CN111073076A - Wet-skid-resistant rubber composition for green tire and preparation method thereof - Google Patents
Wet-skid-resistant rubber composition for green tire and preparation method thereof Download PDFInfo
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Abstract
The invention provides an anti-slippery rubber composition for green tires and a preparation method thereof. According to the invention, alkylphenol polyoxyethylene ether and a silane coupling agent are subjected to copolymerization reaction to generate an organic silicon/alkylphenol polyoxyethylene ether copolymer, the surface of the nano white carbon black particle is subjected to multi-point anchoring modification, then the solution polymerized styrene-butadiene rubber cement is subjected to acylation treatment, and finally the solution polymerized styrene-butadiene rubber cement is coated on the surface of the nano white carbon black particle to form a barrier layer with high connection strength, and finally the barrier layer is directly mixed and condensed with the solution polymerized styrene-butadiene rubber cement to prepare the rubber composition for the wet-resistant pulley tire tread. The invention endows the nano white carbon black with super-dispersibility, not only solves the problem of easy agglomeration of the nano white carbon black, but also can prevent the problem of agglomeration again under the conditions of long-term storage, high temperature and high shear, and simultaneously improves the compatibility of the nano white carbon black and solution polymerized styrene butadiene rubber. The preparation method is green, environment-friendly, simple and feasible, and is suitable for industrial production.
Description
Technical Field
The invention relates to a rubber composition for a tread of an anti-wet-skid tire and a preparation method thereof, in particular to a rubber composition for a tread of an anti-wet-skid tire, which is prepared by solution-polymerized styrene-butadiene rubber filled with ultra-dispersed nano white carbon black, and a preparation method thereof.
Background
Under the background that low carbon, green and environmental protection become common consensus of the whole society, the automobile tire industry is actively adapting and guiding the trend and trend, and the requirement for high performance of tires is higher and higher. This requires that the balance of the "magic triangle" performance of the tire tread rubber must be significantly improved, that is, the tire tread rubber has good wet skid resistance, excellent wear resistance and low rolling resistance.
In addition, the nano white carbon black is used as a reinforcing filler in the tire tread formula in the nineties of the last century, so that the performance of the tread rubber in the 'magic triangle' is obviously balanced and is difficult to replace in the preparation of energy-saving and environment-friendly 'green tire' tread rubber, and the application of the nano white carbon black in the aspect of tires is more and more extensive due to the higher and more requirements of the state on the aspect of tire environment protection and relevant regulations issued in the aspect of tire energy saving in the United states and European Union.
However, the nano white carbon black has small particle size, large specific surface area and high surface energy, and a large number of silicon hydroxyl groups exist on the surface, so that the nano white carbon black has the characteristics of hydrophilicity and easiness in self-polymerization, has poor compatibility with a polymer matrix, and is not easy to disperse uniformly in the mixing process of the nano white carbon black and a rubber material, thereby not only influencing the filling modification effect, but also damaging the performance of the rubber material. From the perspective of the expected effect of the inorganic powder filling modified synthetic rubber, the smaller the particle size of the inorganic powder particles, the better the modification effect, but in the application process of the high-fine inorganic powder, a technical problem inevitably occurs, namely, the high-fine powder is more difficult to be mixed, infiltrated and dispersed by the rubber material because of the reduction of the particle size, the specific surface area is increased, the surface energy is improved, the self-aggregation capability is stronger, and the high-fine powder is more difficult to be mixed, infiltrated and dispersed by the rubber material. Therefore, the problem of dispersion of the high-fine inorganic powder in the rubber has become a bottleneck in preparing high-performance rubber materials.
In the prior art, the research on the modified nano white carbon black filled rubber material is mainly prepared by a method of coating the modified nano white carbon black particle surface filled rubber material by a coupling agent or a surfactant and a graft polymer. Such as: CN200910238122.3 discloses a preparation method of a white carbon black/clay/rubber nano composite material, which comprises the steps of mixing a certain amount of clay and deionized water, strongly stirring for more than 5 hours, standing for more than 24 hours to obtain a stable clay suspension, and ensuring that the mass content of the clay is 1.5-3 wt%. And similarly, mixing a certain amount of white carbon black and deionized water, strongly stirring or ultrasonically vibrating to prepare a stable white carbon black/water suspension, so that the mass content of the white carbon black is 1-4 wt%, preparing a mixed suspension with the mass ratio of clay/white carbon black of 1/5-2/1 according to the content, and performing spray drying to prepare the clay/white carbon black composite filler. Then filling the clay/white carbon black composite filler and the silane coupling agent into the sizing material on an open mill to prepare the white carbon black/clay/rubber nano composite material. CN107189124A discloses a preparation method of an aging-resistant modified natural rubber, which comprises the steps of drying white carbon black for 4-8 hours at the temperature of 200-240 ℃, plastifying the dried white carbon black with abietic acid type resin acid accounting for 4-7% of the weight of the white carbon black and chlorohydrin rubber accounting for 12-18% of the weight of the white carbon black for 20-25 minutes at the temperature of 140-160 ℃, continuously extracting the white carbon black for 24 hours after discharging, and drying the white carbon black at the temperature of 120-150 ℃ after volatilizing the solvent; then mixing the natural rubber, the modified white carbon black and the multi-walled carbon nano-tube according to the weight ratio of 10:1.3-1.6:0.6-0.7, mixing the rubber material in a double-roll open mill, mixing to obtain a sheet, and finally mixing the obtained mixtureAnd granulating by an extruder on the rubber sheet to obtain the ageing-resistant modified natural rubber. CN102558627A discloses a preparation method of white carbon black modified styrene-butadiene rubber for green tires, which comprises the steps of firstly mixing white carbon black and water to obtain white carbon black-water suspension, wherein the mass ratio of the white carbon black to the water is 5% -20%, then carrying out surface treatment on the white carbon black in a water bath environment to enable the surface of the white carbon black to be organic, adjusting the pH value of the white carbon black-water suspension to 9-12, then uniformly mixing the white carbon black-water suspension after the pH value adjustment with styrene-butadiene latex to obtain styrene-butadiene rubber liquid slurry added with the white carbon black, and finally taking the styrene-butadiene rubber liquid slurry containing the white carbon black as a raw material, and preparing the modified styrene-butadiene rubber containing the white carbon black by using an emulsion blending and co-. CN106589485A discloses a modified white carbon black by using AEO (aliphatic polyoxyethylene ether) and silane coupling agent together and a method for compounding the modified white carbon black with rubber, which comprises the steps of firstly mixing white carbon black with water to obtain white carbon black-water suspension, wherein the mass of the white carbon black accounts for 5-20% of the total mass of the suspension, adjusting the temperature of the white carbon black suspension to 35-90 ℃ by a heating device, ensuring that the white carbon black suspension is in a flowing state during the period, then adding silane coupling agent into the white carbon black suspension, then adding AEO for modification, wherein the mass of AEO is 1-100% of the mass of the white carbon black, the mass of the silane coupling agent is 1-100% of the mass of the white carbon black, carrying out white carbon black modification for 0.5-10 hours by matching with ultrasound, finally mixing white carbon black modified by using AEO and silane coupling agent as raw materials, to prepare the rubber/modified white carbon black composite material. CN106832417A discloses a method for modifying white carbon black by using aliphatic polyoxyethylene ether and compounding the white carbon black with rubber, which comprises the steps of firstly mixing white carbon black with water to obtain white carbon black-water suspension, wherein the mass of the white carbon black accounts for 5-20% of the total mass of the suspension, adjusting the temperature of the white carbon black suspension to be higher than the melting point of the aliphatic polyoxyethylene ether, ensuring that the white carbon black suspension is in a flowing state in the period, adding the aliphatic polyoxyethylene ether into the white carbon black suspension, fully modifying the white carbon black for 0.5-10 hours by matching with ultrasound, then dehydrating and drying the white carbon black suspension to obtain modified white carbon black powder, and finally using the aliphatic polyoxyethylene ether toThe white carbon black modified by polyoxyethylene ether is compounded with various rubbers to prepare the rubber/modified white carbon black composite material. CN1323687A discloses a method for preparing a green tire with a rubber-polyurethane elastomer composite structure by using nano white carbon black modified polyurethane, which comprises the steps of selecting fumed silica with the average particle size of 1-40 nm, adding an ethanol solution of a silane coupling agent containing isocyanate groups or amino groups, uniformly mixing, adding the mixture into oligomer polyol, heating to 220-240 ℃ under stirring, simultaneously vacuumizing to-0.095-0.098 Mpa, and dehydrating and dealcoholizing for 2-3 hours; cooling to below 60 ℃, adding diisocyanate, reacting for 1-2 hours at 70-80 ℃ and under the vacuum degree of-0.095-0.098 Mpa to obtain the prepolymer of the nano white carbon black modified polyurethane, and finally mixing the prepolymer of the nano white carbon black modified polyurethane with the polyurethane elastomer to prepare the green tire product with the rubber-polyurethane elastomer composite structure. The high performance NR composites were exemplified by the kukukuuqiang ("latex blending method" natural rubber/silica nanocomposite microstructure and performance control, 2010, master thesis at hainan university): the natural rubber/silicon dioxide nano composite material is prepared by adopting a latex blending method, and the nano silicon dioxide (SiO) is modified by using a gamma-methacryloxypropyltrimethoxysilane coupling agent (MPS)2) Then grafting polymethyl methacrylate (PMMA) through emulsion polymerization to obtain nano silicon dioxide particles (SiO) with a core-shell structure2MPS-PMMA) and finally directly blended with MMA modified natural latex (NR-PMMA) to obtain natural rubber/silica nanocomposites. Lewenji et al prepared clay/white carbon black composite filler by spray drying process for replacing part of white carbon black to jointly reinforce solution polymerized butadiene styrene rubber/butadiene rubber composite material. Although the compatibility of the nano white carbon black and the rubber matrix is improved by the method, the methods have certain limitations, and mainly have the defects of long reaction time, high energy consumption, large environmental pollution, complex operation and the likeAgglomeration and the like occur.
Disclosure of Invention
The invention aims to provide a rubber composition filled with ultra-dispersed nano white carbon black for a tread of a moisture-resistant tire. According to the invention, alkylphenol polyoxyethylene ether and a silane coupling agent are subjected to copolymerization reaction to generate an organic silicon/alkylphenol polyoxyethylene ether copolymer, the surface of the nano white carbon black particle is subjected to multi-point anchoring modification, then the solution polymerized styrene-butadiene rubber cement is subjected to acylation treatment, and finally the solution polymerized styrene-butadiene rubber cement is coated on the surface of the nano white carbon black particle to form a barrier layer with high connection strength, and finally the barrier layer is directly mixed and condensed with the solution polymerized styrene-butadiene rubber cement to prepare the rubber composition for the wet-resistant pulley tire tread. The invention endows the nano white carbon black with super-dispersibility, not only solves the problem of easy agglomeration of the nano white carbon black, but also can prevent the problem of agglomeration again under the conditions of long-term storage, high temperature and high shear, simultaneously improves the compatibility of the nano white carbon black and the solution polymerized styrene butadiene rubber, and ensures that nano white carbon black particles can be uniformly dispersed into a solution polymerized styrene butadiene rubber matrix.
The "parts" in the present invention mean parts by mass.
The invention relates to a rubber composition for tire treads, which mainly comprises the following components in percentage by mass of solution polymerized styrene-butadiene rubber cement (dry rubber):
(1) 100 percent of solution polymerized styrene-butadiene rubber cement (dry rubber)
(2) 60-120% of ultra-dispersed nano white carbon black
The ultra-dispersed nano white carbon black is prepared by performing copolymerization reaction on alkylphenol ethoxylates and a silane coupling agent to generate a product, namely, an organic silicon/alkylphenol ethoxylate copolymer to perform multi-point anchoring modification on the surface of nano white carbon black particles, then acylating solution polymerized styrene-butadiene rubber slurry by using acid anhydride, and finally coating the surface of the nano white carbon black particles, wherein the white carbon black is nano-scale and has the particle size of 10-100 nm, and the alkylphenol ethoxylate is one of nonylphenol ethoxylate (NPEO), octylphenol ethoxylate (OPEO), dodecylphenol ethoxylate (DPEO) and dinonylphenol ethoxylate (DNPEO), preferably the NPEO silane coupling agent can be one of gamma-aminopropyltriethoxysilane (KH-550), 3-glycidoxypropyltrimethoxysilane (KH-560), vinyltriethoxysilane (A-151), N- β -aminoethyl-gamma-aminopropylmethyldimethoxysilane (KH-602), gamma-methacryloxypropyltrimethoxysilane (KH-570- β - (gamma- β) -ethoxysilane (KH- β - (A-35792-172), and preferably one of gamma-ethoxysilane (KH-172, i- β, i).
The initiator is selected from one of sodium hydroxide, potassium hydroxide, magnesium hydroxide, sodium carbonate and sodium bicarbonate, and is preferably sodium hydroxide. The acid anhydride is a binary acid anhydride compound, is selected from one of Maleic Anhydride (MAH), succinic anhydride, maleic anhydride and phthalic anhydride, and is preferably MAH. The catalyst is selected from anhydrous aluminum trichloride (AlCl)3) Boron trifluoride (BF)3) Tin tetrachloride (SnCl)4) Zinc dichloride (ZnCl)2) Preferably AlCl3。
The solution polymerized styrene-butadiene rubber cement is prepared by the solution polymerization copolymerization of a conjugated diene compound and an aryl ethylene compound. Wherein the solid content of the solution polymerized styrene-butadiene rubber cement is 5-20 w%.
The preparation of the rubber composition can be carried out solution compounding in a condensation kettle, and the specific preparation process comprises the following steps:
(1) preparing the ultra-dispersed nano white carbon black:
a, preparing an organic silicon/alkylphenol polyoxyethylene ether copolymer: taking the mass of the silane coupling agent as 100 parts, firstly adding 100 parts of the silane coupling agent and 100-200 parts of the solvent into a reactor, stirring for 1-2 hours, then adding 5-15 parts of alkylphenol polyoxyethylene ether, continuously stirring and heating until the temperature of the reactor reaches 50-70 ℃, rapidly adding 0.5-2.0 parts of initiator under the stirring condition, reacting for 5-10 hours, and then decompressing and distilling to obtain the organic silicon/alkylphenol polyoxyethylene ether.
b, preparing acylated solution polymerized styrene-butadiene rubber cement: taking the mass of the solution polymerized styrene-butadiene rubber cement as 100 parts, firstly adding 100 parts of solution polymerized styrene-butadiene rubber cement and 100-200 parts of solvent into a polymerization kettle, stirring and heating, when the temperature of the polymerization kettle reaches 40-50 ℃, rapidly adding 0.05-0.5 part of catalyst under the stirring condition, adding 5-15 parts of anhydride when the system becomes orange red, stirring and reacting for 2-4 h, adding 5-10 parts of terminator to terminate the reaction, filtering and washing to obtain the acylated solution polymerized styrene-butadiene rubber cement (the acetylation degree of the solution polymerized styrene-butadiene rubber cement is 0.5-5.0%).
c, preparing ultra-dispersed nano white carbon black: taking 100 parts by mass of nano white carbon black, adding 100 parts by mass of nano white carbon black, 5-15 parts by mass of organic silicon/alkylphenol polyoxyethylene ether copolymer and 200-400 parts by mass of solvent into a polymerization kettle, heating to 40-60 ℃, and stirring for reaction for 1-3 hours; then adding 10-30 parts of acylation solution polymerized styrene-butadiene rubber cement, stirring and reacting for 2-4 hr, and then carrying out flash evaporation, drying and grinding to obtain the ultra-dispersed nano white carbon black.
(2) Preparation of anti-wet-skid rubber composition: taking 100 parts of solution-polymerized styrene-butadiene rubber cement dry rubber by mass, adding 100 parts of solution-polymerized styrene-butadiene rubber cement (dry rubber) and 400-600 parts of solvent into a condensation kettle, stirring and mixing for 50-60 min, then adding 60-120 parts of ultra-dispersed nano white carbon black, stirring and mixing for 1-3 hr when the temperature is raised to 50-60 ℃, and finally performing wet deashing, drying and briquetting to obtain the solution-polymerized styrene-butadiene rubber composition for the anti-wet-skid tire tread.
The solvent, the terminating agent and the like adopted by the invention are not particularly limited, and the conventional auxiliary agent commonly used in the field can be adopted, the addition amount is also the conventional amount which can be calculated by the technical personnel in the field according to the amount of the dry glue, and the invention is not particularly limited.
The solvent according to the invention may be selected from cyclohexane, carbon disulphide (CS)2) Nitrobenzene, petroleum ether, tetrachloroethane, toluene, xylene, and preferably cyclohexane.
The terminating agent of the invention can be selected from one of diethylhydroxylamine, hydroxylamine sulfate and sodium dimethyl dithiocarbamate, and sodium dimethyl dithiocarbamate is preferred.
The solution polymerized styrene-butadiene rubber composition for the wet-skid-resistant green tire tread filled with the ultra-dispersed nano white carbon black firstly performs copolymerization reaction on polyether polyol and a silane coupling agent, the siloxane bond (-O-Si), ether bond (-R-O-R-) and hydroxyl (-OH) in the product organosilicon/alkylphenol polyoxyethylene ether copolymer are used as anchoring groups, and are tightly connected with the hydroxyl on the surface of the white carbon black through the action of hydrogen bonds, forming high-density polar anchor points on the surface of the white carbon black particles, then carrying out acylation reaction on the solution polymerized styrene-butadiene rubber cement by using binary acid anhydride, so that the surface of the solution polymerized styrene-butadiene rubber cement is provided with a large amount of polar group carboxyl, and finally, strong mutual attraction between molecules is generated through the polar anchoring point on the surface of the white carbon black particles and the carboxyl on the surface of the acylated solution polymerized styrene-butadiene rubber cement, so that a coating layer of the solution polymerized styrene-butadiene rubber cement is formed on the surface of the white carbon black particles. The coating layer is tightly connected with white carbon black particles, and is difficult to separate even under the action of high temperature and high shear, the chain structure of the coating layer is the same as that of the solution polymerized styrene butadiene rubber, and the nano white carbon black can be super-dispersed in the solution polymerized styrene butadiene rubber matrix without adding any surfactant (see attached figure 1).
And secondly, the ultra-dispersed nano white carbon black contains a great number of silicon-oxygen bonds, ether bonds and hydroxyl groups, has strong hydrophilicity, so that the white carbon black can easily puncture an extruded water film of a grounding part of the tire tread, the thickness of the extruded water film is greatly reduced, the rolling resistance of the tire in wet friction is improved, and the wet-skid resistance of the tread rubber is obviously improved. Meanwhile, the super-dispersibility of the nano white carbon black in the solution polymerized styrene butadiene rubber matrix greatly increases the filling amount of the nano white carbon black in the solution polymerized styrene butadiene rubber, and the modification effect is more obvious. Therefore, the 'magic triangle' performance balance of the solution-polymerized styrene-butadiene rubber composition can be obviously improved under the 'synergistic effect' of the two, and the solution-polymerized styrene-butadiene rubber composition for the wet-skid resistant tire tread with good wet-skid resistance and low rolling resistance is obtained. The method is green, environment-friendly, simple and feasible, and is suitable for industrial production.
Drawings
FIG. 1 is a scanning electron microscope photograph of modified nano white carbon black in solution polymerized styrene butadiene rubber.
As can be seen from the photographs: the ultra-dispersed nano white carbon black particles form a sea-island structure in a solution polymerized styrene butadiene rubber matrix by about 40-90 nm particles, which shows that the modified nano white carbon black particles are uniformly dispersed in the solution polymerized styrene butadiene rubber.
Detailed Description
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.
The following examples and comparative examples are given to illustrate the effects of the present invention, but the scope of the present invention is not limited to these examples and comparative examples. The "parts" described in examples and comparative examples each refer to parts by mass.
⑴ sources of raw materials:
nano white carbon black with particle size of 10-100 nm Weifang Wanli auxiliary agent Limited company
Solution polymerized styrene butadiene rubber cement SSBR2564s, 10% solids content, Mount-petrochemical company
Nonylphenol Polyoxyethylene Ether (NPEO), Haian Yongsheng chemical Co., Ltd
Dodecyl Polyoxyethylene Ether (DPEO), Haian Yongsheng chemical Co., Ltd
Gamma-aminopropyltriethoxysilane (KH-550), Nanjing chemical Co., Ltd
Vinyltriethoxysilane (A-151), Nanjing chemical Co., Ltd
Anhydrous aluminum trichloride (AlCl)3) Ningboxin and chemical Co Ltd
Maleic Anhydride (MAH) with a purity of 99%, Tianjin City Fenghua factory
Other reagents are all commercial products
⑵ analytical test methods:
measurement of acetylation degree: the test was carried out using an infrared spectrometer of Shimadzu, Japan, model IR-460.
Analyzing a sample by an electron microscope: and (3) carrying out dispersibility analysis on the sample before and after the modification of the nano white carbon black by adopting an XL-20 scanning electron microscope produced by Philips corporation in the Netherlands. And carrying out SEM analysis on the sample under the accelerating voltage of 20kV after the sample is subjected to gold spraying treatment by a surface treatment machine.
Loss factors at 0 ℃ and 60 ℃: the analysis was carried out by using a DMA Q800 type dynamic thermo-mechanical analyzer of TA company,
a double cantilever clamp mode is selected. Temperature programming is carried out at the temperature of 150 ℃ below zero to 100 ℃, the heating rate is 3 ℃/min, the amplitude is 10 mu m, the test frequency is 1Hz, 5Hz and 10Hz respectively, and the dynamic force is 1N.
Tensile strength: the method in standard GB/T528-2009 is executed.
Dispersity: the method in the standard GB/T6030-1985 is executed.
Example 1
(1) Preparing the ultra-dispersed nano white carbon black:
a, preparing an organic silicon/alkylphenol polyoxyethylene ether copolymer: adding 100 parts of KH-550 and 100 parts of cyclohexane into a reactor, stirring for 1.0hr, then adding 5.0 parts of NPEO, continuously stirring and heating until the temperature of the reactor reaches 50 ℃, rapidly adding 0.5 part of sodium hydroxide under stirring, reacting for 5.0hr, and then decompressing and distilling to obtain the KH-550/NPEO copolymer a.
b, preparing acylated solution polymerized styrene-butadiene rubber cement: 100 portions of solution polymerized styrene-butadiene rubber cement SSBR2564s and 100 portions of CS are added into a polymerization kettle2Stirring and heating, and when the temperature of the polymerization kettle reaches 40 ℃, quickly adding 0.09 part of AlCl under the stirring condition3Adding 5 parts of MAH when the system becomes orange red, stirring and reacting for 2hr, adding 5 parts of sodium ferbamate to terminate the reaction, filtering, and washing to obtain the acylated solution polymerized styrene-butadiene rubber cement a (the acetylation degree is 1.2%).
c, preparing ultra-dispersed nano white carbon black: adding 100 parts of nano white carbon black (40nm), 5 parts of KH-550/NPEO copolymer a and 200 parts of cyclohexane into a polymerization kettle, heating to 40 ℃, and stirring for reacting for 1.0 hr; then 10 parts of acylation solution polymerized styrene-butadiene rubber cement a is added, after stirring reaction for 2.0 hours, the ultra-dispersed nano white carbon black is prepared by flash evaporation, drying and grinding.
(2) Preparation of anti-wet-skid rubber composition: 100 parts of solution polymerized styrene-butadiene rubber cement SSBR2564s (dry rubber) and 400 parts of cyclohexane are taken and added into a condensation kettle to be stirred and mixed for 50min, then 60 parts of super-dispersed nano white carbon black is added, the mixture is stirred and mixed for 1hr when the temperature is raised to 50 ℃, and finally the solution polymerized styrene-butadiene rubber composition for the wet-skid resistant tire tread is prepared by wet deashing, drying and briquetting. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Example 2
(1) Preparing the ultra-dispersed nano white carbon black:
a, preparing an organic silicon/alkylphenol polyoxyethylene ether copolymer: the same as in example 1.
b, preparing acylated solution polymerized styrene-butadiene rubber cement: the same as in example 1.
c, preparing ultra-dispersed nano white carbon black: adding 100 parts of nano white carbon black (40nm), 6 parts of KH-550/NPEO copolymer a and 230 parts of cyclohexane into a polymerization kettle, heating to 45 ℃, and stirring for reacting for 1.5 hours; then adding 14 parts of acylation solution polymerized styrene-butadiene rubber cement a, stirring and reacting for 2.5 hours, and then carrying out flash evaporation, drying and grinding to obtain the ultra-dispersed nano white carbon black.
(2) Preparation of anti-wet-skid rubber composition: 100 parts of solution polymerized styrene-butadiene rubber cement SSBR2564s (dry rubber) and 450 parts of cyclohexane are taken and added into a condensation kettle to be stirred and mixed for 52min, then 80 parts of ultra-dispersed nano white carbon black is added, the mixture is stirred and mixed for 1.5hr when the temperature is raised to 52 ℃, and finally the solution polymerized styrene-butadiene rubber composition for the wet-skid resistant tire tread is prepared by wet deashing, drying and briquetting. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Example 3
(1) Preparing the ultra-dispersed nano white carbon black:
a, preparing an organic silicon/alkylphenol polyoxyethylene ether copolymer: the same as in example 1.
b, preparing acylated solution polymerized styrene-butadiene rubber cement: the same as in example 1.
c, preparing ultra-dispersed nano white carbon black: adding 100 parts of nano white carbon black (40nm), 8 parts of KH-550/NPEO copolymer a and 280 parts of cyclohexane into a polymerization kettle, heating to 45 ℃, and stirring for reacting for 1.9 hr; then 19 parts of acylation solution polymerized styrene-butadiene rubber cement a is added, after stirring reaction for 2.8 hours, the ultra-dispersed nano white carbon black is prepared by flash evaporation, drying and grinding.
(2) Preparation of anti-wet-skid rubber composition: 100 parts of solution polymerized styrene-butadiene rubber cement SSBR2564s (dry rubber) and 470 parts of cyclohexane are taken and added into a condensation kettle to be stirred and mixed for 54min, then 90 parts of ultra-dispersed nano white carbon black is added, the mixture is stirred and mixed for 1.8hr when the temperature is raised to 53 ℃, and finally the solution polymerized styrene-butadiene rubber composition for the wet-skid resistant tire tread is prepared by wet deashing, drying and briquetting. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Example 4
(1) Preparing the ultra-dispersed nano white carbon black:
a, preparing an organic silicon/alkylphenol polyoxyethylene ether copolymer: adding 100 parts of KH-550 and 150 parts of cyclohexane into a reactor, stirring for 1.5 hours, then adding 10 parts of NPEO, continuously stirring and heating until the temperature of the reactor reaches 60 ℃, rapidly adding 1.5 parts of sodium hydroxide under the stirring condition, reacting for 8.0 hours, decompressing, distilling to obtain the KH-550/NPEO copolymer b.
b, preparing acylated solution polymerized styrene-butadiene rubber cement: 100 portions of solution polymerized styrene-butadiene rubber cement SSBR2564s and 150 portions of CS are added into a polymerization kettle2Stirring and heating, and when the temperature of the polymerization kettle reaches 45 ℃, quickly adding 0.3 part of AlCl under the stirring condition3Adding 11 parts of MAH until the system becomes orange red, stirring for reaction for 3 hours, adding 8 parts of sodium feramete to terminate the reaction, performing suction filtration, and washing to obtain the acylated solution polymerized styrene-butadiene rubber cement b (the acetylation degree is 2.9%).
c, preparing ultra-dispersed nano white carbon black: adding 100 parts of nano white carbon black (40nm), 10 parts of KH-550/NPEO copolymer b and 300 parts of cyclohexane into a polymerization kettle, heating to 50 ℃, and stirring for reacting for 2.0 hr; then 21 parts of acylation solution polymerized styrene-butadiene rubber cement b is added, after stirring reaction for 3.0 hours, the ultra-dispersed nano white carbon black is prepared by flash evaporation, drying and grinding.
(2) Preparation of anti-wet-skid rubber composition: 100 parts of solution polymerized styrene-butadiene rubber cement SSBR2564s (dry rubber) and 500 parts of cyclohexane are taken and added into a condensation kettle to be stirred and mixed for 55min, then 100 parts of ultra-dispersed nano white carbon black is added, the mixture is stirred and mixed for 2.0hr when the temperature is raised to 54 ℃, and finally the solution polymerized styrene-butadiene rubber composition for the wet-skid resistant tire tread is prepared by wet deashing, drying and briquetting. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Example 5
(1) Preparing the ultra-dispersed nano white carbon black:
a, preparing an organic silicon/alkylphenol polyoxyethylene ether copolymer: the same as in example 4.
b, preparing acylated solution polymerized styrene-butadiene rubber cement: the same as in example 4.
c, preparing ultra-dispersed nano white carbon black: adding 100 parts of nano white carbon black (40nm), 11 parts of KH-550/NPEO copolymer b and 320 parts of cyclohexane into a polymerization kettle, heating to 53 ℃, and stirring for reacting for 2.3 hours; then adding 23 parts of acylation solution polymerized styrene-butadiene rubber cement b, stirring and reacting for 3.2 hours, and then carrying out flash evaporation, drying and grinding to obtain the ultra-dispersed nano white carbon black.
(2) Preparation of anti-wet-skid rubber composition: 100 parts of solution polymerized styrene-butadiene rubber cement SSBR2564s (dry rubber) and 530 parts of cyclohexane are taken and added into a condensation kettle to be stirred and mixed for 56min, then 105 parts of ultra-dispersed nano white carbon black is added, the mixture is stirred and mixed for 2.2hr when the temperature is raised to 56 ℃, and finally the solution polymerized styrene-butadiene rubber composition for the wet-skid resistant tire tread is prepared by wet deashing, drying and briquetting. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Example 6
(1) Preparing the ultra-dispersed nano white carbon black:
a, preparing an organic silicon/alkylphenol polyoxyethylene ether copolymer: the same as in example 4.
b, preparing acylated solution polymerized styrene-butadiene rubber cement: the same as in example 4.
c, preparing ultra-dispersed nano white carbon black: adding 100 parts of nano white carbon black (40nm), 12 parts of KH-550/NPEO copolymer b and 350 parts of cyclohexane into a polymerization kettle, heating to 55 ℃, and stirring for reacting for 2.5 hours; then adding 25 parts of acylation solution polymerized styrene-butadiene rubber cement b, stirring and reacting for 3.5 hours, and then carrying out flash evaporation, drying and grinding to obtain the ultra-dispersed nano white carbon black.
(2) Preparation of anti-wet-skid rubber composition: 100 parts of solution polymerized styrene-butadiene rubber cement SSBR2564s (dry rubber) and 550 parts of cyclohexane are taken and added into a condensation kettle to be stirred and mixed for 57min, then 110 parts of ultra-dispersed nano white carbon black is added, the mixture is stirred and mixed for 2.2hr when the temperature is raised to 56 ℃, and finally the solution polymerized styrene-butadiene rubber composition for the wet-skid resistant tire tread is prepared by wet deashing, drying and briquetting. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Example 7
(1) Preparing the ultra-dispersed nano white carbon black:
a, preparing an organic silicon/alkylphenol polyoxyethylene ether copolymer: adding 100 parts of A-151 and 200 parts of cyclohexane into a reactor, stirring for 2.0hr, then adding 15 parts of DPEO, continuously stirring and heating until the temperature of the reactor reaches 70 ℃, rapidly adding 2.0 parts of sodium hydroxide under stirring, reacting for 10hr, and then decompressing and distilling to obtain an A-151/DPEO copolymer c.
b, preparing acylated solution polymerized styrene-butadiene rubber cement: 100 portions of solution polymerized styrene-butadiene rubber cement SSBR2564s and 200 portions of CS are added into a polymerization kettle2Stirring and heating, and when the temperature of the polymerization kettle reaches 50 ℃, quickly adding 0.5 part of AlCl under the stirring condition3Adding 15 parts of MAH until the system becomes orange red, stirring for reacting for 4hr, adding 10 parts of sodium feramete to terminate the reaction, filtering, and washing to obtain the acylated solution polymerized styrene-butadiene rubber cement c (the acetylation degree is 4.1%).
c, preparing ultra-dispersed nano white carbon black: adding 100 parts of nano white carbon black (40nm), 13 parts of A-151/DPEO copolymer c and 370 parts of cyclohexane into a polymerization kettle, heating to 55 ℃, and stirring for reaction for 2.7 hours; then adding 27 parts of acylation solution polymerized styrene-butadiene rubber cement c, stirring and reacting for 3.7 hours, and then carrying out flash evaporation, drying and grinding to obtain the ultra-dispersed nano white carbon black.
(2) Preparation of anti-wet-skid rubber composition: 100 parts of solution polymerized styrene-butadiene rubber cement SSBR2564s (dry rubber) and 560 parts of cyclohexane are taken and added into a condensation kettle to be stirred and mixed for 58min, then 114 parts of ultra-dispersed nano white carbon black is added, the mixture is stirred and mixed for 2.5h when the temperature is raised to 58 ℃, and finally the solution polymerized styrene-butadiene rubber composition for the wet-skid resistant tire tread is prepared by wet deashing, drying and briquetting. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Example 8
(1) Preparing the ultra-dispersed nano white carbon black:
a, preparing an organic silicon/alkylphenol polyoxyethylene ether copolymer: the same as in example 7.
b, preparing acylated solution polymerized styrene-butadiene rubber cement: the same as in example 7.
c, preparing ultra-dispersed nano white carbon black: adding 100 parts of nano white carbon black (40nm), 14 parts of A-151/DPEO copolymer c and 390 parts of cyclohexane into a polymerization kettle, heating to 58 ℃, and stirring for reaction for 2.9 hours; then adding 29 parts of acylation solution polymerized styrene-butadiene rubber cement c, stirring and reacting for 3.8 hours, and then carrying out flash evaporation, drying and grinding to obtain the ultra-dispersed nano white carbon black.
(2) Preparation of anti-wet-skid rubber composition: 100 parts of solution polymerized styrene-butadiene rubber cement SSBR2564s (dry rubber) and 580 parts of cyclohexane are taken and added into a condensation kettle to be stirred and mixed for 58min, then 118 parts of ultra-dispersed nano white carbon black is added, the mixture is stirred and mixed for 2.7hr when the temperature is raised to 58 ℃, and finally the solution polymerized styrene-butadiene rubber composition for the wet-skid resistant tire tread is prepared by wet deashing, drying and briquetting. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Example 9
(1) Preparing the ultra-dispersed nano white carbon black:
a, preparing an organic silicon/alkylphenol polyoxyethylene ether copolymer: the same as in example 7.
b, preparing acylated solution polymerized styrene-butadiene rubber cement: the same as in example 7.
c, preparing ultra-dispersed nano white carbon black: adding 100 parts of nano white carbon black (40nm), 15 parts of A-151/DPEO copolymer c and 400 parts of cyclohexane into a polymerization kettle, heating to 60 ℃, and stirring for reaction for 3.0 hours; then adding 30 parts of acylation solution polymerized styrene-butadiene rubber cement c, stirring and reacting for 4.0hr, and then carrying out flash evaporation, drying and grinding to obtain the ultra-dispersed nano white carbon black.
(2) Preparation of anti-wet-skid rubber composition: 100 parts of solution polymerized styrene-butadiene rubber cement SSBR2564s (dry rubber) and 600 parts of cyclohexane are taken and added into a condensation kettle to be stirred and mixed for 60min, then 120 parts of ultra-dispersed nano white carbon black is added, the mixture is stirred and mixed for 3.0hr when the temperature is raised to 60 ℃, and finally the solution polymerized styrene-butadiene rubber composition for the wet-skid resistant tire tread is prepared by wet deashing, drying and briquetting. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Comparative example 1
(1) Preparing the ultra-dispersed nano white carbon black:
a, preparing an organic silicon/alkylphenol polyoxyethylene ether copolymer: the other conditions were the same as in example 1 except that the amount of NPEO added during the preparation was 3.0 parts, that is: adding 100 parts of KH-550 and 100 parts of cyclohexane into a reactor, stirring for 1.0hr, then adding 5.0 parts of NPEO, continuously stirring and heating until the temperature of the reactor reaches 50 ℃, rapidly adding 0.5 part of sodium hydroxide under stirring, reacting for 5.0hr, decompressing, distilling to obtain the KH-550/NPEO copolymer a-1.
b, preparing acylated solution polymerized styrene-butadiene rubber cement: the same as in example 1.
c, preparing ultra-dispersed nano white carbon black: the other conditions were the same as in example 1, except that KH-550/NPEO copolymer a-1 was added instead of KH-550/NPEO copolymer a-1 during the preparation, namely: adding 100 parts of nano white carbon black (40nm), 5 parts of KH-550/NPEO copolymer a-1 and 200 parts of cyclohexane into a polymerization kettle, heating to 40 ℃, and stirring for reaction for 1.0 hr; then 10 parts of acylation solution polymerized styrene-butadiene rubber cement a is added, after stirring reaction for 2.0 hours, the ultra-dispersion type nano white carbon black a is prepared by flash evaporation, drying and grinding.
(2) Preparation of anti-wet-skid rubber composition: the other conditions are the same as those in example 1, except that the ultra-dispersed nano white carbon black a is added instead of the ultra-dispersed nano white carbon black in the preparation process, namely: 100 parts of solution polymerized styrene-butadiene rubber cement SSBR2564s (dry rubber) and 400 parts of cyclohexane are taken and added into a condensation kettle to be stirred and mixed for 50min, then 60 parts of ultra-dispersed nano white carbon black a is added, the mixture is stirred and mixed for 1hr when the temperature is raised to 50 ℃, and finally the solution polymerized styrene-butadiene rubber composition for the wet-skid resistant tire tread is prepared by wet deashing, drying and briquetting. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Comparative example 2
(1) Preparing the ultra-dispersed nano white carbon black:
a, preparing an organic silicon/alkylphenol polyoxyethylene ether copolymer: the same as in example 2.
b, preparing acylated solution polymerized styrene-butadiene rubber cement: the same as in example 2.
c, preparing ultra-dispersed nano white carbon black: the same as in example 2.
(2) Preparation of anti-wet-skid rubber composition: the other conditions are the same as those in example 2, except that the addition amount of the ultra-dispersed nano white carbon black in the preparation process is 45 parts, namely: 100 parts of solution polymerized styrene-butadiene rubber cement SSBR2564s (dry rubber) and 450 parts of cyclohexane are taken and added into a condensation kettle to be stirred and mixed for 52min, then 45 parts of ultra-dispersed nano white carbon black is added, the mixture is stirred and mixed for 1.5hr when the temperature is raised to 52 ℃, and finally the solution polymerized styrene-butadiene rubber composition for the wet-skid resistant tire tread is prepared by wet deashing, drying and briquetting. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Comparative example 3
(1) Preparing the ultra-dispersed nano white carbon black:
a, preparing acylated solution polymerized styrene-butadiene rubber cement: the same as in example 3.
b, preparing ultra-dispersed nano white carbon black: the other conditions were the same as in example 3, except that KH-550/NPEO copolymer a was not added during the preparation, but KH-550 was added directly, that is: adding 100 parts of nano white carbon black (40nm), 8 parts of KH-550 and 280 parts of cyclohexane into a polymerization kettle, heating to 45 ℃, and stirring for reacting for 1.9 hr; then 19 parts of acylation solution polymerized styrene-butadiene rubber cement a is added, after stirring reaction for 2.8 hours, the ultra-dispersion type nano white carbon black b is prepared by flash evaporation, drying and grinding.
(2) Preparation of anti-wet-skid rubber composition: the other conditions are the same as those in example 3, except that the super-dispersed nano white carbon black b is added instead of the super-dispersed nano white carbon black in the preparation process, namely: 100 parts of solution polymerized styrene-butadiene rubber cement SSBR2564s (dry rubber) and 470 parts of cyclohexane are taken and added into a condensation kettle to be stirred and mixed for 54min, then 90 parts of ultra-dispersed nano white carbon black b is added, the mixture is stirred and mixed for 1.8hr when the temperature is raised to 53 ℃, and finally the solution polymerized styrene-butadiene rubber composition for the wet-skid resistant tire tread is prepared by wet deashing, drying and briquetting. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Comparative example 4
(1) Preparing the ultra-dispersed nano white carbon black:
a, preparing an organic silicon/alkylphenol polyoxyethylene ether copolymer: the other conditions were the same as in example 4 except that the amount of NPEO added during the preparation was 2.0 parts, that is: adding 100 parts of KH-550 and 150 parts of cyclohexane into a reactor, stirring for 1.5 hours, then adding 2.0 parts of NPEO, continuously stirring and heating until the temperature of the reactor reaches 60 ℃, rapidly adding 1.5 parts of sodium hydroxide under stirring, reacting for 8.0 hours, and then decompressing and distilling to obtain the KH-550/NPEO copolymer b-1.
b, preparing acylated solution polymerized styrene-butadiene rubber cement: the same as in example 4.
c, preparing ultra-dispersed nano white carbon black: the other conditions were the same as in example 4, except that KH-550/NPEO copolymer b was not added during the preparation, but KH-550/NPEO copolymer b-1 was added, that is: adding 100 parts of nano white carbon black (40nm), 10 parts of KH-550/NPEO copolymer b-1 and 300 parts of cyclohexane into a polymerization kettle, heating to 50 ℃, and stirring for reaction for 2.0 hr; then 21 parts of acylation solution polymerized styrene-butadiene rubber cement b is added, after stirring reaction for 3.0 hours, the ultra-dispersion type nano white carbon black c is prepared by flash evaporation, drying and grinding.
(2) Preparation of anti-wet-skid rubber composition: the other conditions are the same as those in example 4, except that the ultra-dispersed nano white carbon black c is added instead of the ultra-dispersed nano white carbon black in the preparation process, namely: 100 parts of solution polymerized styrene-butadiene rubber cement SSBR2564s (dry rubber) and 500 parts of cyclohexane are taken and added into a condensation kettle to be stirred and mixed for 55min, then 100 parts of ultra-dispersed nano white carbon black is added, the mixture is stirred and mixed for 2.0hr when the temperature is raised to 54 ℃, and finally the solution polymerized styrene-butadiene rubber composition for the wet-skid resistant tire tread is prepared by wet deashing, drying and briquetting. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Comparative example 5
(1) Preparing the ultra-dispersed nano white carbon black:
a, preparing an organic silicon/alkylphenol polyoxyethylene ether copolymer: the same as in example 5.
b, preparing ultra-dispersed nano white carbon black: the other conditions were the same as in example 5, except that the solution-polymerized styrene-butadiene rubber cement SSBR2564s was added in an amount of 23 parts instead of the acylated solution-polymerized styrene-butadiene rubber cement b: adding 100 parts of nano white carbon black (40nm), 11 parts of KH-550/NPEO copolymer b and 320 parts of cyclohexane into a polymerization kettle, heating to 53 ℃, and stirring for reacting for 2.3 hours; then adding 23 parts of solution polymerized styrene-butadiene rubber cement SSBR2564s, stirring and reacting for 3.2 hours, and then carrying out flash evaporation, drying and grinding to obtain the ultra-dispersed nano white carbon black d.
(2) Preparation of anti-wet-skid rubber composition: the other conditions are the same as those in example 5, except that the super-dispersed nano white carbon black is not added in the preparation process, but the super-dispersed nano white carbon black d is added, namely: 100 parts of solution polymerized styrene-butadiene rubber cement SSBR2564s (dry rubber) and 530 parts of cyclohexane are taken and added into a condensation kettle to be stirred and mixed for 56min, then 105 parts of super-dispersed nano white carbon black d is added, the mixture is stirred and mixed for 2.2hr when the temperature is raised to 56 ℃, and finally the solution polymerized styrene-butadiene rubber composition for the wet-skid resistant tire tread is prepared by wet deashing, drying and briquetting. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Comparative example 6
Preparation of anti-wet-skid rubber composition: the other conditions are the same as those in example 6, except that the ultra-dispersed nano white carbon black is not added in the preparation process, but the unmodified nano white carbon black is directly added, and the addition amount is 110 parts, namely: 100 parts of solution polymerized styrene-butadiene rubber cement SSBR2564s (dry rubber) and 550 parts of cyclohexane are taken and added into a condensation kettle to be stirred and mixed for 57min, then 110 parts of unmodified nano white carbon black is added, the mixture is stirred and mixed for 2.2hr when the temperature is raised to 56 ℃, and finally the solution polymerized styrene-butadiene rubber composition for the wet skid resistant tire tread is prepared by wet deashing, drying and briquetting. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Comparative example 7
(1) Preparing the ultra-dispersed nano white carbon black:
a, preparing an organic silicon/alkylphenol polyoxyethylene ether copolymer: adding 100 parts of A-151 and 200 parts of cyclohexane into a reactor, stirring for 2.0hr, then adding 15 parts of DPEO, continuously stirring and heating until the temperature of the reactor reaches 70 ℃, rapidly adding 2.0 parts of sodium hydroxide under stirring, reacting for 10hr, and then decompressing and distilling to obtain an A-151/DPEO copolymer c.
b, preparing acylated solution polymerized styrene-butadiene rubber cement: the other conditions were the same as in example 7 except that the amount of MAH added during the preparation was 4.0 parts, that is: in the polymerization of100 portions of solution polymerized styrene-butadiene rubber cement SSBR2564s and 200 portions of CS are added into the kettle2Stirring and heating, and when the temperature of the polymerization kettle reaches 50 ℃, quickly adding 0.5 part of AlCl under the stirring condition3Adding 4.0 parts of MAH until the system becomes orange red, stirring for reaction for 4hr, adding 10 parts of sodium feramete to terminate the reaction, filtering, and washing to obtain the acylated solution polymerized styrene-butadiene rubber cement c-1 (acetylation degree of 0.3%).
c, preparing ultra-dispersed nano white carbon black: the other conditions were the same as in example 7, except that the preparation process was carried out without adding the acylated solution-polymerized styrene-butadiene rubber cement c, but with adding the acylated solution-polymerized styrene-butadiene rubber cement c-1, namely: adding 100 parts of nano white carbon black (40nm), 13 parts of A-151/DPEO copolymer c and 370 parts of cyclohexane into a polymerization kettle, heating to 55 ℃, and stirring for reaction for 2.7 hours; then adding 27 parts of acylation solution polymerized styrene-butadiene rubber cement c-1, stirring and reacting for 3.7 hours, and then carrying out flash evaporation, drying and grinding to obtain the ultra-dispersed nano white carbon black e.
(2) Preparation of anti-wet-skid rubber composition: the other conditions are the same as those in example 7, except that the ultra-dispersed nano white carbon black is not added in the preparation process, but ultra-dispersed nano white carbon black e is added, namely: 100 parts of solution polymerized styrene-butadiene rubber cement SSBR2564s (dry rubber) and 560 parts of cyclohexane are taken and added into a condensation kettle to be stirred and mixed for 58min, then 114 parts of ultra-dispersed nano white carbon black e is added, the mixture is stirred and mixed for 2.5hr when the temperature is raised to 58 ℃, and finally the solution polymerized styrene-butadiene rubber composition for the wet-skid resistant tire tread is prepared by wet deashing, drying and briquetting. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Comparative example 8
(1) Preparing the ultra-dispersed nano white carbon black:
a, preparing an organic silicon/alkylphenol polyoxyethylene ether copolymer: the same as in example 8.
b, preparing ultra-dispersed nano white carbon black: the other conditions were the same as in example 8, except that the solution-polymerized styrene-butadiene rubber cement SSBR2564s was directly added without adding the acylated solution-polymerized styrene-butadiene rubber cement c in the preparation process, namely: adding 100 parts of nano white carbon black (40nm), 14 parts of A-151/DPEO copolymer c and 390 parts of cyclohexane into a polymerization kettle, heating to 58 ℃, and stirring for reaction for 2.9 hours; then adding 29 parts of solution polymerized styrene-butadiene rubber cement SSBR2564s, stirring and reacting for 3.8 hours, and then carrying out flash evaporation, drying and grinding to obtain the ultra-dispersed nano white carbon black f.
(2) Preparation of anti-wet-skid rubber composition: the other conditions are the same as those in example 8, except that the ultra-dispersed nano white carbon black is not added in the preparation process, but the ultra-dispersed nano white carbon black f is added, namely: 100 parts of solution polymerized styrene-butadiene rubber cement SSBR2564s (dry rubber) and 580 parts of cyclohexane are taken and added into a condensation kettle to be stirred and mixed for 58min, then 118 parts of ultra-dispersed nano white carbon black f is added, the mixture is stirred and mixed for 2.7hr when the temperature is raised to 58 ℃, and finally the solution polymerized styrene-butadiene rubber composition for the wet-skid resistant tire tread is prepared by wet deashing, drying and briquetting. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
Comparative example 9
(1) Preparing the ultra-dispersed nano white carbon black:
a, preparing an organic silicon/alkylphenol polyoxyethylene ether copolymer: the other conditions were the same as in example 9 except that the amount of DPEO added during the preparation was 4.0 parts, that is: adding 100 parts of A-151 and 200 parts of cyclohexane into a reactor, stirring for 2.0hr, then adding 4.0 parts of DPEO, continuously stirring and heating until the temperature of the reactor reaches 70 ℃, rapidly adding 2.0 parts of sodium hydroxide under stirring, reacting for 10hr, and then decompressing and distilling to obtain the A-151/DPEO copolymer c-1.
b, preparing acylated solution polymerized styrene-butadiene rubber cement: the same as in example 9.
c, preparing ultra-dispersed nano white carbon black: the other conditions were the same as in example 9, except that the A-151/DPEO copolymer c was not added during the preparation, but the A-151/DPEO copolymer c-1 was added, namely: adding 100 parts of nano white carbon black (40nm), 15 parts of A-151/DPEO copolymer c-1 and 400 parts of cyclohexane into a polymerization kettle, heating to 60 ℃, and stirring for reaction for 3.0 hr; then adding 30 parts of acylation solution polymerized styrene-butadiene rubber cement c, stirring and reacting for 4.0hr, and then carrying out flash evaporation, drying and grinding to obtain the ultra-dispersed nano white carbon black g.
(2) Preparation of anti-wet-skid rubber composition: the other conditions are the same as those in example 9, except that the ultra-dispersed nano white carbon black is not added in the preparation process, but ultra-dispersed nano white carbon black g is added, namely: 100 parts of solution polymerized styrene-butadiene rubber cement SSBR2564s (dry rubber) and 600 parts of cyclohexane are taken and added into a condensation kettle to be stirred and mixed for 60min, then 120 parts of ultra-dispersed nano white carbon black g is added, when the temperature is raised to 60 ℃, the stirring and mixing are carried out for 3.0hr, and finally the solution polymerized styrene-butadiene rubber composition for the wet-skid resistant tire tread is prepared by wet deashing, drying and briquetting. Sampling and analyzing: standard samples were prepared and the properties tested are shown in Table 1.
TABLE 1 Properties of solution-polymerized styrene-butadiene rubber composition for wet-resistant tire treads
As can be seen from Table 1: the tan delta (0 ℃) value of the rubber composition containing the high-dispersion nano white carbon black in the embodiment is larger than that of the comparative proportion, which shows that the rubber composition has good wet skid resistance; and tan delta (60 ℃ C.) values are lower than those of the comparative examples, indicating that the rubber composition is small in rolling resistance.
The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (11)
1. An anti-slippery rubber composition for green tires mainly comprises the following components:
(1) 100 parts by mass of solution polymerized styrene-butadiene rubber cement
(2) 60-120 parts by mass of ultra-dispersed nano white carbon black
The super-dispersion type nano white carbon black is characterized in that alkylphenol polyoxyethylene ether and a silane coupling agent are subjected to copolymerization reaction, the generated product, namely organic silicon/alkylphenol polyoxyethylene ether copolymer, is used for carrying out multi-point anchoring modification on the surface of nano white carbon black particles, then, anhydride is used for carrying out acylation treatment on solution polymerized styrene-butadiene rubber cement, and finally, the surface of the nano white carbon black particles is subjected to coating treatment to prepare the super-dispersion type nano white carbon black.
2. The wet-skid resistant rubber composition for green tires according to claim 1, wherein the particle size of the nano white carbon black is 10 to 100 nm.
3. The wet skid resistant rubber composition for green tires according to claim 1, wherein the alkylphenol ethoxylate is one selected from the group consisting of nonylphenol ethoxylate, octylphenol ethoxylate, dodecylphenol ethoxylate, and dinonylphenol ethoxylate.
4. The wet skid resistant rubber composition for green tires according to claim 3, wherein the alkylphenol polyoxyethylene ether is nonylphenol polyoxyethylene ether.
5. The wet skid resistant rubber composition for green tires as claimed in claim 1, wherein the silane coupling agent is one selected from the group consisting of γ -aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, vinyltriethoxysilane, N- β -aminoethyl- γ -aminopropylmethyldimethoxysilane, γ -methacryloxypropyltrimethoxysilane, N- β - (aminoethyl) - γ -aminopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltris (β -methoxyethoxy) silane.
6. The wet skid resistant rubber composition for green tires according to claim 5, wherein the silane coupling agent is γ -aminopropyltriethoxysilane.
7. A method for preparing the anti-slippery rubber composition for green tires according to claim 1, wherein the method comprises the following steps:
(1) preparing the ultra-dispersed nano white carbon black:
a. preparing an organic silicon/alkylphenol polyoxyethylene ether copolymer: adding 100 parts by mass of silane coupling agent and 100-200 parts by mass of solvent into a reactor, stirring for 1-2 hours, then adding 5-15 parts by mass of alkylphenol polyoxyethylene ether, continuously stirring and heating until the temperature of the reactor reaches 50-70 ℃, rapidly adding 0.5-2.0 parts by mass of initiator under the stirring condition, reacting for 5-10 hours, and then decompressing and distilling to obtain organic silicon/alkylphenol polyoxyethylene ether;
b. preparing acylated solution polymerized styrene-butadiene rubber cement: adding 100 parts by mass of solution polymerized styrene-butadiene rubber cement and 100-200 parts by mass of solvent into a polymerization kettle, stirring and heating, when the temperature of the polymerization kettle reaches 40-50 ℃, rapidly adding 0.05-0.5 part by mass of catalyst under the stirring condition, adding 5-15 parts by mass of anhydride until the system becomes orange red, stirring and reacting for 2-4 hours, adding 5-10 parts by mass of terminator to terminate the reaction, and performing suction filtration and washing to obtain acylated solution polymerized styrene-butadiene rubber cement;
c. preparing the ultra-dispersed nano white carbon black: adding 100 parts by mass of nano white carbon black, 5-15 parts by mass of organic silicon/alkylphenol polyoxyethylene ether copolymer and 200-400 parts by mass of solvent into a polymerization kettle, heating to 40-60 ℃, and stirring for reaction for 1-3 hours; then adding 10-30 parts by mass of acylated solution-polymerized styrene-butadiene rubber cement, stirring and reacting for 2-4 hours, and then carrying out flash evaporation, drying and grinding to obtain the ultra-dispersed nano white carbon black;
(2) preparation of anti-wet-skid rubber composition: adding 100 parts by mass of solution-polymerized styrene-butadiene rubber cement and 400-600 parts by mass of solvent into a condensation kettle, stirring and mixing for 50-60 min, then adding 60-120 parts by mass of super-dispersed nano white carbon black, heating to 50-60 ℃, stirring and mixing for 1-3 hr, and finally performing wet deashing, drying and briquetting to obtain the solution-polymerized styrene-butadiene rubber composition for the anti-slippery tire tread.
8. The method of claim 7, wherein the initiator is selected from the group consisting of sodium hydroxide, potassium hydroxide, magnesium hydroxide, sodium carbonate, and sodium bicarbonate.
9. The method of claim 8, wherein the initiator is sodium hydroxide.
10. The method of claim 7, wherein the catalyst is selected from the group consisting of anhydrous aluminum trichloride, boron trifluoride, tin tetrachloride, and zinc dichloride.
11. The process of claim 10, wherein the catalyst is anhydrous aluminum trichloride.
Priority Applications (1)
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| CN101220177A (en) * | 2008-01-25 | 2008-07-16 | 北京化工大学 | Process for producing white carbon black/solution polymerized butadiene styrene rubber nano-composite material |
| CN108192141A (en) * | 2016-12-08 | 2018-06-22 | 中国石油天然气股份有限公司 | A kind of method of modifying of gum filler carbon nanotube |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101220177A (en) * | 2008-01-25 | 2008-07-16 | 北京化工大学 | Process for producing white carbon black/solution polymerized butadiene styrene rubber nano-composite material |
| CN108192141A (en) * | 2016-12-08 | 2018-06-22 | 中国石油天然气股份有限公司 | A kind of method of modifying of gum filler carbon nanotube |
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