain a low rolling resistance, anti-slip semi-steel radial tire.

[0012] Preferably, the preparation method of the modified solution-polymerized styrene-butadiene rubber comprises the following steps:

[0013] The solution polymerized styrene butadiene rubber, cyclohexane and 3-chloroperoxybenzoic acid are mixed, stirred evenly, heated, reacted, the reaction is completed, the pH is adjusted, and dried to obtain the epoxidized solution polymerized styrene butadiene rubber;

[0014] In a nitrogen atmosphere, epoxidized solution-polymerized styrene-butadiene rubber, maleic anhydride grafted polypropylene, xylene and an initiator are uniformly mixed, heated, reacted, and after the reaction is completed, vacuum distilled and dried to obtain a modified solution-polymerized styrene-butadiene rubber.

[0015] Preferably, the mass ratio of solution polymerized styrene-butadiene rubber, cyclohexane and 3-chloroperoxybenzoic acid is 100:(600-1000):(10-20); the reaction temperature is 30-50° C., and the reaction time is 8-12 h.

[0016] Preferably, the mass ratio of epoxidized solution polystyrene butadiene rubber, maleic anhydride grafted polypropylene, xylene and initiator is 100:(30-50):(800-1000):(2-4); the reaction temperature is 100-130° C., and the reaction time is 4-8 h.

[0017] Preferably, in S1, the mass ratio of modified solution-polymerized styrene-butadiene rubber, natural rubber, butadiene rubber, accelerator, antioxidant, solid silane and white carbon black is (70-90):(20-30):(10-20):(0.6-1):(0.8-1.2):(3-5):(16-28).

[0018] Preferably, in S2, the mass ratio of MB1, zinc oxide, antioxidant composition, wax, stearic acid, solid silane, white carbon, carbon black and oil is (140-160):(1-3):(2-4):(1.2-1.6):(1.8-2.6):(6-8):(40-55):(18-26):(14-18).

[0019] Preferably, in S3, the upper push bolt pressure is 5-5.5 MPa, the rotation speed is 40-50 rpm, and the mixing time is 85-100 s.

[0020] Preferably, in S4, the mass ratio of MB3, accelerator CBS and oil-extended sulfur powder is (220-260):(2.2-2.6):(1.1-1.5).

[0021] Preferably, the debinding temperature in S1 is 152°C; the debinding temperature in S2 is 141-148°C; the debinding temperature in S3 is 140°C; and the debinding temperature in S4 is 110°C.

[0022] Preferably, in S5, the tread rubber is extruded by a screw extruder at a temperature of 80-100° C.; the parameters of the vulcanizer are: 150-160° C., 15-20 MPa, and vulcanization for 10-15 min.

[0023] Preferably, in S1, the accelerator is accelerator DPG, and the accelerator DPG is diphenylguanidine.

[0024] Preferably, the butadiene rubber is BR9000.

[0025] Preferably, the solid silane is any one of Si-69 and Si-75.

[0026] Preferably, the substance used to adjust the pH is a 0.01 mol / L sodium hydroxide aqueous solution.

[0027] Preferably, the pH range is 7-9.

[0028] Preferably, the initiator is any one of dicumyl peroxide (DCP) or benzoyl peroxide (BPO).

[0029] Preferably, the white carbon black is MP1165.

[0030] Preferably, the sulfur content in the oil-extended sulfur powder is 80%, and the extended oil is cyclohexane oil.

[0031] Preferably, the concentration of the epoxidized solution-polymerized styrene-butadiene rubber is 8-20 g / 100 mL.

[0032] Preferably, the carbon black type is N234.

[0033] Compared with the prior art, the present invention has the following beneficial effects:

[0034] 1. In the present invention, the double bonds in the solution-polymerized styrene-butadiene rubber are oxidized to epoxy groups, and the epoxy groups can improve the interfacial bonding force with the white carbon black filler. At the same time, with the action of the solid silane coupling agent, the white carbon black is more evenly dispersed in the rubber matrix, which significantly reduces the damage of the filler network caused by dynamic strain (i.e., the Payne effect) and reduces energy dissipation. The introduction of maleic anhydride grafted polypropylene further enhances the chemical bonding of the rubber-filler interface, forms a stable three-dimensional network structure, reduces the dynamic modulus, and reduces the rolling resistance. At the same time, the anhydride groups contained in the maleic anhydride grafted polypropylene can react with the epoxy groups in the epoxidized solution-polymerized styrene-butadiene rubber to obtain a modified solution-polymerized styrene-butadiene rubber containing an ester group. The ester bond enhances the rubber-filler interfacial bonding energy, and the oxygen atoms contained in it can form hydrogen bonds with hydrogen atoms, further limiting the movement and friction between molecular chains; and the long-chain alkyl in the modified solution-polymerized styrene-butadiene rubber limits the large-scale slippage of the chain segment through molecular entanglement, reduces the friction of the rubber chain segment, reduces the hysteresis loss, and is conducive to reducing the rolling resistance.

[0035] 2. In the present invention, a staged mixing process is adopted to avoid filler agglomeration and realize filler hierarchical dispersion. At the same time, the sulfur is released in the rubber matrix by combining with additives such as oil-filled sulfur powder and accelerators. The surface cross-linking density is higher than that of the interior, taking into account both the local rigidity required for anti-slip and the overall flexibility required for low rolling resistance.

[0036] 3. In the present invention, the epoxy groups contained in the epoxidized solution-polymerized styrene-butadiene rubber and the carboxylic acid groups of maleic anhydride grafted polypropylene give the tread rubber polarity, which can form hydrogen bonds with water molecules in the road water film, destroy the continuity of the water film, increase the contact area between the tread and the road surface, and improve the grip on wet and slippery roads. During the vulcanization process, the interface between the filler and the modified rubber shrinks differentially, which is conducive to the formation of a microscopic concave-convex structure on the surface of the tread rubber. The structure enhances the drainage capacity through the mechanical interlocking effect, while increasing the roughness contact points, which is conducive to improving the anti-slip performance. DETAILED DESCRIPTION

[0037] The technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0038] Example 1

[0039] This embodiment provides a method for preparing a low rolling resistance and anti-slip semi-steel radial tire, comprising the following steps:

[0040] S1: Add modified solution polystyrene butadiene rubber, natural rubber, butadiene rubber, accelerator DPG, antioxidant 6PPD and Si-69 into an internal mixer, rotate at 70 r / min, press on the top plug and mix for 45 seconds; raise the plug, add white carbon black, keep the speed at 60 r / min, press on the top plug and mix for 40 seconds; raise the top plug to clean it, reduce the speed to 50 r / min, mix for 30 seconds, the temperature reaches 128°C, reduce the speed to 40 r / min, press on the top plug and mix; raise the temperature to 140°C and keep the temperature for 100 seconds; discharge the glue at 152°C, cool to room temperature, and obtain MB1;

[0041] Among them, the mass ratio of modified solution-polymerized styrene-butadiene rubber, natural rubber, butadiene rubber, accelerator DPG, antioxidant 6PPD, Si-69, and white carbon black is 70:20:10:0.6:0.8:3:16;

[0042] S2: MB1, zinc oxide, antioxidant composition, wax, stearic acid and Si-69 were put into an internal mixer at a speed of 70 r / min, and the top bolt was pressed, and the mixture was mixed for 35 seconds; the bolt was raised, white carbon black and carbon black N234 were added, the speed was 60 r / min, the top bolt was pressed, and the mixture was mixed to 105°C; the bolt was raised, environmentally friendly oil was added, and the mixture was mixed to 128°C at a speed of 50 r / min; the bolt was raised, the speed was reduced to 20 r / min, the top bolt was pressed, and the mixture was mixed at 135°C for 65 seconds; the glue was discharged at a temperature of 141°C, and the mixture was cooled to room temperature to obtain MB2;

[0043] The mass ratio of MB1, zinc oxide, antioxidant composition, wax, stearic acid, Si-69, white carbon black, carbon black N234 and environmentally friendly oil is 140:1:2:1.2:1.8:6:40:18:14;

[0044] Wherein, the mass ratio of antioxidant 4020 to antioxidant PD in the antioxidant composition is 1:1.1;

[0045] S3: MB2 was put into an internal mixer with a top bolt pressure of 5 MPa and a rotation speed of 40 rpm. The mixer was mixed for 100 s, and the mixture was discharged at 140°C. The mixture was cooled to room temperature to obtain MB3.

[0046] S4: MB3, accelerator CBS, and oil-extended sulfur powder were added into an internal mixer at a mass ratio of 220:2.2:1.1, at a temperature of 80°C and a speed of 20 rpm, with a push pin pressed on and mixed for 90 seconds, and the rubber was discharged at a temperature of 110°C to obtain a tread rubber;

[0047] S5: The tread rubber is extruded through a screw extruder at 80°C, and then assembled with the carcass cord, belt layer and other components on a molding machine to form a tire blank. The tire is then vulcanized in a vulcanizer at 150°C and 15MPa for 15 minutes to obtain a low rolling resistance and anti-slip semi-steel radial tire;

[0048] Wherein, the preparation method of modified solution-polymerized styrene-butadiene rubber comprises the following steps:

[0049] The solution polymerized styrene butadiene rubber, cyclohexane and 3-chloroperoxybenzoic acid were mixed in a mass ratio of 100:600:10, stirred evenly, reacted at 30°C for 12 hours, and after the reaction was completed, the pH was adjusted to 7 with a 0.01 mol / L sodium hydroxide aqueous solution, and dried at -0.1 MPa and 50°C for 24 hours to obtain an epoxidized solution polymerized styrene butadiene rubber;

[0050] Under a nitrogen atmosphere, epoxidized solution polymerized styrene butadiene rubber, maleic anhydride grafted polypropylene, xylene and diisopropylbenzene peroxide were mixed in a mass ratio of 100:30:800:2, reacted at 100°C for 8 hours, and after the reaction was completed, the mixture was distilled at 0.08 MPa and 70°C under reduced pressure for 12 hours, and dried at 90°C for 8 hours to obtain modified solution polymerized styrene butadiene rubber.

[0051] Example 2

[0052] This embodiment provides a method for preparing a low rolling resistance and anti-slip semi-steel radial tire, comprising the following steps:

[0053] S1: Add modified solution polystyrene butadiene rubber, natural rubber, butadiene rubber, accelerator DPG, antioxidant 6PPD and Si-69 into an internal mixer, rotate at 72 r / min, press on the top plug and mix for 43 s; raise the plug, add white carbon black, keep the speed at 62 r / min, press on the top plug and mix for 35 s; raise the top plug to clean it, reduce the speed to 52 r / min, mix for 28 s, the temperature reaches 128°C, reduce the speed to 42 r / min, press on the top plug and mix; raise the temperature to 143°C and keep it constant for 90 s; discharge the glue at 152°C, cool to room temperature, and obtain MB1;

[0054] Among them, the mass ratio of modified solution-polymerized styrene-butadiene rubber, natural rubber, butadiene rubber, accelerator DPG, antioxidant 6PPD, Si-69, and white carbon black is 75:22:12:0.7:0.9:3.5:19;

[0055] S2: MB1, zinc oxide, antioxidant composition, wax, stearic acid and Si-69 were put into an internal mixer at a speed of 72 r / min, the top bolt was pressed, and mixing was performed for 33 s; the bolt was raised, white carbon black and carbon black N234 were added, the speed was 62 r / min, the top bolt was pressed, and mixing was performed to 106°C; the bolt was raised, environmentally friendly oil was added, and mixing was performed to 128°C at a speed of 52 r / min; the bolt was raised, the speed was reduced to 24 r / min, the top bolt was pressed, and mixing was performed at 138°C for 63 s; the glue was discharged at a temperature of 142°C, and the mixture was cooled to room temperature to obtain MB2;

[0056] The mass ratio of MB1, zinc oxide, antioxidant composition, wax, stearic acid, Si-69, white carbon black, carbon black N234 and environmentally friendly oil is 145:1.5:2.5:1.3:2:6.5:43:20:15;

[0057] Wherein, the mass ratio of antioxidant 4020 to antioxidant PD in the antioxidant composition is 1:1.2;

[0058] S3: MB2 was put into an internal mixer with a top bolt pressure of 5.1 MPa and a rotation speed of 42 rpm. The mixer was mixed for 97 seconds, and the mixture was discharged at 140°C. The mixture was cooled to room temperature to obtain MB3.

[0059] S4: MB3, accelerator CBS, and oil-extended sulfur powder were added into an internal mixer at a mass ratio of 230:2.3:1.2, at a temperature of 82°C and a speed of 22 rpm, with a push pin pressed on for mixing for 83 seconds, and the rubber was discharged at a temperature of 110°C to obtain a tread rubber;

[0060] S5: The tread rubber is extruded through a screw extruder at 85°C, and then assembled with the carcass cord, belt layer and other components on a molding machine to form a tire blank. The tire is then vulcanized in a vulcanizer at 152°C and 16MPa for 14 minutes to obtain a low rolling resistance, anti-slip semi-steel radial tire;

[0061] Wherein, the preparation method of modified solution-polymerized styrene-butadiene rubber comprises the following steps:

[0062] The solution polymerized styrene butadiene rubber, cyclohexane and 3-chloroperoxybenzoic acid were mixed in a mass ratio of 100:700:12, stirred evenly, reacted at 35°C for 11 hours, and after the reaction was completed, the pH was adjusted to 7 with a 0.01 mol / L sodium hydroxide aqueous solution, and dried at -0.1 MPa and 52°C for 23 hours to obtain an epoxidized solution polymerized styrene butadiene rubber;

[0063] Under a nitrogen atmosphere, epoxidized solution polymerized styrene butadiene rubber, maleic anhydride grafted polypropylene, xylene and diisopropylbenzene peroxide were mixed in a mass ratio of 100:35:850:2.5, reacted at 107°C for 7 hours, and after the reaction was completed, the mixture was distilled at 0.08 MPa and 75°C under reduced pressure for 11.5 hours, and dried at 92°C for 7.5 hours to obtain modified solution polymerized styrene butadiene rubber.

[0064] Example 3

[0065] This embodiment provides a method for preparing a low rolling resistance and anti-slip semi-steel radial tire, comprising the following steps:

[0066] S1: Add modified solution polystyrene butadiene rubber, natural rubber, butadiene rubber, accelerator DPG, antioxidant 6PPD and Si-69 into an internal mixer, rotate at 75 r / min, press on the top plug and mix for 40 s; raise the plug, add white carbon black, keep the speed at 65 r / min, press on the top plug and mix for 30 s; raise the top plug to clean it, reduce the speed to 55 r / min, mix for 25 s, the temperature reaches 128°C, reduce the speed to 45 r / min, press on the top plug and mix; raise the temperature to 146°C and keep it constant for 80 s; discharge the glue at 152°C, cool to room temperature, and obtain MB1;

[0067] Among them, the mass ratio of modified solution-polymerized styrene-butadiene rubber, natural rubber, butadiene rubber, accelerator DPG, antioxidant 6PPD, Si-69, and white carbon black is 80:25:15:0.8:1:4:22;

[0068] S2: MB1, zinc oxide, antioxidant composition, wax, stearic acid and Si-69 were put into an internal mixer at a speed of 75 r / min, the top bolt was pressed, and mixing was performed for 30 seconds; the bolt was raised, white carbon black and carbon black N234 were added, the speed was 65 r / min, the top bolt was pressed, and mixing was performed to 108°C; the bolt was raised, environmentally friendly oil was added, and mixing was performed to 129°C at a speed of 55 r / min; the bolt was raised, the speed was reduced to 23 r / min, the top bolt was pressed, and mixing was performed at 142°C for 60 seconds; the glue was discharged at a temperature of 144°C, and the mixture was cooled to room temperature to obtain MB2;

[0069] The mass ratio of MB1, zinc oxide, antioxidant composition, wax, stearic acid, Si-69, white carbon black, carbon black N234 and environmentally friendly oil is 150:2:3:1.4:2.2:7:47:22:16;

[0070] Wherein, the mass ratio of antioxidant 4020 to antioxidant PD in the antioxidant composition is 1:1.3;

[0071] S3: MB2 was put into an internal mixer with a top bolt pressure of 5.2 MPa and a rotation speed of 45 rpm. The mixer was mixed for 93 seconds, and the mixture was discharged at 140°C. The mixture was cooled to room temperature to obtain MB3.

[0072] S4: MB3, accelerator CBS, and oil-extended sulfur powder were added into an internal mixer at a mass ratio of 240:2.4:1.3, at a temperature of 85°C and a speed of 25 rpm, with a push pin pressed on and mixed for 75 seconds, and the rubber was discharged at a temperature of 110°C to obtain a tread rubber;

[0073] S5: The tread rubber is extruded through a screw extruder at 90°C, and then assembled with the carcass cord, belt layer and other components on a molding machine to form a tire blank. The tire is then vulcanized in a vulcanizer at 155°C and 18MPa for 13 minutes to obtain a low rolling resistance, anti-slip semi-steel radial tire;

[0074] Wherein, the preparation method of modified solution-polymerized styrene-butadiene rubber comprises the following steps:

[0075] The solution polymerized styrene butadiene rubber, cyclohexane and 3-chloroperoxybenzoic acid were mixed in a mass ratio of 100:800:15, stirred evenly, reacted at 40°C for 10 hours, and after the reaction was completed, the pH was adjusted to 8 with a 0.01 mol / L sodium hydroxide aqueous solution, and dried at -0.1 MPa and 55°C for 22 hours to obtain an epoxidized solution polymerized styrene butadiene rubber;

[0076] Under a nitrogen atmosphere, epoxidized solution polymerized styrene butadiene rubber, maleic anhydride grafted polypropylene, xylene and diisopropylbenzene peroxide were mixed in a mass ratio of 100:40:900:3, reacted at 115°C for 6 hours, and after the reaction was completed, the mixture was distilled at 0.08 MPa and 80°C under reduced pressure for 11 hours, and dried at 95°C for 7 hours to obtain modified solution polymerized styrene butadiene rubber.

[0077] Example 4

[0078] This embodiment provides a method for preparing a low rolling resistance and anti-slip semi-steel radial tire, comprising the following steps:

[0079] S1: Add modified solution polystyrene butadiene rubber, natural rubber, butadiene rubber, accelerator DPG, antioxidant 6PPD and Si-69 into an internal mixer, rotate at 77 r / min, press on the top plug and mix for 37 s; raise the plug, add white carbon black, keep the speed at 67 r / min, press on the top plug and mix for 25 s; raise the top plug to clean it, reduce the speed to 57 r / min, mix for 22 s, the temperature reaches 128°C, reduce the speed to 47 r / min, press on the top plug and mix; raise the temperature to 148°C and keep it constant for 70 s; discharge the glue at 152°C, cool to room temperature, and obtain MB1;

[0080] Among them, the mass ratio of modified solution-polymerized styrene-butadiene rubber, natural rubber, butadiene rubber, accelerator DPG, antioxidant 6PPD, Si-69, and white carbon black is 85:27:17:0.9:1.1:4.5:25;

[0081] S2: MB1, zinc oxide, antioxidant composition, wax, stearic acid and Si-69 were put into an internal mixer at a speed of 77 r / min, the top bolt was pressed, and mixing was performed for 27 seconds; the bolt was raised, white carbon black and carbon black N234 were added, the speed was 67 r / min, the top bolt was pressed, and mixing was performed to 109°C; the bolt was raised, environmentally friendly oil was added, and mixing was performed to 130°C at a speed of 57 r / min; the bolt was raised, the speed was reduced to 22 r / min, the top bolt was pressed, and mixing was performed at 145°C for 57 seconds; the glue was discharged at a temperature of 146°C, and the mixture was cooled to room temperature to obtain MB2;

[0082] Among them, the mass ratio of MB1, zinc oxide, antioxidant composition, wax, stearic acid, Si-69, white carbon black, carbon black N234 and environmentally friendly oil is 155:2.5:3.5:1.5:2.4:7.5:51:24:17;

[0083] Wherein, the mass ratio of antioxidant 4020 to antioxidant PD in the antioxidant composition is 1:1.3;

[0084] S3: MB2 was put into an internal mixer with a top bolt pressure of 5.4 MPa and a rotation speed of 47 rpm. The mixer was mixed for 89 seconds, and the mixture was discharged at 140°C. The mixture was cooled to room temperature to obtain MB3.

[0085] S4: MB3, accelerator CBS, and oil-extended sulfur powder were added into an internal mixer at a mass ratio of 250:2.5:1.4, at a temperature of 87°C and a speed of 27 rpm, with a push pin pressed on for mixing for 68 seconds, and the rubber was discharged at a temperature of 110°C to obtain a tread rubber;

[0086] S5: The tread rubber is extruded through a screw extruder at 95°C, and then assembled with the carcass cord, belt layer and other components on a molding machine to form a tire blank. The tire is then vulcanized in a vulcanizer at 157°C and 19MPa for 12 minutes to obtain a low rolling resistance, anti-slip semi-steel radial tire;

[0087] Wherein, the preparation method of modified solution-polymerized styrene-butadiene rubber comprises the following steps:

[0088] The solution polymerized styrene butadiene rubber, cyclohexane and 3-chloroperoxybenzoic acid were mixed in a mass ratio of 100:900:17, stirred evenly, reacted at 45°C for 9 hours, and after the reaction was completed, the pH was adjusted to 9 with a 0.01 mol / L sodium hydroxide aqueous solution, and dried at -0.1 MPa and 57°C for 21 hours to obtain an epoxidized solution polymerized styrene butadiene rubber;

[0089] Under a nitrogen atmosphere, epoxidized solution polymerized styrene butadiene rubber, maleic anhydride grafted polypropylene, xylene and diisopropylbenzene peroxide were mixed in a mass ratio of 100:45:950:3.5, reacted at 123°C for 5 hours, and after the reaction was completed, the mixture was distilled at 0.08 MPa and 85°C under reduced pressure for 10.5 hours, and dried at 98°C for 6.5 hours to obtain modified solution polymerized styrene butadiene rubber.

[0090] Example 5

[0091] This embodiment provides a method for preparing a low rolling resistance and anti-slip semi-steel radial tire, comprising the following steps:

[0092] S1: Add modified solution polystyrene butadiene rubber, natural rubber, butadiene rubber, accelerator DPG, antioxidant 6PPD and Si-69 into an internal mixer, rotate at 80 r / min, press on the top plug and mix for 35 seconds; raise the plug, add white carbon black, keep the speed at 70 r / min, press on the top plug and mix for 20 seconds; raise the top plug to clean it, reduce the speed to 60 r / min, mix for 20 seconds, the temperature reaches 128°C, reduce the speed to 50 r / min, press on the top plug and mix; raise the temperature to 152°C and keep it constant for 60-100 seconds; discharge the glue at 152°C, cool to room temperature, and obtain MB1;

[0093] Among them, the mass ratio of modified solution-polymerized styrene-butadiene rubber, natural rubber, butadiene rubber, accelerator DPG, antioxidant 6PPD, Si-69, and white carbon black is 90:30:20:1:1.2:5:28;

[0094] S2: MB1, zinc oxide, antioxidant composition, wax, stearic acid and Si-69 were put into an internal mixer, the speed was 80 r / min, the top bolt was pressed, and the mixing was carried out for 25 seconds; the bolt was raised, white carbon black and carbon black N234 were added, the speed was 70 r / min, the top bolt was pressed, and the mixing was carried out to 110°C; the bolt was raised, environmentally friendly oil was added, and the mixing was carried out to 130°C at a speed of 60 r / min; the bolt was raised, the speed was reduced to 25 r / min, the top bolt was pressed, and the mixing was carried out at 148°C for 55 seconds; the glue was discharged at a temperature of 148°C, and the mixture was cooled to room temperature to obtain MB2;

[0095] The mass ratio of MB1, zinc oxide, antioxidant composition, wax, stearic acid, Si-69, white carbon black, carbon black N234 and environmentally friendly oil is 160:3:4:1.6:2.6:8:55:26:18;

[0096] Wherein, the mass ratio of antioxidant 4020 to antioxidant PD in the antioxidant composition is 1:1.4;

[0097] S3: MB2 was put into an internal mixer with a top bolt pressure of 5.5 MPa and a rotation speed of 50 rpm. The mixer was mixed for 85 seconds, and the mixture was discharged at 140°C. The mixture was cooled to room temperature to obtain MB3.

[0098] S4: MB3, accelerator CBS, and oil-extended sulfur powder were added into an internal mixer at a mass ratio of 260:2.6:1.5, at a temperature of 90°C and a speed of 30 rpm, and a top bolt was pressed to mix for 60 seconds, and the rubber was discharged at a temperature of 110°C to obtain a tread rubber;

[0099] S5: The tread rubber is extruded through a screw extruder at a temperature of 100°C, and then parked for 24 hours before being assembled with carcass cords, belt layers and other components on a molding machine to form a tire blank, which is then vulcanized in a vulcanizer at 160°C and 20MPa for 10 minutes to obtain a low rolling resistance, anti-slip semi-steel radial tire;

[0100] Wherein, the preparation method of modified solution-polymerized styrene-butadiene rubber comprises the following steps:

[0101] The solution polymerized styrene butadiene rubber, cyclohexane and 3-chloroperoxybenzoic acid were mixed in a mass ratio of 100:1000:20, stirred evenly, reacted at 50°C for 8h, and after the reaction was completed, the pH was adjusted to 9 with a 0.01 mol / L sodium hydroxide aqueous solution, and dried at -0.1 MPa and 60°C for 20h to obtain an epoxidized solution polymerized styrene butadiene rubber;

[0102] Under a nitrogen atmosphere, epoxidized solution polymerized styrene butadiene rubber, maleic anhydride grafted polypropylene, xylene and diisopropylbenzene peroxide were mixed in a mass ratio of 100:50:1000:4, reacted at 130°C for 4 hours, and after the reaction was completed, the mixture was distilled at 0.08 MPa and 90°C under reduced pressure for 10 hours, and dried at 100°C for 6 hours to obtain modified solution polymerized styrene butadiene rubber.

[0103] Comparative Example 1

[0104] The difference between this comparative example and embodiment 1 is that step S3 is eliminated.

[0105] Comparative Example 2

[0106] The difference between this comparative example and Example 1 is that step S3 is eliminated, and an equal mass of epoxidized solution polymerized styrene butadiene rubber is used in S1 to replace the modified solution polymerized styrene butadiene rubber.

[0107] Comparative Example 3

[0108] The difference between this comparative example and Example 1 is that step S3 is eliminated, and an equal mass of solution polymerized styrene butadiene rubber is used in S1 to replace the modified solution polymerized styrene butadiene rubber.

[0109] Comparative Example 4

[0110] The difference between this comparative example and Example 1 is that the tread rubber used in this comparative example is the high-performance epoxidized solution-polymerized styrene-butadiene rubber composite material disclosed in Example 4 of Chinese patent application CN117264298A.

[0111] Comparative Example 5

[0112] The difference between this comparative example and Example 1 is that the tread rubber used in this comparative example is the tire tread rubber material disclosed in Example 3 of Chinese patent application CN103788422B.

[0113] In the present invention, cis-butadiene rubber BR9000 comes from Yanshan Petrochemical Company. Based on the total amount of cis-butadiene rubber BR9000, the cis structure content is 96%, the number average molecular weight is 66,000, the molecular weight distribution is 5.2, and the Mooney viscosity is 45; natural rubber comes from Shanghai Duokang Industrial Co., Ltd., brand CV60; solution polystyrene butadiene rubber comes from Xiamen Mingjia New Materials Co., Ltd., specifically SSBR2564, model 2564T; antioxidant RD comes from Jiangsu Shengao Chemical Technology Co., Ltd.; antioxidant 6PPD comes from Shanghai Jiacheng Chemical Co., Ltd. Company; stearic acid comes from Hong Kong Siwen Chemical Co., Ltd., brand name SA1801; accelerator CBS comes from Wuhan Chengtian Fine Chemical Co., Ltd.; environmentally friendly oil comes from softener oil of Guangzhou Dagang Petroleum; Si-69 comes from Dongguan Kangjin New Material Technology Co., Ltd.; zinc oxide comes from Nanjing Baoket New Materials Co., Ltd., model: PZT-30, particle size: 30nm; environmentally friendly oil: purchased from Ningbo Hansheng Company, brand name N65; maleic anhydride grafted polypropylene comes from Shanghai Rizhisheng New Technology Development Co., Ltd., model CMG9801.

[0114] Performance Testing:

[0115] The tires prepared in Examples 1-5 and Comparative Examples 1-5 were tested, and the specific test results are shown in Table 1; the tread rubbers in Examples 1-5 and Comparative Examples 1-5 were tested, and the wear resistance of the tread rubbers was tested according to GBT1689-2014; the dynamic mechanical properties of the tread rubbers were tested by temperature scanning using dynamic mechanical thermal analysis (DMTA), the temperature test scanning range was -10°C-70°C, the heating rate was set to 5°C / min, the frequency was 10 Hz, and the strain was 0.20%; the specific test results are shown in Table 2;

[0116] Table 1

[0117]

[0118] Table 2

[0119]

[0120]

[0121] It can be seen from the above results that the tread rubber in Examples 1-5 better balances low rolling resistance and anti-wet skid performance. The tread rubber prepared by the present invention is used in low rolling resistance, anti-wet skid semi-steel radial tires, has good performance, reduced energy consumption, and helps to improve cruising range. The 60°C·tanδ values ​​in Example 1 are all smaller than those in Comparative Examples 1-3, indicating that the preparation method provided by the present invention effectively improves the dynamic properties of the tread rubber and effectively reduces rolling resistance. At the same time, it can be seen from the data in Table 1 that the temperature of the tire prepared in Example 1 at the end of the test was 42.1°C, which is lower than the values ​​in Comparative Examples 1-3, which strongly proves the advantages of the present invention in optimizing tire performance.

[0122] The above contents are merely examples and explanations of the structure of the present invention. The technicians in this technical field may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the structure of the invention or exceed the scope defined by the claims, they should all fall within the protection scope of the present invention.

[0123] In the description of this specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0124] The preferred embodiments of the present invention disclosed above are only used to help explain the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to only specific implementation methods. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A method for preparing a low rolling resistance, anti-slip semi-steel radial tire, characterized in that: The following steps are involved: S1: Put modified solution polymerized styrene-butadiene rubber, natural rubber, butadiene rubber, accelerator, antioxidant and solid silane into an internal mixer, press the top bolt and mix; raise the bolt, add white carbon black, press the top bolt and mix and adjust; discharge the rubber and cool to obtain MB1; S2: MB1, zinc oxide, antioxidant composition, wax, stearic acid, and solid silane are put into an internal mixer, and the top bolt is pressed, and mixing is performed; the bolt is raised, and white carbon black and carbon black are added, and mixing is performed; the bolt is raised, and oil is added, the temperature is increased, the speed is reduced, and mixing is performed; the glue is discharged, and the mixture is cooled to obtain MB2; S3: MB2 is put into an internal mixer, the top bolt is pressed, mixing, debonding, and cooling are performed to obtain MB3; S4: MB3, accelerator CBS, and oil-extended sulfur powder are put into an internal mixer, a top bolt is pressed, mixing is performed, and the bolt is lifted to discharge the rubber to obtain the tread rubber; S5: The tread rubber is extruded through a screw extruder, parked for 24 hours, assembled with carcass cords, belt layers and other components on a molding machine to form a tire blank, and vulcanized in a vulcanizer to obtain a low rolling resistance, anti-slip semi-steel radial tire.

2. The method for preparing a low rolling resistance and anti-wet skid semi-steel radial tire according to claim 1, characterized in that: The preparation method of modified solution-polymerized styrene-butadiene rubber comprises the following steps: The solution polymerized styrene butadiene rubber, cyclohexane and 3-chloroperoxybenzoic acid are mixed, stirred evenly, heated, reacted, the reaction is completed, the pH is adjusted, and dried to obtain the epoxidized solution polymerized styrene butadiene rubber; In a nitrogen atmosphere, epoxidized solution-polymerized styrene-butadiene rubber, maleic anhydride grafted polypropylene, xylene and an initiator are uniformly mixed, heated, reacted, and after the reaction is completed, vacuum distilled and dried to obtain a modified solution-polymerized styrene-butadiene rubber.

3. The method for preparing a low rolling resistance and anti-wet skid semi-steel radial tire according to claim 2, characterized in that: The mass ratio of solution-polymerized styrene-butadiene rubber, cyclohexane and 3-chloroperoxybenzoic acid is 100:(600-1000):(10-20); the reaction temperature is 30-50° C., and the reaction time is 8-12 hours.

4. The method for preparing a low rolling resistance and anti-slip semi-steel radial tire according to claim 2, characterized in that: The mass ratio of epoxidized solution polystyrene butadiene rubber, maleic anhydride grafted polypropylene, xylene and initiator is 100:(30-50):(800-1000):(2-4); the reaction temperature is 100-130°C, and the reaction time is 4-8h.

5. The method for preparing a low rolling resistance and anti-wet skid semi-steel radial tire according to claim 1, characterized in that: In S1, the mass ratios of modified solution-polymerized styrene-butadiene rubber, natural rubber, butadiene rubber, accelerator, antioxidant, solid silane and white carbon black are (70-90):(20-30):(10-20):(0.6-1):(0.8-1.2):(3-5):(16-28).

6. The method for preparing a low rolling resistance and anti-wet skid semi-steel radial tire according to claim 1, characterized in that: In S2, the mass ratios of MB1, zinc oxide, antioxidant composition, wax, stearic acid, solid silane, white carbon, carbon black and oil are (140-160):(1-3):(2-4):(1.2-1.6):(1.8-2.6):(6-8):(40-55):(18-26):(14-18).

7. The method for preparing a low rolling resistance and wet skid resistant semi-steel radial tire according to claim 1, characterized in that: In S3, the upper push pin pressure is 5-5.5 MPa, the rotation speed is 40-50 rpm, and the mixing time is 85-100 s.

8. The method for preparing a low rolling resistance and anti-wet skid semi-steel radial tire according to claim 1, characterized in that: In S4, the mass ratio of MB3, accelerator CBS and oil-extended sulfur powder is (220-260):(2.2-2.6):(1.1-1.5).

9. The method for preparing a low rolling resistance and anti-wet semi-steel radial tire according to claim 1, characterized in that: The debinding temperature in S1 is 152°C; the debinding temperature in S2 is 141-148°C; the debinding temperature in S3 is 140°C; and the debinding temperature in S4 is 110°C.

10. The method for preparing a low rolling resistance and anti-wet skid semi-steel radial tire according to claim 1, characterized in that: In S5, the tread rubber is extruded by a screw extruder at a temperature of 80-100°C; the parameters of the vulcanizer are: 150-160°C, 15-20MPa, and vulcanization for 10-15min.

Images