CN114276586A - Tire bead protection rubber and preparation method and application thereof - Google Patents
Tire bead protection rubber and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a tire bead filler and a preparation method and application thereof. The tire bead protection rubber comprises the following raw material components in parts by weight: 10-90 parts of natural rubber, 10-90 parts of bifunctional polybutadiene rubber, 0.01-7.5 parts of graphene oxide, 20-60 parts of white carbon black, 10-20 parts of carbon black and 4-10 parts of silane coupling agent, wherein functional groups of the bifunctional polybutadiene rubber are amino and siloxane groups. The tire bead protection rubber provided by the invention is obtained by designing the material composition and content, and solves the problems of low mechanical strength, low hardness, high heat generation and the like of the tire bead protection rubber.
Description
Technical Field
The invention belongs to the technical field of rubber, and particularly relates to tire bead protection rubber as well as a preparation method and application thereof.
Background
The tire seam is also called a toe seam, which refers to the part of the tire rubber contacting with the tire rim, and mainly plays the role of protecting the tire body cord fabric and the steel wire seam wrapping cloth of the tire framework. The tire bead position of the all-steel radial tire is a concentrated area bearing load stress, and meanwhile, a high-temperature area which generates frictional heat due to the fact that power is required to be transmitted through friction between the bead protection rubber and the rim needs to have more excellent performance in high-temperature and high-stress environments, and the bead protection rubber is prevented from being rapidly reduced in performance or being torn and damaged under the action of high stress due to high-temperature aging.
Natural rubber is generally used in the traditional formula of the bead protection rubber, but the natural rubber is high in price and difficult to process. Therefore, most tire enterprises reduce the production cost while solving the processing problem by adding polybutadiene rubber in the formula. However, the performance of the tire is difficult to ensure after the polybutadiene rubber is added, and the mechanical strength, hardness and heat buildup performance of the product are obviously reduced.
Therefore, a new bead filler needs to be developed, the mixing processing requirement of the bead filler is reduced on the premise of not upgrading equipment and not increasing energy consumption, and the wear resistance and fatigue failure resistance of the bead filler are enhanced, so that the tire performance is improved, and a high-performance tire is obtained.
Disclosure of Invention
The invention provides a tire bead protection rubber, which is a high-hardness, deflection-resistant and low-heat-generation tire bead protection rubber for a semisteel radial tire, and solves the problems of low mechanical strength, low hardness, high heat generation and the like of the tire bead protection rubber by designing material composition and content.
The invention also provides a preparation method of the tire bead protection rubber, which is simple to operate, convenient for industrial production and low in cost, can prepare the high-hardness, flex-resistant and low-heat-generation bead protection rubber for the semi-steel radial tire, and solves the problems of low mechanical strength and hardness, high heat generation and the like of the tire bead protection rubber.
The technical scheme provided by the invention is as follows:
the invention provides a tire bead protection rubber which comprises the following raw material components in parts by weight: 10-90 parts of natural rubber, 10-90 parts of bifunctional polybutadiene rubber, 0.01-7.5 parts of graphene oxide, 20-60 parts of white carbon black, 10-20 parts of carbon black and 4-10 parts of silane coupling agent;
wherein the functional groups of the bifunctional polybutadiene rubber are amine groups and siloxane groups.
Specifically, in the invention, bifunctional polybutadiene rubber with amino and siloxane groups is used as a raw material, and a composite material with excellent mechanical properties can be obtained by utilizing dehydration condensation reaction of the amino functional group and carboxyl in graphene oxide. The mechanism should be that the bifunctional polybutadiene rubber and graphene oxide can be combined more stably, a larger interface effect is generated, and the agglomeration between graphene oxide polar groups is prevented or destroyed, so that the dispersibility of graphene oxide in the polybutadiene rubber is improved, and the mechanical property of the graphene oxide is improved. The reaction mechanism can be reflected by fig. 1.
Compared with the structure of the polybutadiene rubber, the bifunctional polybutadiene rubber with amino and siloxane groups, which is one of the raw materials of the present invention, has amino and siloxane groups introduced into two end groups respectively, and is commercially available, or can be obtained by selecting appropriate monomers through polymerization reaction, for example, the amino and siloxane groups can be introduced into a butadiene monomer simultaneously or step by step in the polymerization reaction process by using a metal lithium or alkyl lithium catalyst, and as a synthesis method of a specific embodiment, the present invention can include the following steps:
(1) reacting an ammonia-containing organic compound, a solvent and alkyl lithium under a protective gas atmosphere to obtain an initiator solution. Wherein, the general formula of the organic compound containing amine is: AmR1R2Wherein Am is an arylamino group, R1Is an alkyl group having 1 to 10 carbon atoms, R2The amine-containing organic compound may include N, N-dimethylbenzylamine, N-methylbenzylaniline, N-dibenzylaniline, and the like, which are alkyl or aryl groups having 1 to 10 carbon atoms. The alkyllithium may be methyllithium, ethyllithium, isopropyllithium, n-butyllithium, primary butyllithium, t-butyllithium, pentyllithium, hexyllithium, phenyllithium, vinyllithium, propenyl lithium, etc. For example, when n-butyllithium is used as the catalyst, the amount of the catalyst to be added may be such that the molar ratio of the organic amide to the n-butyllithium is from 1:1 to 1.5. The solvent can be aromatic hydrocarbon, aliphatic hydrocarbon or cycloalkane, such as one or more of benzene, toluene, xylene, ethylbenzene, butane, hexane, heptane, cyclopentane, cyclohexane and methylcyclohexane.
(2) Adding a regulator and a butadiene polymerization solution into the initiator solution, and reacting at the temperature of 50-120 ℃ for 1-2 h. The above reaction can be carried out in a reaction vessel. The regulators are conventional in the art and are, for example, tetrahydrofuran, dioxane, triethylamine, pentamethyldiethylenetriamine, benzofuran, N-dimethyltetrahydrofurfuryl amine, tetrahydrofurfuryl alcohol ethyl ether, and the like. The butadiene mass monomer concentration may be from 6% to 20%, for example from 8% to 12%.
(3) And (3) adding a siloxane compound into the product obtained in the step (2), continuously reacting for 1-2 h, flocculating and drying to obtain the bifunctional polybutadiene rubber. The siloxane compound may be represented by the formula: (XR)2)mSi(OR3)n. Wherein R is2Is an alkyl radical having from 1 to 10 carbon atoms, R3Is an alkyl group having 1 to 5 carbon atoms, m is 1 to 3, n is 4-m, and X is chlorine or bromine. The siloxane compound includes: chloropropyltrimethoxysilane, chloroethyltrimethoxysilane, bromopropyltrimethoxysilane, bromopropyltriethoxysilane, bromobutyltrimethoxysilane, and the like. Wherein the temperature of the end-capping reaction is 50 ℃ to 120 ℃, for example 50 ℃ to 70 ℃.
(4) Optionally, the bifunctional polybutadiene rubber may be kneaded with an auxiliary and vulcanized. The manner and conditions of mixing may be conventional in the art. Generally, the mixing can be carried out in an open mill, an internal mixer, or a two-roll mill. The mixing of the respective substances may be carried out simultaneously or stepwise. The vulcanization may be carried out in a vulcanization bed or a press. The method and conditions for vulcanizing the rubber compound can be selected conventionally in the field, for example, the conditions of the vulcanization reaction include that the vulcanization temperature can be 150-180 ℃, the vulcanization pressure can be 10-15MPa, and the vulcanization time can be 10-30 min.
The graphene oxide has a plurality of oxygen-containing groups on the sheet layer, so that the graphene oxide also has higher specific surface energy, good hydrophilicity and mechanical properties, and the graphene oxide monomer with proper oxygen content can be better combined with polybutadiene. For example, graphene oxide with an oxygen content of 30% or higher may be advantageously selected. In the present invention, the oxygen content of graphene oxide is the sum of the oxygen contents of all oxygen-containing functional groups including hydroxyl, carboxyl, carbonyl, and the like. If the oxygen content of the graphene oxide is too low, the performance of the material may be affected, and if the oxygen content of the graphene oxide is too high, the preparation requirement of the graphene oxide is higher, so that the preparation difficulty is increased, and the cost of raw materials and products is also increased. The research of the applicant finds that when graphene oxide with the oxygen content of about 30-40% is used as a filler to be dispersed in a composite material, an amino functional group can be better combined with a carboxyl group in the graphene oxide, the mechanical property of the composite material can be improved, and the cost can be reduced. The graphene oxide used in the scheme of the present invention, or the graphene oxide having an appropriate oxygen content, for example, the graphene oxide having an oxygen content of 30% to 40%, may be commercially available or homemade, and the source of the graphene oxide is not limited in the present invention.
In the embodiment of the present invention, the weight ratio of the graphene oxide to the bifunctional polybutadiene is not particularly limited, and in order to improve the performance of the material and to obtain better dispersion of the graphene oxide in the material, the weight ratio of the graphene oxide to the bifunctional polybutadiene may be (0.1 to 15): 100, for example, (1 to 10): 100.
in addition, other white carbon black and carbon black which respectively act with the amino functional group and the siloxane functional group are added to further improve the mechanical property of the material. In the bifunctional modified polybutadiene, the amino functional group and the siloxane functional group can respectively and simultaneously react with the carbon black and the white carbon black, so that the white carbon black and the carbon black can be better dispersed in the polybutadiene rubber. In particular, when graphene oxide is added to bifunctional polybutadiene to perform the above reaction, a small amount of graphene oxide is added to achieve the desired effect.
The tire bead protection rubber provided by the invention is obtained by designing the material composition and content, and solves the problems of low mechanical strength, low hardness, high heat generation and the like of the tire bead protection rubber.
As a specific embodiment of the invention, the tire bead protection rubber further comprises the following raw material components in parts by weight: 3-12 parts of operating oil, 1-5 parts of zinc oxide, 2-6 parts of stearic acid, 1-5 parts of anti-aging agent, 0.1-4 parts of sulfur, 0.1-4 parts of accelerator and 0.1-0.5 part of anti-scorching agent.
The silane coupling agent, the process oil, the anti-aging agent, the accelerator and the scorch retarder are all common raw materials in the field, and can be selected according to the performance of the required bead protection rubber, and the inventor does not particularly limit the performance. For example, the silane coupling agent can be a silane coupling agent Si-69, the process oil can be a petroleum plasticizer such as aromatic hydrocarbons and naphthenic hydrocarbons, the anti-aging agent can be RD and 4010, the accelerator can be thiazole, sulfenamide and thiuram accelerators, and the scorch retarder can be nitroso compounds, organic acids and thioamides.
As a specific embodiment of the present invention, the mass ratio of the bifunctional polybutadiene rubber to the natural rubber is greater than or equal to 1: 1. Therefore, the consumption of the natural rubber is reduced, the cost is reduced, and the performance of the tire is improved.
As a specific embodiment of the invention, the hardness of the tire bead protection rubber is not lower than 70, the crack-free flexing times are not lower than 30 ten thousand, and the compression fatigue temperature rise is not higher than 28 ℃.
In a second aspect, the invention provides a preparation method of a tire bead filler.
The preparation method of the tire bead protection rubber comprises the following steps:
the method comprises the following steps: and (3) preparing a bifunctional polybutadiene rubber/graphene oxide composite material.
Dispersing the graphene oxide in a first organic solvent to obtain a graphene oxide suspension;
dissolving the difunctional polybutadiene rubber in a second organic solvent to form a rubber solution; wherein the first organic solvent and the second organic solvent are mutually soluble or are the same organic solvent;
mixing the graphene oxide suspension with the rubber solution, and then removing the first organic solvent and the second organic solvent to obtain a bifunctional polybutadiene rubber/graphene oxide composite precursor;
and (3) carrying out dehydration condensation reaction on the bifunctional polybutadiene rubber/graphene oxide composite precursor under the action of an initiator to obtain the bifunctional polybutadiene rubber/graphene oxide composite material.
Step two: preparing the tire bead protection rubber.
Mixing the natural rubber and the dual-functionalized polybutadiene rubber/graphene oxide composite material in a first step;
adding the rest raw material components for further mixing to obtain the tire bead rubber.
According to the preparation method of the tire bead protection rubber, firstly, the bifunctional polybutadiene rubber/graphene oxide composite material is prepared, then the raw material components are added in batches through multi-step mixing, and particularly, the white carbon black is added in two steps, so that the seasoning can be well dispersed in the rubber, the dispersion performance of the filler in the rubber is improved, and the mechanical property of the tire bead protection rubber is further improved. In addition, the preparation method is simple to operate, convenient for industrial production and low in cost, can prepare the semi-steel radial tire bead protection rubber with high hardness, flex resistance and low heat generation, and solves the problems of low mechanical strength and hardness, high heat generation and the like of the tire bead protection rubber.
The composite material is a dehydration condensation reaction product of bifunctional polybutadiene rubber and graphene oxide through amino and carboxyl at the temperature of 130-170 ℃. The reaction is carried out at the temperature of 130-170 ℃, so that unnecessary side reactions can be avoided, and the effective combination of carboxyl in the graphene oxide and amino in the bifunctional polybutadiene rubber can be ensured.
The graphene oxide can be dispersed in the bifunctional polybutadiene rubber by ultrasonic dispersion or stirring, which is not limited, and the mixing time can be adjusted according to the conditions such as specific solvent. In general, the stirring can be continued for 6 hours at the rotating speed of 300r/min-500r/min, and a good effect can be achieved. When the stirring time is less than 6 hours, the performance of the composite material is possibly affected due to uneven dispersion; and when the stirring time is too long, for example, more than 12 hours, the waste of manpower and material resources is caused.
When the organic solvent is removed, a rotary evaporation mode or a film drying mode and the like can be selected according to the property of the organic solvent, for example, when the organic solvent is tetrahydrofuran, the organic solvent can be dried in a vacuum drying oven at the temperature of 40-60 ℃ until the quality is basically not changed.
In general, when the blending operation is carried out, the blending can be carried out by an apparatus such as a chain opener or an internal mixer. The reaction operation can be selected but not limited to mold pressing vulcanization, for example, the reaction can be carried out at the temperature of 130-170 ℃ and the mold pressing pressure of 10-15Mpa, and in the specific operation process, the reaction time can be determined by a rotor-free vulcanizing instrument, generally 10-60 min, so as to obtain the bifunctional polybutadiene/graphene oxide composite material.
In the present invention, the initiator may be a peroxide initiator, an azo initiator, a redox initiator, etc., as long as the above reaction can be initiated, and in the embodiment of the present invention, it is not limited, and may be one selected from Azobisisobutyronitrile (AIBN), dibenzoyl peroxide (BPO), dicumyl peroxide (DCP), di-t-butyl peroxide (DTBP), for example, dicumyl peroxide (DCP).
As will be understood by those skilled in the art, when initiating the polymerization reaction, the amount of the initiator is suitable, and should not be too much or too little, and too much will result in too fast reaction speed to control; if the amount is too small, the initiation is not easy, the reaction can not be normally carried out, and the performance of the polymer is influenced. In the present invention, the amount of the initiator can be controlled to 1% to 2.5% of the total mass of the polymer monomers, with reference to the amount added in the conventional polymerization reaction.
In the present invention, the specific operation of further kneading may be:
3/10-7/10 parts by weight of the white carbon black, the silane coupling agent, the carbon black, the zinc oxide, the stearic acid, the anti-aging agent and the process oil are added for second-step mixing;
and adding the rest white carbon black, the rest zinc oxide, the rest stearic acid and the rest anti-aging agent to carry out the third step of mixing, and then extruding the mixed raw material components to obtain the rubber material. Typically, the compound will be allowed to stand at room temperature to facilitate further processing.
And mixing the rubber material in the fourth step, adding the sulfur, the accelerator and the anti-scorching agent into the rubber material, and mixing in the fifth step to obtain the tire bead protection rubber.
As a specific embodiment of the present invention, the kneading in each step can be adjusted according to the melting properties of the raw materials. For example, the temperature of the first mixing step may be adjusted to 80 ℃ to 100 ℃, such as 85 ℃ to 95 ℃; the temperature of the second mixing step can be adjusted to 90-110 ℃, for example, 95-105 ℃; the temperature of the third mixing step can be adjusted to 145-155 ℃, for example, 148-152 ℃; adjusting the mixing temperature of the fourth step to be 80-100 ℃, for example, 85-95 ℃; the temperature of the mixing in the fifth step is adjusted to 80 ℃ to 110 ℃, for example, 90 ℃ to 100 ℃.
The time for kneading also affects the dispersibility of the filler, and if the kneading time is too short, the filler tends to be unevenly distributed, thereby affecting the mechanical properties. The inventor researches and discovers that when the mixing time of each step is controlled respectively, even dispersion of the filler can be further realized after multiple steps are coordinated, and thus the product performance required by the inventor is obtained. In a particular practice of the invention, the time of the first mixing step is not less than 30s, for example from 30s to 60 s; the time of the second step of mixing is not less than 30s, for example, 30s-60 s; the third step of mixing for not less than 150s, such as 150s-200 s; the mixing time of the fourth step is not less than 30s, such as 30s-60 s; the time for the fifth step of mixing is not less than 60s, for example, 60s to 90 s. The inventors do not specifically limit the rotation speed during kneading, and can further adjust the rotation speed by the kneading time, and all of them fall within the scope of the present invention.
The inventors have found that the degree of dispersion of the filler in the rubber can be further adjusted by the pressure at the time of kneading. If the pressure is too high, the uniformity of the filler dispersion is reduced, whereas if the pressure is too low, the effect of improving the dispersion performance cannot be achieved. In one embodiment of the present invention, the inventors have found that by adjusting the pressure of each kneading step to about 0.5MPa to about 0.65MPa, for example, about 0.55MPa to about 0.65MPa, both the filler dispersing ability and the mechanical properties of the product can be improved.
The tire bead protection rubber of the present invention can be prepared by an open mill or an internal mixer, and can also be prepared by other conventional equipment in the art, and the present invention is not particularly limited thereto.
The preparation method of the tire bead protection rubber has the advantages of simple operation, convenience for industrial production and low cost, can prepare the high-hardness, flex-resistant and low-heat generation semisteel radial tire bead protection rubber, and solves the problems of low mechanical strength and hardness, high heat generation and the like of the tire bead protection rubber.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
FIG. 1 is a schematic representation of the reaction of a difunctional polybutadiene rubber of the present invention with graphene oxide;
FIG. 2 shows the preparation of a difunctional polybutadiene rubber used in the examples of the present invention1H-NMR spectrum.
Detailed Description
The following detailed description of embodiments of the invention is intended to be illustrative, and not to be construed as limiting the invention.
The graphene oxide adopted in the embodiment of the invention is prepared in a laboratory.
The bifunctional polybutadiene rubber is produced by the Mount-mountain petrochemical company and can also be prepared by the following method:
(1) 100mL of cyclohexane, 10mL of N-butyllithium and 1.1-fold molar amount of N, N-dimethylbenzylamine were added to a 250mL three-necked flask with a stirrer under protection of dry nitrogen, and stirred in a water bath at 35 ℃ for 1 hour to prepare an amine lithium initiator, the concentration of which was 0.28mol/L by titration.
(2) Taking a 250mL three-necked flask, baking by using a high-temperature gas lamp, purging by using nitrogen, adding 12.4g of butadiene, 120mL of cyclohexane and 15mL of tetrahydrofuran with the concentration of 2mol/L, adding 6.4mL of amine lithium initiator, reacting for 2h at 60 ℃, adding 0.54mL of 3-chloropropyl-trimethoxy silane, heating to 75 ℃, stirring for reacting for 45min, flocculating by using ethanol, and drying the product in a vacuum oven to obtain the bifunctional polybutadiene rubber.
The number average molecular weight by GPC was 7000, and the molecular weight distribution was 1.15.
The results of NMR spectroscopy on the bifunctional polybutadiene rubber are shown in FIG. 2.
In the following examples and comparative examples, the test equipment and conditions for the composite materials are listed below:
1. nuclear magnetic resonance spectroscopy test (1H-NMR)
AV400 type nuclear magnetic resonance spectroscopy by Bruker1H-NMR measurement, the testing frequency is 400MHz, and scanning is carried out 16 times. The test solvent was deuterated chloroform (CDCl)3)。
2. Mechanical Property test
1) The samples were subjected to tensile testing according to ASTM D412 using an electronic tensile machine of the type CMT 4104, with a test tensile rate of 500 mm/min.
2) Shore A hardness was measured by HPE type II durometer according to ASTM D2240.
3) The no-crack flex test was carried out in accordance with GB/T13943-2006 "determination of flex cracking and crack growth in vulcanized or thermoplastic rubber (Demo subtype)".
4) The compression heat generation test was carried out in accordance with GB T1687-93, part 2 compression deflection test for determination of the temperature rise and fatigue resistance of vulcanizates in the deflection test.
The invention is described in detail below by means of specific examples:
example 1
Example 1 provides a high-hardness, deflection-resistant and low-heat-generation semi-steel radial tire bead protection rubber and a preparation method thereof.
The components are as follows: 50 parts of natural rubber, 50 parts of bifunctional polybutadiene rubber, 0.01 part of graphene oxide, 30 parts of white carbon black, 10 parts of carbon black, Si-696 parts of a silane coupling agent, 3 parts of operation oil TDAE, 3 parts of zinc oxide, 4 parts of stearic acid, 2 parts of an anti-aging agent RD, 1 part of sulfur, 1 part of an accelerator CZ and 0.3 part of a scorch retarder CTP.
Preparation of tire bead protection rubber of example 1
(1) Preparation of bifunctional polybutadiene rubber/graphene oxide composite (bifunctional BR/GO)
S101: mixing 2g of graphene oxide (with oxygen content of 30%) with 500mL of tetrahydrofuran, performing ultrasonic dispersion on the suspension, simultaneously assisting mechanical stirring at a rotation speed of 400 r/min, uniformly stirring for 6h, and standing the solution for 12h without obvious layering after stirring.
S102: 100g of bifunctional BR was weighed, cut into small particles and added to 300mL of tetrahydrofuran solution until the bifunctional BR had dissolved and formed a homogeneous solution.
S103: pouring the bifunctional BR solution into the graphene oxide solution dispersed in the step (1), magnetically stirring the mixed solution for 8 hours at the rotation speed of 400 r/min, obtaining a uniform tetrahydrofuran mixed solution of the bifunctional BR/GO after stirring, pouring the mixed solution onto a polytetrafluoroethylene membrane, putting the polytetrafluoroethylene membrane into a fume hood, air-drying for 12 hours, removing most tetrahydrofuran, and then putting the polytetrafluoroethylene membrane into a vacuum oven at 50 ℃ for drying to constant weight.
S104: 100 parts by mass of the prepared raw rubber of amino-siloxane-based bifunctional BR/GO and 2 parts by mass of DCP are mixed by an internal mixer, and the mixture is subjected to mould pressing and vulcanization at 150 ℃ to prepare the bifunctional BR/GO.
(2) Preparation of tire bead protection rubber
S201: putting the bifunctional polybutadiene rubber/graphene oxide composite material and natural rubber into an internal mixer, mixing for 30s at 90 ℃ under 0.60 MPa;
s202: 1/2 adding white carbon black, a silane coupling agent, carbon black, zinc oxide, stearic acid, an anti-aging agent and operating oil, mixing for 60s at the mixing temperature of 100 ℃ and under the pressure of 0.60 MPa;
s203: adding the rest white carbon black, silane coupling agent and carbon black, and mixing for 200s at the mixing temperature of 151 ℃ and the pressure of 0.60 MPa; then extruding the materials into sheets, standing for 2-24 h, and reducing the temperature of the rubber material to room temperature;
s204: adding the rubber material into an internal mixer, mixing for 60s at 85 ℃ and under 0.60 MPa;
s205: adding sulfur, an accelerant and an anti-scorching agent, mixing for 90s at 100 ℃ under 0.60MPa, and then extruding the materials to obtain the tire bead protection rubber.
Comparative example 1
The preparation and parameters of comparative example 1 are identical to those of example 1, except that comparative example 1 uses a conventional unfunctionalized polybutadiene rubber.
Example 2 provides a high-hardness, deflection-resistant and low-heat-generation bead filler for a semisteel radial tire and a preparation method thereof.
The components are as follows: 20 parts of natural rubber, 80 parts of bifunctional polybutadiene rubber, 0.01 part of graphene oxide, 30 parts of white carbon black, 10 parts of carbon black, Si-696 parts of a silane coupling agent, 3 parts of operation oil TDAE, 3 parts of zinc oxide, 4 parts of stearic acid, 2 parts of an anti-aging agent RD, 1 part of sulfur, 1 part of an accelerator CZ and 0.3 part of a scorch retarder CTP.
Preparation of tire bead protection rubber
(2) Preparation of bifunctional polybutadiene rubber/graphene oxide composite (bifunctional BR/GO)
S101: mixing 2g of graphene oxide (with oxygen content of 30%) with 500mL of tetrahydrofuran, performing ultrasonic dispersion on the suspension, simultaneously assisting mechanical stirring at a rotation speed of 400 r/min, uniformly stirring for 6h, and standing the solution for 12h without obvious layering after stirring.
S102: 100g of bifunctional BR was weighed, cut into small particles and added to 300mL of tetrahydrofuran solution until the bifunctional BR had dissolved and formed a homogeneous solution.
S103: pouring the bifunctional BR solution into the graphene oxide solution dispersed in the step (1), magnetically stirring the mixed solution for 8 hours at the rotation speed of 400 r/min, obtaining a uniform tetrahydrofuran mixed solution of the bifunctional BR/GO after stirring, pouring the mixed solution onto a polytetrafluoroethylene membrane, putting the polytetrafluoroethylene membrane into a fume hood, air-drying for 12 hours, removing most tetrahydrofuran, and then putting the polytetrafluoroethylene membrane into a vacuum oven at 50 ℃ for drying to constant weight.
S104: 100 parts by mass of the raw rubber of the prepared sulfydryl-siloxane-based bifunctional BR/GO and 2 parts by mass of DCP are mixed by an internal mixer, and the mixture is subjected to mould pressing and vulcanization at 150 ℃ to prepare the bifunctional BR/GO.
(2) Preparation of tire bead protection rubber
S201: putting the bifunctional polybutadiene rubber/graphene oxide composite material and natural rubber into an internal mixer, mixing for 30s at 90 ℃ under 0.60 MPa;
s202: 1/2 adding white carbon black, a silane coupling agent, carbon black, zinc oxide, stearic acid, an anti-aging agent and operating oil, mixing for 60s at the mixing temperature of 100 ℃ and under the pressure of 0.60 MPa;
s203: adding the rest white carbon black, silane coupling agent and carbon black, and mixing for 200s at the mixing temperature of 151 ℃ and the pressure of 0.60 MPa; then extruding the materials into sheets, standing for 2-24 h, and reducing the temperature of the rubber material to room temperature;
s204: adding the rubber material into an internal mixer, mixing for 60s at 85 ℃ and under 0.60 MPa;
s205: adding sulfur, an accelerant and an anti-scorching agent, mixing for 90s at 100 ℃ under 0.60MPa, and then extruding the materials to obtain the tire bead protection rubber.
Comparative example 2
Comparative example 2 was prepared using the same procedure and parameters as in example 2 except that comparative example 2 used a conventional unfunctionalized polybutadiene rubber.
Example 3
Example 3 provides a high-hardness, deflection-resistant and low-heat-generation bead filler for a semisteel radial tire and a preparation method thereof.
The components are as follows: 20 parts of natural rubber, 80 parts of bifunctional polybutadiene rubber, 0.01 part of graphene oxide, 30 parts of white carbon black, 10 parts of carbon black, Si-696 parts of a silane coupling agent, 3 parts of operation oil TDAE, 3 parts of zinc oxide, 4 parts of stearic acid, 2 parts of an anti-aging agent RD, 1 part of sulfur, 1 part of an accelerator CZ and 0.3 part of a scorch retarder CTP.
Preparation of tire bead protection rubber
(1) Preparation of bifunctional polybutadiene rubber/graphene oxide composite (bifunctional BR/GO)
S101: mixing 2g of graphene oxide (with oxygen content of 30%) with 500mL of tetrahydrofuran, performing ultrasonic dispersion on the suspension, simultaneously assisting mechanical stirring at a rotation speed of 400 r/min, uniformly stirring for 6h, and standing the solution for 12h without obvious layering after stirring.
S102: 100g of bifunctional BR was weighed, cut into small particles and added to 300mL of tetrahydrofuran solution until the bifunctional BR had dissolved and formed a homogeneous solution.
S103: pouring the bifunctional BR solution into the graphene oxide solution dispersed in the step (1), magnetically stirring the mixed solution for 8 hours at the rotation speed of 400 r/min, obtaining a uniform tetrahydrofuran mixed solution of the bifunctional BR/GO after stirring, pouring the mixed solution onto a polytetrafluoroethylene membrane, putting the polytetrafluoroethylene membrane into a fume hood, air-drying for 12 hours, removing most tetrahydrofuran, and then putting the polytetrafluoroethylene membrane into a vacuum oven at 50 ℃ for drying to constant weight.
S104: 100 parts by mass of the raw rubber of the prepared sulfydryl-siloxane-based bifunctional BR/GO and 2 parts by mass of DCP are mixed by an internal mixer, and the mixture is subjected to mould pressing and vulcanization at 150 ℃ to prepare the bifunctional BR/GO.
(2) Preparation of tire bead protection rubber
S201: putting the bifunctional polybutadiene rubber/graphene oxide composite material and natural rubber into an internal mixer, mixing for 30s at 90 ℃ under 0.60 MPa;
s202: 1/2 adding white carbon black, a silane coupling agent, carbon black, zinc oxide, stearic acid, an anti-aging agent and operating oil, mixing for 60s at the mixing temperature of 100 ℃ and under the pressure of 0.60 MPa;
s203: adding the rest white carbon black, silane coupling agent and carbon black, and mixing for 200s at the mixing temperature of 151 ℃ and the pressure of 0.60 MPa; then extruding the materials into sheets, standing for 2-24 h, and reducing the temperature of the rubber material to room temperature;
s204: adding the rubber material into an internal mixer, mixing for 60s at 85 ℃ and under 0.60 MPa;
s205: adding sulfur, an accelerant and an anti-scorching agent, mixing for 90s at 100 ℃ under 0.60MPa, and then extruding the materials to obtain the tire bead protection rubber.
Comparative example 3
Comparative example 3 was prepared using the same procedure and parameters as in example 3 except that comparative example 3 contained 80 parts of natural rubber and 20 parts of difunctional polybutadiene rubber.
Example 4
Example 4 provides a high-hardness, deflection-resistant and low-heat-generation bead filler for a semisteel radial tire and a preparation method thereof.
The components are as follows: 40 parts of natural rubber, 60 parts of bifunctional polybutadiene rubber, 0.01 part of graphene oxide, 30 parts of white carbon black, 10 parts of carbon black, Si-696 parts of a silane coupling agent, 3 parts of operating oil TDAE, 3 parts of zinc oxide, 4 parts of stearic acid, 2 parts of an anti-aging agent RD, 1 part of sulfur, 1 part of an accelerator CZ and 0.3 part of a scorch retarder CTP.
Preparation of tire bead protection rubber
(1) Preparation of bifunctional polybutadiene rubber/graphene oxide composite (bifunctional BR/GO)
S101: mixing 2g of graphene oxide (with oxygen content of 30%) with 500mL of tetrahydrofuran, performing ultrasonic dispersion on the suspension, simultaneously assisting mechanical stirring at a rotation speed of 400 r/min, uniformly stirring for 6h, and standing the solution for 12h without obvious layering after stirring.
S102: 100g of bifunctional BR was weighed, cut into small particles and added to 300mL of tetrahydrofuran solution until the bifunctional BR had dissolved and formed a homogeneous solution.
S103: pouring the bifunctional BR solution into the graphene oxide solution dispersed in the step (1), magnetically stirring the mixed solution for 8 hours at the rotation speed of 400 r/min, obtaining a uniform tetrahydrofuran mixed solution of the bifunctional BR/GO after stirring, pouring the mixed solution onto a polytetrafluoroethylene membrane, putting the polytetrafluoroethylene membrane into a fume hood, air-drying for 12 hours, removing most tetrahydrofuran, and then putting the polytetrafluoroethylene membrane into a vacuum oven at 50 ℃ for drying to constant weight.
S104: 100 parts by mass of the raw rubber of the prepared sulfydryl-siloxane-based bifunctional BR/GO and 2 parts by mass of DCP are mixed by an internal mixer, and the mixture is subjected to mould pressing and vulcanization at 150 ℃ to prepare the bifunctional BR/GO.
(2) Preparation of tire bead protection rubber
S201: putting the bifunctional polybutadiene rubber/graphene oxide composite material and natural rubber into an internal mixer, mixing for 30s at 90 ℃ under 0.60 MPa;
s202: 1/2 adding white carbon black, a silane coupling agent, carbon black, zinc oxide, stearic acid, an anti-aging agent and operating oil, mixing for 60s at the mixing temperature of 100 ℃ and under the pressure of 0.60 MPa;
s203: adding the rest white carbon black, silane coupling agent and carbon black, and mixing for 200s at the mixing temperature of 151 ℃ and the pressure of 0.60 MPa; then extruding the materials into sheets, standing for 2-24 h, and reducing the temperature of the rubber material to room temperature;
s204: adding the rubber material into an internal mixer, mixing for 60s at 85 ℃ and under 0.60 MPa;
s205: adding sulfur, an accelerant and an anti-scorching agent, mixing for 90s at 100 ℃ under 0.60MPa, and then extruding the materials to obtain the tire bead protection rubber.
Comparative example 4
The preparation method and parameters of comparative example 4 are the same as those of example 4 except that 0.01 parts of graphene oxide is not added to comparative example 4.
TABLE 1 mechanical Properties of tire bead protectors for examples and comparative examples
As can be seen from Table 1, compared with the comparative examples, the tire bead filler prepared by the method of the embodiment of the invention has the advantages of improved tensile strength and hardness, obviously improved crack-free deflection times and obviously reduced compression heat generation temperature.
In conclusion, the tire bead protection rubber provided by the invention is obtained by designing the material composition and content, and solves the problems of low mechanical strength, low hardness, high heat generation and the like of the tire bead protection rubber.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. The tire bead protection rubber is characterized by comprising the following raw material components in parts by weight: 10-90 parts of natural rubber, 10-90 parts of bifunctional polybutadiene rubber, 0.01-7.5 parts of graphene oxide, 20-60 parts of white carbon black, 10-20 parts of carbon black and 4-10 parts of silane coupling agent;
wherein the functional groups of the bifunctional polybutadiene rubber are amine groups and siloxane groups.
2. The tire bead protection rubber as claimed in claim 1, further comprising the following raw material components in parts by weight: 3-12 parts of operating oil, 1-5 parts of zinc oxide, 2-6 parts of stearic acid, 1-5 parts of anti-aging agent, 0.1-4 parts of sulfur, 0.1-4 parts of accelerator and 0.1-0.5 part of anti-scorching agent.
3. The tire bead filler of claim 1 or 2, wherein the mass ratio of the difunctional polybutadiene rubber to the natural rubber is greater than or equal to 1: 1.
4. The tire bead filler according to any one of claims 1 to 3, wherein the tire bead filler has a hardness of not less than 70, a no-crack number of flexing times of not less than 30 ten thousand, and a compression fatigue temperature rise of not more than 28 ℃.
5. The method for preparing the tire bead filler according to any one of claims 1 to 4, comprising the steps of:
dispersing the graphene oxide in a first organic solvent to obtain a graphene oxide suspension;
dissolving the difunctional polybutadiene rubber in a second organic solvent to form a rubber solution; wherein the first organic solvent and the second organic solvent are mutually soluble or are the same organic solvent;
mixing the graphene oxide suspension with the rubber solution, and then removing the first organic solvent and the second organic solvent to obtain a bifunctional polybutadiene rubber/graphene oxide composite precursor;
carrying out dehydration condensation reaction on the bifunctional polybutadiene rubber/graphene oxide composite precursor under the action of an initiator to obtain a bifunctional polybutadiene rubber/graphene oxide composite material;
mixing the natural rubber and the dual-functionalized polybutadiene rubber/graphene oxide composite material in a first step;
adding the rest raw material components for further mixing to obtain the tire bead rubber.
6. The preparation method of the tire bead filler according to claim 5, wherein the tire bead filler further comprises the following raw material components in parts by weight: 3-12 parts of operating oil, 1-5 parts of zinc oxide, 2-6 parts of stearic acid, 1-5 parts of anti-aging agent, 0.1-4 parts of sulfur, 0.1-4 parts of accelerator and 0.1-0.5 part of anti-scorching agent;
the further mixing specifically comprises the following steps:
3/10-7/10 parts by weight of the white carbon black, the silane coupling agent, the carbon black, the zinc oxide, the stearic acid, the anti-aging agent and the process oil are added for second-step mixing;
adding the rest white carbon black, the rest zinc oxide, the rest stearic acid and the rest anti-aging agent to carry out the third step of mixing, and then extruding the mixed raw material components to obtain a sizing material;
and mixing the rubber material in the fourth step, adding the sulfur, the accelerator and the anti-scorching agent into the rubber material, and mixing in the fifth step to obtain the tire bead protection rubber.
7. The method for preparing the tire bead filler according to claim 5 or 6, wherein the temperature of the dehydration condensation reaction is 130-170 ℃, the reaction pressure is 10-15MPa, and the reaction time is at least 10 min.
8. The preparation method of the tire bead filler according to claim 6, wherein the mixing temperature of the first step is 80-100 ℃, the mixing temperature of the second step is 90-110 ℃, the mixing temperature of the third step is 145-155 ℃, the mixing temperature of the fourth step is 80-100 ℃, and the mixing temperature of the fifth step is 80-110 ℃.
9. The method for preparing a tire bead filler according to claim 6, wherein the mixing time of the first step is not less than 30s, the mixing time of the second step is not less than 30s, the mixing time of the third step is not less than 150s, the mixing time of the fourth step is not less than 30s, and the mixing time of the fifth step is not less than 60 s.
10. The method for preparing a tire bead filler according to claim 5 or 6, wherein the pressure of each step of mixing is 0.5MPa to 0.65 MPa.
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| CN109929151A (en) * | 2019-04-09 | 2019-06-25 | 江苏通用科技股份有限公司 | Glue and preparation method thereof is protected in all-steel radial tyre rim of the mouth |
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| CN102911411A (en) * | 2012-10-29 | 2013-02-06 | 北京化工大学 | Antistatic low-rolling-resistance tyre tread material and preparation method thereof |
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