Hot-melt rubber composition, hot-melt rubber and preparation method of hot-melt rubber

Abstract

The invention provides a hot-melt rubber composition, hot-melt rubber and a preparation method thereof. The hot-melt rubber composition is prepared from the following components in parts by weight: 100 parts of a raw rubber system, 30 to 180 parts of grip resin, 80 to 155 parts of carbon black, 8 to 35 parts of a softening agent, 3.1 to 7.3 parts of an activation system, 3.5 to 8.5 parts of a protection system and 3.0 to 4.7 parts of a vulcanization system, wherein the ground gripping resin comprises first ground gripping resin, second ground gripping resin and third ground gripping resin. According to the invention, the grip resin with three ring and ball softening point temperature gradients in a temperature range of more than 80 DEG C is creatively adopted, so that the hot-melt rubber is ensured to have good hot melting performance, grip performance and control performance. In addition, the carbon black with higher parts by weight is used in the tread, so that the thermal stability and the dry grip performance of the tire in the running process can be further ensured. Under the synergistic effect of other auxiliaries, the hot-melt rubber has more excellent comprehensive performance.

Description

Technical Field

[0001] The present invention relates to the technical field of tire rubber material preparation, and in particular to a hot melt rubber composition, hot melt rubber and a preparation method thereof. Background Art

[0002] With the rapid development of social economy and technology, people's performance requirements for vehicles and their corresponding tires are constantly increasing, and their enthusiasm for racing sports, which have been inherited and developed for hundreds of years, is also increasing. The demand for tire grip in current related racing sports such as formula competitions, drift competitions, and rally competitions is constantly refreshing the limits of technical development capabilities. The tire tread rubber material currently used in racing sports is a hot melt rubber composition. Its working principle is that when the tire tread and the ground rub against each other during driving, a certain temperature is generated. At this time, the tread rubber composition can present a molten gel state under heat, thereby improving the adhesion to the ground, and then providing a strong grip and driving effect for the vehicle.

[0003] In the Chinese patent application with the publication number of patent application CN 112778593 A, a semi-hot melt tread rubber composition is mentioned. The composition is mainly composed of solution-polymerized styrene butadiene rubber as the main matrix, and is combined with thermoplastic resin and a certain amount of white carbon black and carbon black mixture. Comprehensive analysis shows that the composition can achieve a certain grip target. In the Chinese patent application with the publication number of patent application CN117164971 A, a full hot melt tread rubber composition with ultra-high dry grip performance and its preparation method are reported. The composition mainly uses non-modified solution styrene butadiene rubber, liquid-solid grip resin and carbon black, and finally provides good grip performance under the comprehensive effect of multiple materials.

[0004] At present, there are few reports on the application and development of hot melt rubber composite materials in racing tire formulations. According to the known reports on related hot melt adhesive materials, high grip rubber materials and corresponding softeners and fillers are used to achieve this. However, due to the limitations of the formulation development level and rubber processing technology level, the related hot melt rubber composites have high viscosity and low modulus in the internal mixer, making it difficult to achieve good uniform mixing, dispersion and processing, thus limiting the realization of the material's optimal grip performance.

[0005] Therefore, how to solve the above technical problems, develop a hot melt rubber composition with high grip performance, and achieve good mixing and processing of related composition materials are technical problems that technicians in this field urgently need to solve. Summary of the invention

[0006] The main purpose of the present invention is to provide a hot melt rubber composition, hot melt rubber and a preparation method thereof, so as to solve the problem that the hot melt rubber composition in the prior art has high viscosity and low modulus in an internal mixer, making it difficult to achieve good uniform mixing, dispersion and processing, thereby limiting the realization of better grip performance of the material.

[0007] In order to achieve the above-mentioned purpose, according to one aspect of the present invention, a hot melt rubber composition is provided, which comprises, by weight, 100 parts of a raw rubber system, 30 to 180 parts of a grip resin, 80 to 155 parts of carbon black, 8 to 35 parts of a softener, 2.2 to 7.3 parts of an activation system, 3.5 to 8.5 parts of a protection system and 3.0 to 4.7 parts of a vulcanization system; wherein the grip resin comprises a first grip resin, a second grip resin and a third grip resin, the first grip resin has a ring and ball softening point temperature of 80°C to 100°C, the second grip resin has a ring and ball softening point temperature of 101°C to 135°C, and the third grip resin has a ring and ball softening point temperature of 136°C to 150°C.

[0008] Furthermore, in parts by weight, the grip resin is selected from a combination of 10 to 90 parts of a first grip resin, 10 to 45 parts of a second grip resin and 10 to 45 parts of a third grip resin; and / or the mass ratio of the first grip resin, the second grip resin and the third grip resin is 1 to 9: 1 to 3: 1 to 3, preferably 1 to 3: 1 to 3: 1 to 3.

[0009] Furthermore, the first grip resin is C 9 Copolymer resin, preferably the monomer forming the first grip resin is selected from any one or more of styrene, methyl styrene, indene and its derivatives and coumarone; preferably the number average molecular weight of the first grip resin is between 1500 and 2500, and preferably the specific structure of the first grip resin is as shown in Formula I:

[0010]

[0011] Wherein, n in Formula I is ≥ 1; and / or, the second grip resin is a hydrogenated cyclopentadiene resin, and the number average molecular weight of the second grip resin is between 1600 and 2000; and / or, the third grip resin is a terpene phenol resin, and the number average molecular weight of the third grip resin is preferably between 1200 and 3000, and the specific structure of the third grip resin is preferably as shown in Formula II:

[0012]

[0013] Wherein, in formula II, n≥1, m≥1.

[0014] Further, the glass transition temperature of the raw rubber system is -20°C to 10°C; in parts by weight, the raw rubber system includes 35 to 60 parts of emulsion-polymerized styrene-butadiene rubber, 35 to 60 parts of solution-polymerized styrene-butadiene rubber and 5 to 30 parts of auxiliary rubber; and / or, the mass content of styrene in the emulsion-polymerized styrene-butadiene rubber is 15% to 45%, 1,2-vinyl accounts for 10% to 30% of the total mass of the diene components in the emulsion-polymerized styrene-butadiene rubber, and the glass transition temperature of the emulsion-polymerized styrene-butadiene rubber is -25°C to -20°C; and / or, the mass content of styrene in the solution-polymerized styrene-butadiene rubber is 15% to 45%, 1,2-vinyl accounts for 10% to 30% of the total mass of the diene components in the emulsion-polymerized styrene-butadiene rubber The auxiliary rubber is 25% to 55% of the total mass of the diene component of the styrene rubber, and the glass transition temperature of the solution-polymerized styrene-butadiene rubber is -38°C to -22°C; and / or the auxiliary rubber is a rubber polymer formed by homopolymerization or copolymerization of butadiene, styrene, pentadiene, C4 olefin monomer or C5 olefin monomer, and the auxiliary rubber is selected from any one or more of butadiene-styrene copolymer rubber, epoxidized natural rubber, cis-butadiene rubber, isoprene rubber and butadiene-pentadiene rubber; and / or the molecular weight of the auxiliary rubber is 3000 to 1000000, and / or the glass transition temperature of the auxiliary rubber is -120°C to -40°C.

[0015] Furthermore, the carbon black is 95 to 145 parts by weight, and / or the particle size of the carbon black is distributed between 5.0 nm and 25 nm, and / or the specific surface area STSA of the carbon black is between 150 m 2 / g~230m 2 / g, and / or the compressed DBP oil absorption value of carbon black is between 80mL / 100g and 120mL / 100g, and / or the grade of carbon black is selected from any one or more of series 1 and series 2 in ASTM standards.

[0016] Further, the softener is selected from any one or more of liquid butadiene-styrene copolymer rubber, liquid isoprene rubber, liquid cis-butadiene rubber, naphthenic oil, heavy naphthenic oil, environmentally friendly aromatic oil, modified environmentally friendly aromatic oil and modified vegetable soybean oil; and / or the molecular weight of the softener is between 4000 and 8500, and / or the kinematic viscosity of the softener is between 4.0 mm 2 / s~12mm 2 / s.

[0017] Furthermore, the activation system comprises, by weight, 2.0 to 5.0 parts of zinc oxide, 0.1 to 1.5 parts of stearic acid and 0.1 to 0.8 parts of magnesium oxide.

[0018] Furthermore, in parts by weight, the protective system comprises 1.5 to 3.5 parts of protective wax and 2.0 to 5.0 parts of antioxidant; and / or the protective wax is selected from any one or more of PE wax, microcrystalline protective wax and paraffin wax; and / or the antioxidant is selected from any one or more of N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine 4020, 2,2,4-trimethyl-1,2-dihydroquinoline polymer RD, N,N'-xylyl-p-phenylenediamine DTPD, N-isopropyl-N'-phenyl-p-phenylenediamine 4010NA, 2-mercaptobenzimidazole MB and N-cyclohexyl-N'-phenyl-p-phenylenediamine 4010.

[0019] Further, in parts by weight, the above-mentioned vulcanization system includes 1.5 to 2.5 parts of an accelerator and 1.5 to 2.2 parts of a vulcanizing agent; and / or the vulcanization system is selected from any one or more of insoluble sulfur, soluble sulfur, 2-mercaptobenzothiazole M, diisopropylbenzyl peroxide, zinc dibenzyldithiocarbamate ZBEC, 2,2'-dithiodibenzothiazole DM, N-cyclohexyl-2-benzothiazole sulfenamide CZ, diphenylguanidine DPG, N-tert-butyl-2-benzothiazole sulfenamide NS, N,N-2-dicyclohexyl-2,2-dibenzothiazole sulfenamide DZ and zinc dimethyldithiocarbamate ZDMC.

[0020] According to another aspect of the present invention, a method for preparing hot melt rubber is provided, which comprises: step S1, stirring and mixing raw materials including a raw rubber system, a grip resin, carbon black, a softener, an activation system, a protective system and an organic solvent to obtain a mixture; step S2, flocculating and devolatilizing the mixture in sequence to obtain a mixed masterbatch; step S3, mixing, debonding and vulcanizing the materials including the mixed masterbatch and a vulcanization system in sequence to obtain a hot melt rubber; wherein, additives including a softener, an activator and a protective system are added in step S1 or step S3; and the formulas of the raw rubber system, grip resin, carbon black, softener, activation system, protective system, organic solvent, softener, activator, protective system and vulcanization system are independently selected from the aforementioned hot melt rubber composition.

[0021] Further, the above step S1 includes: step S11, crushing the raw rubber system and mixing it with the first organic solvent for the first time to obtain a rubber solution; step S12, crushing the carbon black and mixing it with the second organic solvent for the second time to obtain a carbon black slurry; step S13, stirring and mixing the grip resin with the third organic solvent for the third time to obtain a resin solution; step S14, mixing the rubber solution, the carbon black slurry and the resin solution for the first time to obtain a mixture; preferably step S14 includes: mixing the rubber solution with the carbon black slurry for the second time to obtain a carbon black-rubber solution; mixing the carbon black-rubber solution with the resin solution for the third time three mixing to obtain a mixture; wherein, in step S11, the average particle size of the raw rubber system after crushing is 1.0 mm to 3.0 mm, and / or the mass concentration of the rubber solution is 8.0% to 25%, and / or the temperature of the first stirring and mixing is 45°C to 80°C, and / or the rotation speed of the first stirring and mixing is 30rpm to 300rpm, and / or the time of the first stirring and mixing is 2.0h to 10h; in step S12, the average particle size of the carbon black after crushing is 0.1μm to 20μm, and / or the solid content of the carbon black slurry is 20% to 50%, and / or the temperature of the second stirring and mixing is 35°C to 60°C, and / or or the second stirring and mixing speed is 50rpm~1000rpm, and / or the second stirring and mixing time is 30min~60min; in step S13, the mass concentration of the resin solution is 10%~30%, and / or the third stirring and mixing temperature is 60℃~80℃, and / or the third stirring and mixing speed is 30rpm~300rpm, and / or the third stirring and mixing time is 0.5h~10h; and / or the first mixing, second mixing and third mixing conditions are independently selected from the mixing temperature between 40℃~60℃, the stirring speed between 30rpm~300rpm, the mixing The mixing time is between 30 min and 180 min; and / or, the first organic solvent, the second organic solvent and the third organic solvent are each independently selected from any one or more of aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, chlorinated hydrocarbon solvents, ketone solvents, ether solvents and ester solvents; preferably, the aliphatic hydrocarbon solvent is selected from any one or more of gasoline, cycloalkanes, substituted cycloalkanes and normal alkanes; preferably, the aromatic hydrocarbon solvent is selected from any one or more of benzene, toluene, xylene and styrene; preferably, the chlorinated hydrocarbon solvent is selected from any one or more of dichloromethane, chloroform, carbon tetrachloride, dichloroethane, chlorobenzene, tetrachloroethylene and chlorotoluene.

[0022] Furthermore, in the above step S2, the flocculation method includes: contacting the mixture with a coagulation medium for flocculation, the coagulation medium is selected from any one or more of nitrogen, carbon dioxide, liquid water and water vapor; or, flocculating the mixture by shear drying, preferably the shear drying method is selected from any one or more of spray drying, high temperature flash evaporation and mechanical compression.

[0023] Furthermore, in the above step S2, the above devolatilization method is selected from any one or more of continuous extrusion devolatilization by a single screw extruder, continuous extrusion devolatilization by a twin screw extruder, continuous microwave radiation devolatilization, open mill devolatilization and internal mixer high temperature devolatilization.

[0024] According to another aspect of the present invention, a hot melt rubber is provided. The hot melt rubber is prepared by the above-mentioned preparation method.

[0025] By applying the technical solution of the present application, the present invention creatively adopts a grip resin having three ring softening point temperature gradients in the above temperature range, thereby ensuring that the hot melt rubber has good hot melt performance, grip performance, and handling performance. Specifically, when the car is in the race, the tread temperature is often between 80°C and 100°C at a lower running speed. At this time, the first grip resin undergoes hot melt gelation to ensure the grip performance of the hot melt rubber. As the running intensity increases, the second grip resin under the condition of 100°C to 135°C is activated and acts together with the first grip resin on the grip performance, that is, compared with the traditional racing tire formula, the hot melt rubber composition of the present application has a better temperature response hot melt performance, that is, the grip resin can exert hot melt performance at a lower tire temperature, while avoiding the tire warming step at room temperature, so as to fully meet the requirements of various hot melt racing events commonly used in the market. At the same time, the third grip resin can ensure the thermal stability and rigid support of the tire under high temperature operation. In addition, the use of a higher weight portion of the above carbon black in the tread can further ensure the thermal stability and dry grip performance of the tire during operation. With the synergistic effect of other additives such as softener, activation system, protection system and vulcanization system, hot melt rubber has better comprehensive properties. DETAILED DESCRIPTION

[0026] It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of the present application can be combined with each other. The present invention will be described in detail below in conjunction with the embodiments.

[0027] As analyzed in the background technology of the present application, in the prior art, there is a problem that the hot-melt rubber composition has high viscosity and low modulus in an internal mixer, which makes it difficult to achieve good uniform mixing, dispersion and processing, limiting the realization of better grip performance of the material. In order to solve the above problems, the present application provides a hot-melt rubber composition, hot-melt rubber and a preparation method thereof.

[0028] In a typical embodiment of the present application, a hot melt rubber composition is provided, which includes, by weight, 100 parts of a raw rubber system, 30 to 180 parts of a grip resin, 80 to 155 parts of carbon black, 8 to 35 parts of a softener, 2.2 to 7.3 parts of an activation system, 3.5 to 8.5 parts of a protection system and 3.0 to 4.7 parts of a vulcanization system; wherein the grip resin includes a first grip resin, a second grip resin and a third grip resin, the first grip resin has a ring and ball softening point temperature of 80°C to 100°C, the second grip resin has a ring and ball softening point temperature of 101°C to 135°C, and the third grip resin has a ring and ball softening point temperature of 136°C to 150°C.

[0029] The present invention creatively adopts a grip resin with three ring softening point temperature gradients in the above temperature range, thereby ensuring that the hot melt rubber has good hot melt performance, grip performance, and handling performance. Specifically, when the car is in the race, the tread temperature is often between 80°C and 100°C at a lower running speed. At this time, the first grip resin undergoes hot melt gelation to ensure the grip performance of the hot melt rubber. As the running intensity increases, the second grip resin under the condition of 100°C to 135°C is activated and acts together with the first grip resin on the grip performance, that is, compared with the traditional racing tire formula, the hot melt rubber composition of the present application has a better temperature response hot melt performance, that is, the grip resin can exert hot melt performance at a lower tire temperature, while avoiding the tire warming step at room temperature, so as to fully meet the requirements of various hot melt racing events commonly used in the market. At the same time, the third grip resin can ensure the thermal stability and rigid support of the tire under high temperature operation. In addition, the use of a higher weight portion of the above carbon black in the tread can further ensure the thermal stability and dry grip performance of the tire during operation. With the synergistic effect of other additives such as softener, activation system, protection system and vulcanization system, hot melt rubber has better comprehensive properties.

[0030] In one embodiment of the present application, the above-mentioned grip resin is selected from a combination of 10 to 90 parts of a first grip resin, 10 to 45 parts of a second grip resin and 10 to 45 parts of a third grip resin, in parts by weight; and / or the mass ratio of the first grip resin, the second grip resin and the third grip resin is 1 to 9:1 to 3:1 to 3, preferably 1 to 3:1 to 3:1 to 3.

[0031] The preferred contents and mass ratios of the first grip resin, the second grip resin and the third grip resin are more helpful in controlling the grip resins under various temperature conditions to synergistically play an excellent complementary role, thereby improving the overall performance of the hot melt rubber of the entire racing car during the race.

[0032] In one embodiment of the present application, the first grip resin is C 9Copolymer resin, preferably the monomers forming the first grip resin are selected from any one or more of styrene, methyl styrene, indene and its derivatives and coumarone; preferably the number average molecular weight of the first grip resin is between 1500 and 2500, and preferably the specific structure of the first grip resin is as shown in Formula I:

[0033]

[0034] Wherein, n in Formula I is ≥ 1; and / or, the second grip resin is a hydrogenated cyclopentadiene resin, and the number average molecular weight of the second grip resin is between 1600 and 2000; and / or, the third grip resin is a terpene phenol resin, and preferably the number average molecular weight of the third grip resin is between 1200 and 3000, and preferably the specific structure of the third grip resin is as shown in Formula II:

[0035]

[0036] Wherein, in formula II, n≥1, m≥1.

[0037] The synergistic effect among the first grip resin, the second grip resin, and the third grip resin of the above preferred types is more excellent.

[0038] In one embodiment of the present application, the glass transition temperature of the raw rubber system is -20°C to 10°C; in parts by weight, the raw rubber system includes 35 to 60 parts of emulsion-polymerized styrene-butadiene rubber, 35 to 60 parts of solution-polymerized styrene-butadiene rubber and 5 to 30 parts of auxiliary rubber; and / or, the mass content of styrene in the emulsion-polymerized styrene-butadiene rubber is 15% to 45%, 1,2-vinyl accounts for 10% to 30% of the total mass of the diene component in the emulsion-polymerized styrene-butadiene rubber, and the glass transition temperature of the emulsion-polymerized styrene-butadiene rubber is -25°C to -20°C; and / or, the mass content of styrene in the solution-polymerized styrene-butadiene rubber is 15% to 45%, 1,2-vinyl accounts for 25% to 55% of the total mass of the diene component of the solution-polymerized styrene-butadiene rubber, and the glass transition temperature of the solution-polymerized styrene-butadiene rubber is -38°C to -22°C; and / or, the auxiliary rubber is composed of butadiene, styrene, pentadiene, C 4 Olefin monomer or C 5 The rubber polymer is formed by homopolymerization or copolymerization of olefin monomers, the auxiliary rubber is selected from any one or more of butadiene-styrene copolymer rubber, epoxidized natural rubber, cis-butadiene rubber, isoprene rubber and butadiene-pentadiene copolymer rubber; and / or the auxiliary rubber has a molecular weight of 3000 to 1000000, and / or the auxiliary rubber has a glass transition temperature of -120°C to -40°C.

[0039] The preferred raw rubber system has a high styrene content, which helps to improve the grip performance of the hot melt rubber composition of the present application. At the same time, the use of emulsion-polymerized styrene-butadiene rubber, solution-polymerized styrene-butadiene rubber and auxiliary rubber with low glass transition temperature is conducive to keeping the glass transition temperature of the raw rubber system at a low level, which helps to reduce the risk of long-term tire warming during use and transportation and storage damage in a low-temperature environment. In addition, the solution-polymerized styrene-butadiene rubber is preferably unmodified or one or more of chain single-end modification, chain double-end modification, chain mid-modification, and star structure.

[0040] In one embodiment of the present application, the carbon black is 95 to 145 parts by weight, and / or the particle size of the carbon black is distributed between 5.0 nm and 25 nm, and / or the specific surface area STSA of the carbon black is between 150 m 2 / g~230m 2 / g, and / or the compressed DBP oil absorption value of carbon black is between 80mL / 100g and 120mL / 100g, and / or the grade of carbon black is selected from any one or more of series 1 and series 2 in ASTM standards.

[0041] The carbon black preferably has the above parameter ranges because it has better aggregation and surface activity, thereby having better dispersibility in the hot melt rubber composition, as well as better reinforcing and filling effects.

[0042] In one embodiment of the present application, the above-mentioned softener is selected from any one or more of liquid butadiene-styrene copolymer rubber, liquid isoprene rubber, liquid cis-butadiene rubber, cyclohexane oil, heavy cyclohexane oil, environmentally friendly aromatic oil, modified environmentally friendly aromatic oil and modified vegetable soybean oil; and / or the molecular weight of the softener is between 4000 and 8500, and / or the kinematic viscosity of the softener is between 4.0 mm 2 / s~12mm 2 / s.

[0043] The above preferred softeners help to control the hardness of the hot melt rubber composition as a whole, thereby improving the molding and processability of the hot melt rubber composition.

[0044] In order to improve the processability, physical and mechanical properties and service life of the hot melt rubber, in one embodiment of the present application, the activation system preferably includes 2.0 to 5.0 parts of zinc oxide, 0.1 to 1.5 parts of stearic acid and 0.1 to 0.8 parts of magnesium oxide, in parts by weight.

[0045] In order to extend the service life of the hot-melt rubber, in one embodiment of the present application, the above-mentioned protective system preferably includes 1.5 to 3.5 parts of protective wax and 2.0 to 5.0 parts of antioxidant, by weight; and / or the protective wax is selected from any one or more of PE wax, microcrystalline protective wax and paraffin wax; and / or the antioxidant is selected from any one or more of N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine 4020, 2,2,4-trimethyl-1,2-dihydroquinoline polymer RD, N,N'-xylyl-p-phenylenediamine DTPD, N-isopropyl-N'-phenyl-p-phenylenediamine 4010NA, 2-mercaptobenzimidazole MB and N-cyclohexyl-N'-phenyl-p-phenylenediamine 4010.

[0046] In order to improve the conversion effect of the linear rubber molecular structure to the three-dimensional network structure rubber molecule, in one embodiment of the present application, the above-mentioned vulcanization system preferably includes 1.5 to 2.5 parts of an accelerator and 1.5 to 2.2 parts of a vulcanizing agent, by weight; and / or the vulcanization system is selected from any one or more of insoluble sulfur, soluble sulfur, 2-mercaptobenzothiazole M, diisopropylbenzene peroxide, zinc dibenzyldithiocarbamate ZBEC, 2,2'-dithiodibenzothiazole DM, N-cyclohexyl-2-benzothiazole sulfenamide CZ, diphenylguanidine DPG, N-tert-butyl-2-benzothiazole sulfenamide NS, N,N-2-dicyclohexyl-2,2-dibenzothiazole sulfenamide DZ and zinc dimethyldithiocarbamate ZDMC.

[0047] In another typical embodiment of the present application, a method for preparing hot melt rubber is provided, which comprises: step S1, stirring and mixing raw materials including a raw rubber system, a grip resin, carbon black, a softener, an activation system, a protective system and an organic solvent to obtain a mixture; step S2, flocculating and devolatilizing the mixture in sequence to obtain a mixed masterbatch; step S3, mixing, debinding and vulcanizing the materials including the mixed masterbatch and the vulcanization system in sequence to obtain a hot melt rubber; wherein, additives including a softener, an activator and a protective system are added in step S1 or step S3; and the formulas of the raw rubber system, grip resin, carbon black, softener, activation system, protective system, organic solvent, softener, activator, protective system and vulcanization system are independently selected from the above-mentioned hot melt rubber composition.

[0048] On the one hand, the hot melt rubber composition of the present application has the above formula composition; on the other hand, the present application creatively develops a liquid phase mixing processing method for the hot melt rubber composition. Compared with the traditional dry mechanical mixing process, the preparation method of the present application reduces energy consumption, dust pollution, noise pollution, etc. to a large extent; it also solves the problems of difficult dispersion of additives, high viscosity of rubber, rotor slippage, and difficult rubber removal of the hot melt rubber composition under high temperature of dry mechanical processing; through the synergistic effect of the above two aspects, the hot melt rubber obtained by the preparation method of the present application has good hot melt performance, grip performance, and handling performance. And the above preparation method is simple and low cost.

[0049] In one embodiment of the present application, the above-mentioned step S1 includes: step S11, crushing the raw rubber system and mixing it with the first organic solvent for the first time to obtain a rubber solution; step S12, crushing the carbon black and mixing it with the second organic solvent for the second time to obtain a carbon black slurry; step S13, stirring and mixing the grip resin with the third organic solvent for the third time to obtain a resin solution; step S14, mixing the rubber solution, the carbon black slurry and the resin solution for the first time to obtain a mixture; preferably step S14 includes: mixing the rubber solution with the carbon black slurry for the second time to obtain a carbon black-rubber solution; mixing the carbon black-rubber solution with the resin The solution is mixed for the third time to obtain a mixture; wherein, in step S11, the average particle size of the raw rubber system after crushing is 1.0 mm to 3.0 mm, and / or the mass concentration of the rubber solution is 8.0% to 25%, and / or the temperature of the first stirring and mixing is 45°C to 80°C, and / or the speed of the first stirring and mixing is 30rpm to 300rpm, and / or the time of the first stirring and mixing is 2.0h to 10h; in step S12, the average particle size of the carbon black after crushing is 0.1μm to 20μm, and / or the solid content of the carbon black slurry is 20% to 50%, and / or the temperature of the second stirring and mixing is 35°C to 60°C , and / or the second stirring and mixing speed is 50rpm~1000rpm, and / or the second stirring and mixing time is 30min~60min; in step S13, the mass concentration of the resin solution is 10%~30%, and / or the third stirring and mixing temperature is 60℃~80℃, and / or the third stirring and mixing speed is 30rpm~300rpm, and / or the third stirring and mixing time is 0.5h~10h; and / or, the conditions of the first mixing, the second mixing and the third mixing are independently selected from the mixing temperature between 40℃~60℃, the stirring speed between 30rpm~300rpm , the mixing time is between 30min and 180min; and / or, the first organic solvent, the second organic solvent and the third organic solvent are each independently selected from any one or more of aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, chlorinated hydrocarbon solvents, ketone solvents, ether solvents and ester solvents; preferably, the aliphatic hydrocarbon solvent is selected from any one or more of gasoline, cycloalkanes, substituted cycloalkanes and normal alkanes; preferably, the aromatic hydrocarbon solvent is selected from any one or more of benzene, toluene, xylene and styrene; preferably, the chlorinated hydrocarbon solvent is selected from any one or more of dichloromethane, chloroform, carbon tetrachloride, dichloroethane, chlorobenzene, tetrachloroethylene and chlorotoluene.

[0050] The preferred method of preparing the rubber solution, carbon black slurry and resin solution in steps above makes the raw rubber system, grip resin, carbon black and other components dispersed more evenly after mixing. The preferred type of organic solvent is within the above range, which helps to improve the solubility and dispersibility of each component therein. The preferred stirring conditions and mixing temperature are within the above range, which further improves the mixing effect between the components.

[0051] In one embodiment of the present application, in the above step S2, the temperature during the flocculation process is 20-300°C, preferably 95-115°C; the flocculation method includes: contacting the mixture with a coagulation medium for flocculation, and the coagulation medium is selected from any one or more of nitrogen, carbon dioxide, liquid water and water vapor; or, flocculating the mixture by shear drying, and the preferred shear drying method is selected from any one or more of spray drying, high-temperature flash evaporation and mechanical compression; the preferred flocculation method is coagulation medium flocculation and / or shear drying flocculation.

[0052] Step S1 of the present application is a wet mixing system, and therefore, the above flocculation process preferred in the present application is helpful to improve the flocculation effect of the wet mixing system of the present application.

[0053] In order to improve the devolatilization effect, in one embodiment of the present application, in the above step S2, the temperature during the devolatilization process is preferably 60-200°C, preferably 98°C-165°C, and the devolatilization method is preferably selected from any one or more of continuous extrusion devolatilization by a single-screw extruder, continuous extrusion devolatilization by a twin-screw extruder, continuous microwave radiation devolatilization, open mill devolatilization and internal mixer mixing high temperature devolatilization.

[0054] In another typical embodiment of the present application, a hot melt rubber is provided. The hot melt rubber is prepared by the above-mentioned preparation method.

[0055] The hot-melt rubber prepared by the preparation method of the present application has good hot-melt performance, grip performance, and handling performance, making it more suitable for use as a racing tire.

[0056] The beneficial effects of the present application will be further illustrated below in conjunction with embodiments.

[0057] The materials and reagents used in the following examples, unless otherwise specified, can all be obtained from commercial sources. The raw material units "parts" in the examples are all parts by weight unless otherwise specified.

[0058] The following embodiments are implemented using emulsion polymerized styrene butadiene rubber ESBR, solution polymerized styrene butadiene rubber SSBR, epoxidized natural rubber, ultra-wear-resistant fine particle carbon black CB, a first grip resin (molecular weight of 1800), a second grip resin (molecular weight of 1700), a third grip resin (molecular weight of 2000), environmentally friendly aromatic oil TDAE, zinc oxide ZnO, stearic acid SA, magnesium oxide MgO, protective wax Wax, antioxidant RD, antioxidant 4020, sulfur S, accelerator NS, and accelerator ZBEC.

[0059] Example 1

[0060] The invention adopts 45 parts of emulsion-polymerized styrene-butadiene rubber, 45 parts of solution-polymerized styrene-butadiene rubber, 10 parts of epoxidized natural rubber, 125 parts of carbon black, 25 parts of the first grip resin, 25 parts of the second grip resin, 25 parts of the third grip resin, 16 parts of environmentally friendly aromatic oil, 3.5 parts of zinc oxide, 1.0 parts of stearic acid, 0.5 parts of magnesium oxide, 1.0 parts of protective wax, 3.0 parts of antioxidant 4020, 2.0 parts of antioxidant RD, 1.8 parts of sulfur, 1.9 parts of accelerator NS and 0.1 parts of accelerator ZBEC; the specific contents are shown in formula Table 1.

[0061] Example 2

[0062] The invention adopts 45 parts of emulsion-polymerized styrene-butadiene rubber, 45 parts of solution-polymerized styrene-butadiene rubber, 10 parts of epoxidized natural rubber, 135 parts of carbon black, 30 parts of the first grip resin, 30 parts of the second grip resin, 25 parts of the third grip resin, 24 parts of environmentally friendly aromatic oil, 3.5 parts of zinc oxide, 1.0 parts of stearic acid, 0.5 parts of magnesium oxide, 1.0 parts of protective wax, 3.0 parts of antioxidant 4020, 2.0 parts of antioxidant RD, 1.8 parts of sulfur, 1.9 parts of accelerator NS and 0.1 parts of accelerator ZBEC; the specific contents are shown in formula Table 1.

[0063] Example 3

[0064] The invention adopts 45 parts of emulsion-polymerized butadiene styrene rubber, 45 parts of solution-polymerized butadiene styrene rubber, 10 parts of epoxidized natural rubber, 145 parts of carbon black, 35 parts of the first grip resin, 35 parts of the second grip resin, 25 parts of the third grip resin, 32 parts of environmentally friendly aromatic oil, 3.5 parts of zinc oxide, 1.0 parts of stearic acid, 0.5 parts of magnesium oxide, 1.0 parts of protective wax, 3.0 parts of antioxidant 4020, 2.0 parts of antioxidant RD, 1.8 parts of sulfur, 1.9 parts of accelerator NS and 0.1 parts of accelerator ZBEC; the specific contents are shown in formula Table 1.

[0065] Example 4

[0066] The difference from Example 1 is that the first grip resin is 45 parts by weight, the second grip resin is 30 parts by weight, the third grip resin is 15 parts by weight, and the mass ratio of the first grip resin, the second grip resin and the third grip resin is 3:2:1, and finally a hot melt rubber is obtained.

[0067] Example 5

[0068] The difference from Example 1 is that the first grip resin is 30 parts by weight, the second grip resin is 30 parts by weight, the third grip resin is 10 parts by weight, and the mass ratio of the first grip resin, the second grip resin and the third grip resin is 3:3:1, and finally a hot melt rubber is obtained.

[0069] Example 6

[0070] The difference from Example 1 is that the first grip resin is 15 parts by weight, the second grip resin is 20 parts by weight, the third grip resin is 45 parts by weight, and the mass ratio of the first grip resin, the second grip resin and the third grip resin is 1:2:3, and finally a hot melt rubber is obtained.

[0071] Example 7

[0072] The difference from Example 1 is that the first grip resin is 90 parts by weight, the second grip resin is 10 parts by weight, the third grip resin is 10 parts by weight, and the mass ratio of the first grip resin, the second grip resin and the third grip resin is 9:1:1, and finally a hot melt rubber is obtained.

[0073] Example 8

[0074] The difference from Example 1 is that 40 parts of emulsion-polymerized butadiene styrene rubber, 40 parts of solution-polymerized butadiene styrene rubber, 20 parts of epoxidized natural rubber, 140 parts of carbon black, 30 parts of the first grip resin, 30 parts of the second grip resin, 30 parts of the third grip resin, 32 parts of environmentally friendly aromatic oil, 3.5 parts of zinc oxide, 1.0 part of stearic acid, 0.5 part of magnesium oxide, 1.0 part of protective wax, 3.0 parts of antioxidant 4020, 2.0 parts of antioxidant RD, 1.8 parts of sulfur, 1.9 parts of accelerator NS, and 0.1 part of accelerator ZBEC are used to finally obtain hot-melt rubber.

[0075] The above embodiments are all carried out in the same mixing manner as follows:

[0076] Step (1) Preparation of rubber solution: The raw rubber is crushed to 2.0 mm by a rubber crusher and then dissolved in n-hexane solvent for the first stirring and mixing. The temperature of the first stirring and mixing is 60° C., the speed of the first stirring and mixing is 100 rpm, and the stirring time of the first stirring and mixing is 5 hours to form a uniformly dispersed mixed rubber solution with a mass concentration of 15%.

[0077] Step (2) Preparation of carbon black slurry: After the carbon black is dispersed and crushed to 10 μm in a ball mill, it is added to n-hexane and mixed and dispersed at a temperature of 50° C. and a speed of 500 rpm for 40 minutes to form a uniformly dispersed n-hexane suspension slurry with a mass concentration of 30%.

[0078] Step (3) Preparation of resin solution: The resin was dissolved in n-hexane solvent, and the mixture was stirred at 70° C. and 100 rpm for 5 h until a uniformly dispersed mixed resin solution was formed with a mass concentration of 20%.

[0079] Step (4) Preparation of mixed rubber solution: Stirring and mixing the carbon black slurry obtained in step (2) and the rubber solution obtained in step (1), controlling the stirring temperature to be between 50° C., the stirring speed to be 100 rpm, and the time to be controlled to be 80 min, until the carbon black and the rubber are evenly contacted and mixed;

[0080] Step (5) final rubber solution preparation: gradually adding the mixed resin solution obtained in step (3) to the carbon black-rubber solution obtained in step (4), and adding additives such as a softener, an activation system, and a protective system to obtain a mixed masterbatch solution;

[0081] Step (6) Preparation of mixed masterbatch: The mixed solution obtained in step (5) is flocculated and precipitated in a coagulator, the temperature during the flocculation process is 105°C, the flocculation medium is liquid water, and the rubber masterbatch is obtained after solvent devolatilization, the temperature during the devolatilization process is 125°C, and the devolatilization method is continuous extrusion devolatilization by a single screw extruder.

[0082] Step (7) Preparation of final rubber mix: The mixed masterbatch prepared in step (6) is added into an internal mixer, the temperature is controlled at 60° C., the rotation speed is 55 rpm, and the top plug is installed after mixing for 30 seconds. Then, a vulcanization system additive is added and mixed for 40 seconds, and the top plug is cleaned. Then, the masterbatch is internally mixed for 30 seconds and the rubber is discharged to obtain the final rubber mix;

[0083] Step (8) vulcanization: Add the final rubber mix into a vulcanization mold, control the vulcanizer temperature at 175° C., and vulcanize for a period of time in accordance with the process positive vulcanization time to obtain hot melt rubber.

[0084] The physical and mechanical effects of the comparative rubber compositions are listed in Table 1.

[0085] Comparative Example 1

[0086] The solution polymerized styrene-butadiene rubber is 100 parts, the carbon black N115 is 90 parts, the uniform resin is SL-300 30 parts, the environmentally friendly aromatic hydrocarbon is 16 parts, the zinc oxide ZnO is 3.0 parts, the antioxidant 4020 is 3.0 parts, the stearic acid SA is 2.0 parts, the antioxidant RD is 2.0 parts, the sulfur is 1.5 parts, and the accelerator NS is 2.0 parts; among them, see the specific formula Table 1.

[0087] Comparative Example 2

[0088] The composition comprises 50 parts of emulsion-polymerized butadiene styrene rubber, 50 parts of solution-polymerized butadiene styrene rubber, 115 parts of carbon black, 20 parts of a first grip resin, 20 parts of a second grip resin, 25 parts of a third grip resin, 6 parts of environmentally friendly aromatic oil, 3.5 parts of zinc oxide, 1.0 parts of stearic acid, 0.5 parts of magnesium oxide, 1.0 parts of protective wax, 3.0 parts of antioxidant 4020, 2.0 parts of antioxidant RD, 1.8 parts of sulfur, 1.9 parts of accelerator NS and 0.1 parts of accelerator ZBEC; see formula Table 1 for details.

[0089] Comparative Example 3

[0090] The composition includes 45 parts of emulsion-polymerized butadiene styrene rubber, 45 parts of solution-polymerized butadiene styrene rubber, 10 parts of epoxidized natural rubber, 125 parts of carbon black, 25 parts of the first grip resin, 25 parts of the second grip resin, 25 parts of the third grip resin, 16 parts of environmentally friendly aromatic oil, 3.5 parts of zinc oxide, 1.0 parts of stearic acid, 0.5 parts of magnesium oxide, 1.0 parts of protective wax, 3.0 parts of antioxidant 4020, 2.0 parts of antioxidant RD, 1.8 parts of sulfur, 1.9 parts of accelerator NS and 0.1 parts of accelerator ZBEC. For details, see formula Table 1.

[0091] Comparative Example 4

[0092] The difference from Example 1 is that 70 parts of emulsion-polymerized butadiene styrene rubber, 30 parts of solution-polymerized butadiene styrene rubber, 75 parts of carbon black, 8 parts of the first grip resin, 20 parts of the second grip resin, 32 parts of the third grip resin, 5.0 parts of environmentally friendly aromatic oil, 3.5 parts of zinc oxide, 1.0 parts of stearic acid, 0.5 parts of magnesium oxide, 1.0 parts of protective wax, 3.0 parts of antioxidant 4020, 2.0 parts of antioxidant RD, 1.8 parts of sulfur, 1.9 parts of accelerator NS, and 0.1 parts of accelerator ZBEC are used; finally, hot-melt rubber is obtained.

[0093] Comparative Example 5

[0094] The difference from Example 1 is that the grip resin only includes the first grip resin and the second grip resin, and hot melt rubber is finally obtained.

[0095] Comparative Example 6

[0096] The difference from Example 1 is that the grip resin only includes the second grip resin and the third grip resin, and hot melt rubber is finally obtained.

[0097] Comparative Example 7

[0098] The difference from Example 1 is that the grip resin only includes the first grip resin and the third grip resin, and hot melt rubber is finally obtained.

[0099] The above comparative examples were all mixed in the same manner as follows:

[0100] One-stage mixing:

[0101] (1) Set the mixer temperature to 100°C and the speed to 55 rpm. Add the raw rubber to the mixer and mix for 30 seconds. Lift the top plug. Then add 2 / 3 carbon black and 2 / 3 resin to the mixer. Mix for 40 seconds and lift the top plug to clean. Then add 1 / 3 carbon black, 1 / 3 resin and oil. Mix for 40 seconds and lift the top plug. Mix for 40 seconds and lift the top plug to clean. Mix for 30 seconds and control the temperature at 155°C to discharge the rubber.

[0102] Second stage mixing:

[0103] Add the first stage of rubber prepared in step (1) into an internal mixer and control the temperature at 100°C and the speed at 55 rpm. Mix for 30 seconds and then close the top bolt. Then add softener, activation system and protective system into the internal mixer and mix for 40 seconds and then clean the top bolt. Then mix for 40 seconds and then close the top bolt. Then mix for 30 seconds and control the temperature at 150°C to discharge the rubber.

[0104] (3) Preparation of final rubber mix: The mixed masterbatch prepared in step (6) is added to an internal mixer, the temperature is controlled at 60° C., the speed is 55 rpm, and the top plug is installed after mixing for 30 seconds. Then, a vulcanization system additive is added, mixed for 40 seconds, the top plug is cleaned, and then the masterbatch is internally mixed for 30 seconds to remove the glue, thereby obtaining the final rubber mix;

[0105] (4) Vulcanization: Add the final rubber mix into a vulcanization mold, control the temperature of the vulcanizer to 175° C., and vulcanize for a period of time in accordance with the process positive vulcanization time to obtain a hot melt rubber composition.

[0106] The physical and mechanical effects of the comparative rubber compositions are listed in Tables 1 and 2.

[0107] Performance Testing

[0108] The tensile properties are tested according to GB / T 528-2009 (Determination of tensile stress-strain properties of vulcanized rubber or thermoplastic rubber);

[0109] The hardness test is carried out in accordance with GB / T 531.1-2008 (Test method for indentation hardness of vulcanized rubber or thermoplastic rubber Part 1: Shore hardness method (Shore hardness);

[0110] The dispersion of fillers (such as carbon black) is tested in accordance with GB / T 6030-2006 (Rapid comparative method for evaluation of carbon black / silica dispersion in rubber);

[0111] The dynamic thermomechanical properties are tested in accordance with GB / T 9870.1-2006 (Determination of dynamic properties of vulcanized rubber or thermoplastic rubber Part 1: General rules); tanδ@80℃ characterizes the grip performance of the rubber composition at 80℃ under the actual use conditions of racing tires, and the higher the value, the better; E'@80℃ characterizes the handling performance of the rubber composition under 80℃, and the higher the value, the better; Tg characterizes the glass transition temperature of the material.

[0112] Processing properties are subjective observations of rubber masterbatch during the mixing process and can be divided into:

[0113] "Poor" means that fillers (such as carbon black) and resins are difficult to add and slip during the masterbatch processing, and the viscosity is high during the discharge process, making it difficult to discharge.

[0114] "General" means that during the masterbatch processing, fillers (such as carbon black) and resins are added slowly and slightly slippery. During the discharge process, the viscosity is slightly high and manual assistance is required for discharge.

[0115] "Good" means that during the masterbatch processing, there is no difficulty in adding fillers (such as carbon black) and resins, no slipping, etc., the debonding process is smooth, and the surface of the sheets coming out of the mixing mill is smooth.

[0116] The hot melt rubber compositions prepared in the examples and comparative examples were tested for processing performance, filler (carbon black) dispersion performance, tensile properties, hardness, and dynamic thermomechanical properties. The specific test results are shown in Tables 1 and 2.

[0117] Table 1

[0118]

[0119]

[0120] Table 2

[0121]

[0122] It can be seen from the experimental implementation results of the comparative examples and embodiments given in Table 1 that, compared with the ordinary racing tire formulation in comparative example 1, the formulations of embodiments 1 to 3 have better hardness, elongation, grip, control and other properties, and can provide excellent comprehensive performance for the racing tire tread to meet the needs of the competition.

[0123] Compared with Comparative Examples 1-2, the introduction of low glass transition temperature rubber in Examples 1-3 can reduce the glass transition temperature of the formula, meeting the requirements of tire transportation and storage at lower temperatures. At the same time, in a regular racing environment, the tires can be used to run hot tires by themselves to avoid the tire warming process.

[0124] At the same time, from the comparison between Examples 1 to 3 and Comparative Example 2, it can be seen that, compared with dry mixing, the wet mixing method developed by the rubber composition can fill more carbon black and resin and other materials to promote performance improvement. Comparative Example 3 compared with Example 1 shows that under the conditions of filling carbon black with 125 parts, resin with 75 parts, and oil with 16 parts, the wet process has good processing performance, avoiding slipping during processing and the phenomenon that the rubber in the mixer is difficult to discharge, while the dry process can hardly meet the processing requirements.

[0125] From the comparison between comparative examples 5 to 7 and embodiments 1 to 7, it can be seen that the use of the first grip resin, the second grip resin and the third grip resin with three ring and ball softening point temperature gradients can improve the synergistic effect of the three grip resins, thereby ensuring that the hot melt rubber has good grip performance.

[0126] From the comparison between Example 1 and Examples 4 to 7, it can be seen that, compared with the mass ratio of the first grip resin, the second grip resin and the third grip resin of 9:1:1 in Example 7, the mass ratio of the first grip resin, the second grip resin and the third grip resin in the preferred Examples 1 and 4 to 6 is 1-3:1-3:1-3, which is more helpful to improve the synergistic effect of the three grip resins.

[0127] From the comparison between Comparative Example 4 and Examples 1 to 7, it can be seen that the synergistic effect of each component can be optimized only by controlling the weight of each component within a certain range. If it exceeds the range, the comprehensive synergistic effect of each component is poor.

[0128] From the comparison between Example 8 and Example 1, it can be seen that by changing the weight of each component within the preferred range of each component, the synergistic effect of each component can still be ensured, thereby ensuring that the hot melt rubber has good grip performance.

[0129] From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects:

[0130] The present invention creatively adopts a grip resin with a temperature gradient of three ring softening points in a temperature range of 80°C or above, thereby ensuring that the hot melt rubber has good hot melt performance, grip performance, and handling performance. Specifically, when the car is in the race, the tread temperature is often between 80°C and 100°C at a lower running speed. At this time, the first grip resin undergoes hot melt gelation to ensure the grip performance of the hot melt rubber. As the running intensity increases, the second grip resin under the condition of 100°C to 135°C is activated and acts together with the first grip resin on the grip performance, that is, compared with the traditional racing tire formula, the hot melt rubber composition of the present application has a better temperature response hot melt performance, that is, the grip resin can exert hot melt performance at a lower tire temperature, while avoiding the tire warming step at room temperature, so as to fully meet the requirements of various hot melt racing events commonly used in the market. At the same time, the third grip resin can ensure the thermal stability and rigid support of the tire under high temperature operation. In addition, the use of a higher weight portion of the above carbon black in the tread can further ensure the thermal stability and dry grip performance of the tire during operation. With the synergistic effect of other additives such as softener, activation system, protection system and vulcanization system, hot melt rubber has better comprehensive properties.

[0131] The above are only embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A hot melt rubber composition, characterized in that: In parts by weight, the hot melt rubber composition comprises: 100 parts of raw rubber system; 30 to 180 parts of grip resin; 80-155 parts of carbon black; 8 to 35 parts of softener; 2.2 to 7.3 parts of activation system; 3.5 to 8.5 parts of protection system; 3.0 to 4.7 parts of the vulcanization system; The grip resin includes a first grip resin, a second grip resin and a third grip resin, the first grip resin has a ring and ball softening point temperature of 80°C to 100°C, the second grip resin has a ring and ball softening point temperature of 101°C to 135°C, and the third grip resin has a ring and ball softening point temperature of 136°C to 150°C.

2. The hot melt rubber composition according to claim 1, characterized in that: In parts by weight, the grip resin is selected from a combination of 10 to 90 parts of the first grip resin, 10 to 45 parts of the second grip resin and 10 to 45 parts of the third grip resin; and / or the mass ratio of the first grip resin, the second grip resin and the third grip resin is 1 to 9: 1 to 3: 1 to 3, preferably 1 to 3: 1 to 3: 1 to 3.

3. The hot melt rubber composition according to claim 1, characterized in that: The first grip resin is a C9 copolymer resin, and the monomers forming the first grip resin are preferably selected from any one or more of styrene, methyl styrene, indene and its derivatives and coumarone; the number average molecular weight of the first grip resin is preferably between 1500 and 2500, and the specific structure of the first grip resin is preferably as shown in Formula I: Wherein, n in the formula I is ≥ 1; and / or, the second grip resin is a hydrogenated cyclopentadiene resin, and the number average molecular weight of the second grip resin is between 1600 and 2000; And / or, the third grip resin is a terpene phenol resin, preferably the number average molecular weight of the third grip resin is between 1200 and 3000, and preferably the specific structure of the third grip resin is as shown in Formula II: Wherein, in the formula II, n≥1, m≥1.

4. The hot melt rubber composition according to any one of claims 1 to 3, characterized in that The glass transition temperature of the raw rubber system is -20°C to 10°C; the raw rubber system comprises 35 to 60 parts by weight of emulsion-polymerized styrene-butadiene rubber, 35 to 60 parts by weight of solution-polymerized styrene-butadiene rubber and 5 to 30 parts by weight of auxiliary rubber; And / or, the mass content of styrene in the emulsion polystyrene butadiene rubber is 15% to 45%, 1,2-vinyl accounts for 10% to 30% of the total mass of diene components in the emulsion polystyrene butadiene rubber, and the glass transition temperature of the emulsion polystyrene butadiene rubber is -25°C to -20°C; And / or, the mass content of styrene in the solution polymerized styrene butadiene rubber is 15% to 45%, 1,2-vinyl accounts for 25% to 55% of the total mass of the diene component of the solution polymerized styrene butadiene rubber, and the glass transition temperature of the solution polymerized styrene butadiene rubber is -38°C to -22°C; And / or, the auxiliary rubber is a rubber polymer formed by homopolymerization or copolymerization of butadiene, styrene, pentadiene, C4 olefin monomer or C5 olefin monomer, and the auxiliary rubber is selected from any one or more of butadiene-styrene copolymer rubber, epoxidized natural rubber, butadiene rubber, isoprene rubber and butadiene-pentadiene rubber; and / or the molecular weight of the auxiliary rubber is 3000 to 1000000, and / or the glass transition temperature of the auxiliary rubber is -120°C to -40°C.

5. The hot melt rubber composition according to any one of claims 1 to 3, characterized in that: The carbon black is 95 to 145 parts by weight, and / or the particle size of the carbon black is distributed between 5.0 nm and 25 nm, and / or the specific surface area STSA of the carbon black is between 150 m 2 / g~230m 2 / g, and / or the compressed DBP oil absorption value of the carbon black is between 80mL / 100g and 120mL / 100g, and / or the grade of the carbon black is selected from any one or more of series 1 and series 2 in the ASTM standard.

6. The hot melt rubber composition according to any one of claims 1 to 3, characterized in that: The softener is selected from any one or more of liquid butadiene-styrene copolymer rubber, liquid isoprene rubber, liquid cis-butadiene rubber, naphthenic oil, heavy naphthenic oil, environmentally friendly aromatic oil, modified environmentally friendly aromatic oil and modified vegetable soybean oil; and / or the molecular weight of the softener is between 4000 and 8500, and / or the kinematic viscosity of the softener is between 4.0 mm 2 / s~12mm 2 / s.

7. The hot melt rubber composition according to any one of claims 1 to 3, characterized in that: In parts by weight, the activation system includes 2.0 to 5.0 parts of zinc oxide, 0.1 to 1.5 parts of stearic acid and 0.1 to 0.8 parts of magnesium oxide.

8. The hot melt rubber composition according to any one of claims 1 to 3, characterized in that: In parts by weight, the protective system includes 1.5 to 3.5 parts of protective wax and 2.0 to 5.0 parts of antioxidant; and / or the protective wax is selected from any one or more of PE wax, microcrystalline protective wax and paraffin wax; and / or the antioxidant is selected from any one or more of N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine 4020, 2,2,4-trimethyl-1,2-dihydroquinoline polymer RD, N,N'-xylyl-p-phenylenediamine DTPD, N-isopropyl-N'-phenyl-p-phenylenediamine 4010NA, 2-mercaptobenzimidazole MB and N-cyclohexyl-N'-phenyl-p-phenylenediamine 4010.

9. The hot melt rubber composition according to any one of claims 1 to 3, characterized in that: In parts by weight, the vulcanization system includes 1.5 to 2.5 parts of an accelerator and 1.5 to 2.2 parts of a vulcanizing agent; and / or the vulcanization system is selected from any one or more of insoluble sulfur, soluble sulfur, 2-mercaptobenzothiazole M, dicumyl peroxide, zinc dibenzyldithiocarbamate ZBEC, 2,2'-dithiodibenzothiazole DM, N-cyclohexyl-2-benzothiazole sulfenamide CZ, diphenylguanidine DPG, N-tert-butyl-2-benzothiazole sulfenamide NS, N,N-2-dicyclohexyl-2,2-dibenzothiazole sulfenamide DZ and zinc dimethyldithiocarbamate ZDMC.

10. A method for preparing hot melt rubber, characterized in that: The preparation method comprises: Step S1, stirring and mixing raw materials including a raw rubber system, a grip resin, carbon black, a softener, an activation system, a protective system and an organic solvent to obtain a mixture; Step S2, flocculating and devolatilizing the mixture in sequence to obtain a mixed masterbatch; Step S3, subjecting the materials including the mixed masterbatch and the vulcanization system to mixing, debonding and vulcanization treatment in sequence to obtain the hot melt rubber; Wherein, the auxiliary agents including softener, activator and protective system are added in step S1 or step S3; The formula of the raw rubber system, the grip resin, the carbon black, the softener, the activation system, the protective system, the organic solvent, the softener, the activator, the protective system and the vulcanization system is independently selected from the hot melt rubber composition according to any one of claims 1 to 9.

11. The preparation method according to claim 10, characterized in that: The step S1 comprises: Step S11, crushing the raw rubber system and mixing it with a first organic solvent to obtain a rubber solution; Step S12, crushing the carbon black and mixing it with a second organic solvent to obtain a carbon black slurry; Step S13, performing a third stirring mixing process on the grip resin and the third organic solvent to obtain a resin solution; Step S14, first mixing the rubber solution, the carbon black slurry and the resin solution to obtain the mixture; Preferably, step S14 includes: The rubber solution and the carbon black slurry are mixed for a second time to obtain a carbon black-rubber solution; performing a third mixing of the carbon black-rubber solution and the resin solution to obtain the mixture; Wherein, in the step S11, the average particle size of the raw rubber system after crushing is 1.0 mm to 3.0 mm, and / or the mass concentration of the rubber solution is 8.0% to 25%, and / or the temperature of the first stirring and mixing is 45° C. to 80° C., and / or the speed of the first stirring and mixing is 30 rpm to 300 rpm, and / or the time of the first stirring and mixing is 2.0 h to 10 h; In the step S12, the average particle size of the carbon black after crushing is 0.1 μm to 20 μm, and / or the solid content of the carbon black slurry is 20% to 50%, and / or the temperature of the second stirring and mixing is 35° C. to 60° C., and / or the speed of the second stirring and mixing is 50 rpm to 1000 rpm, and / or the time of the second stirring and mixing is 30 min to 60 min; In the step S13, the mass concentration of the resin solution is 10% to 30%, and / or the temperature of the third stirring and mixing is 60° C. to 80° C., and / or the rotation speed of the third stirring and mixing is 30 rpm to 300 rpm, and / or the time of the third stirring and mixing is 0.5 h to 10 h; And / or, the conditions of the first mixing, the second mixing and the third mixing are independently selected from the following: a mixing temperature between 40° C. and 60° C., a stirring speed between 30 rpm and 300 rpm, and a mixing time between 30 min and 180 min; And / or, the first organic solvent, the second organic solvent and the third organic solvent are each independently selected from any one or more of aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, chlorinated hydrocarbon solvents, ketone solvents, ether solvents and ester solvents; preferably, the aliphatic hydrocarbon solvent is selected from any one or more of gasoline, cycloalkanes, substituted cycloalkanes and normal alkanes; preferably, the aromatic hydrocarbon solvent is selected from any one or more of benzene, toluene, xylene and styrene; preferably, the chlorinated hydrocarbon solvent is selected from any one or more of dichloromethane, chloroform, carbon tetrachloride, dichloroethane, chlorobenzene, tetrachloroethylene and chlorotoluene.

12. The preparation method according to claim 10, characterized in that: In the step S2, The flocculation method includes: contacting the mixture with a coagulation medium to perform the flocculation, wherein the coagulation medium is selected from any one or more of nitrogen, carbon dioxide, liquid water and water vapor; Alternatively, the mixture is flocculated by shear drying, and preferably the shear drying method is selected from any one or more of spray drying, high temperature flash evaporation and mechanical compression.

13. The preparation method according to claim 10, characterized in that: In the step S2, the devolatilization method is selected from any one or more of continuous extrusion devolatilization by a single screw extruder, continuous extrusion devolatilization by a twin screw extruder, continuous microwave radiation devolatilization, open mill devolatilization and internal mixer mixing high temperature devolatilization.

14. A hot melt rubber, characterized in that: The hot melt rubber is prepared by the preparation method according to any one of claims 10 to 13.

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