CN113502135B - Self-repairing rubber composition for tire and preparation method thereof - Google Patents
Self-repairing rubber composition for tire and preparation method thereof Download PDFInfo
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- CN113502135B CN113502135B CN202110874492.7A CN202110874492A CN113502135B CN 113502135 B CN113502135 B CN 113502135B CN 202110874492 A CN202110874492 A CN 202110874492A CN 113502135 B CN113502135 B CN 113502135B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J119/00—Adhesives based on rubbers, not provided for in groups C09J107/00 - C09J117/00
- C09J119/003—Precrosslinked rubber; Scrap rubber; Used vulcanised rubber
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D30/00—Producing pneumatic or solid tyres or parts thereof
- B29D30/06—Pneumatic tyres or parts thereof (e.g. produced by casting, moulding, compression moulding, injection moulding, centrifugal casting)
- B29D30/0681—Parts of pneumatic tyres; accessories, auxiliary operations
- B29D30/0685—Incorporating auto-repairing or self-sealing arrangements or agents on or into tyres
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
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Abstract
The invention belongs to the technical field of self-repairing tires. Aiming at the problems of non-recyclability, poor flow sealing effect and influence on the balance performance of the tire of the existing tire self-sealing repair material, the self-repairing rubber composition for the tire and the preparation method thereof are provided. The composite material is prepared by matching and using a plurality of materials such as a reversely vulcanized rubber prepolymer, liquid isoprene, triglyceride, silicon dioxide-gel-catalytic repair polymerization agent double-shell microspheres, modified white carbon black, tackifying resin and the like. The prepared self-repairing rubber material has excellent repairing speed and repairing effect, simultaneously has recoverability, can be applied to the inner wall of a tire to play a self-sealing role, and can obviously improve the life safety of drivers and passengers in the running process of the tire and effectively delay the service life of the tire.
Description
Technical Field
The invention belongs to the technical field of self-repairing tires, and particularly relates to a self-repairing rubber composition for a tire and a preparation method thereof.
Background
The tyre is a rubber product which is formed by combining fiber cords, steel wire materials, rubber and the like at a certain temperature, time and pressure, is filled with high-pressure gas to keep a certain outline, and mainly plays a role in supporting and traction in the driving process of an automobile. If the soft rubber is punctured by sharp foreign matters such as nails and the like in the running process of the tire, the tire can be subjected to pressure loss, tire burst and other dangers, and the life safety of drivers and passengers in the running process is seriously influenced by the problem.
In order to solve the problem of driving safety caused by tire puncture pressure loss, a layer of rubber composition with a sealing function is adhered to the inner wall of an inner liner of a tire in the existing tire production technology to achieve the effect of tire puncture pressure maintaining. Researchers have extensively studied and explored the repair sealing material of the tire, for example, chinese patent CN 106795350A introduced a viscous cross-linking repair type rubber composition attached to the inner side of the tire, which is composed of halogenated butyl rubber, liquid polybutene and cross-linking activator, and aims to achieve the effect of stabilizing the tire pressure by viscous flow self-repair after the tire is punctured. The invention patent CN 101254736A reports a rubber composition with repairing and sealing performance, the composition comprises 30-80 parts of SEBS (styrene-ethylene-butadiene-styrene), 10-70 parts of a mixture of natural rubber and butyl rubber and 0-10 parts of resin in parts by weight, and the rubber composition can enable a tire to achieve repairing and sealing effects on a puncture hole through the flowing of self viscosity when the tire is punctured.
The known self-sealing materials for application to the inner wall of a tyre are mainly divided into crosslinked and non-crosslinked flow-type sealing and repairing rubber compositions. When the adhesive layer rubber is in a cross-linked state after sulfur vulcanization, the sealing material after cross-linking and curing has no flowability, so that the phenomena of low plugging rate and poor sealing effect can occur; and the sealing layer material after crosslinking and curing belongs to an irreversible material (converted from a crosslinking state to a non-crosslinking state), and cannot be reused, so that resource waste and environmental pollution are caused. When the attached sealing layer is a non-crosslinked fluid rubber material, although the sealing layer has good flow blocking performance under the action of tire pressure, abnormal flow can be generated under the action of centripetal force when the tire is at a high temperature and a high speed, so that the problem of dynamic unbalance of the tire can be caused, and the life safety of drivers and passengers can be threatened.
Disclosure of Invention
The invention aims to overcome the problems of unrecoverable performance, poor flow sealing effect and influence on tire balance performance of the existing tire self-sealing repair material, and provides a self-repairing rubber composition for a tire and a preparation method thereof. The rubber composition has excellent repairing speed and repairing effect, simultaneously has recyclability, and does not influence the dynamic balance performance of the tire.
The invention is realized by the following technical scheme:
the self-repairing rubber composition for the tire comprises the following components in parts by weight: 90-100 parts of a reverse vulcanized rubber prepolymer, 0-10 parts of liquid isoprene rubber, 3.0-9.0 parts of silica-gel-catalytic repair polymerizer double-shell microspheres, 2.0-5.0 parts of an anti-aging agent, 0-15 parts of modified white carbon black, 0-1.5 parts of a white carbon black dispersing agent and 3.0-5.0 parts of tackifying resin; the core material of the silica-gel-catalytic repair polymerizing agent double-shell microsphere is a nucleophilic reagent capable of initiating double decomposition reaction of S-S cross-linked bonds in the reversely vulcanized rubber prepolymer.
The self-repairing rubber is adhered to the inner wall of an airtight layer of a tire after the tire is vulcanized and molded, when the tire is punctured, double-shell microspheres of a silicon dioxide-gel-catalytic repair polymerizing agent are cracked, a catalytic self-repairing polymerizing agent is released, and the catalytic self-repairing polymerizing agent reacts with a pre-polymer of the reverse vulcanized rubber and a biochemical reaction to be rapidly cross-linked and polymerized, so that the effect of gas barrier property sealing is achieved; the introduction of the tackifying resin can ensure that the material has enough fitting viscosity; meanwhile, the vulcanized rubber composition has the reinforcing effect of the modified white carbon black and a fixed cross-linked network structure, so that the shape can be kept stable in the automobile running process, and the dynamic balance performance of the tire is ensured. When the tire reaches a certain driving mileage, the rubber composition with the self-repairing function can be actively cured and repaired again after being crushed and formed, so that the effects of recycling and environmental resource protection are achieved.
Further, the rubber composition comprises the following components in parts by weight: 90 parts of a reverse vulcanized rubber prepolymer, 10 parts of liquid isoprene rubber, 9.0 parts of silica-gel-catalytic repair polymerizer double-shell microspheres, 2.5 parts of an anti-aging agent, 10 parts of modified white carbon black, 1 part of a white carbon black dispersing agent and 4 parts of tackifying resin.
Further, the silica-gel-catalytic repair polymerization agent microsphere is prepared by the following method:
the first step is as follows: mixing deionized water and a surfactant according to a volume ratio of 5.0-5.5; mixing and fully stirring styrene monomer, toluene, benzoyl peroxide and catalytic repair polymerization agent according to the mass ratio of 30-35; pouring an oil phase dispersing agent into the aqueous phase solution, controlling the temperature to be 40-50 ℃, stirring at the speed of 600-800 rpm, carrying out crosslinking reaction for 12-14 hours to coat the oil phase dispersing agent into balls, washing and centrifuging to remove unreacted impurities to obtain crosslinked styrene coated catalytic repair polymerization agent gel microspheres;
the second step is that: mixing deionized water and a surfactant according to a volume ratio of 5.0-5.5; simultaneously mixing toluene, ethyl orthosilicate, (3-aminopropyl) triethoxysilane and crosslinked styrene-coated catalytic repair polymerization agent gel microspheres in a mass ratio of (15-18); pouring the oil phase mixed solution into the water phase solution, mixing and stirring at the stirring speed of 1000rpm-1200rpm, and running for 1.0-1.5 hours at room temperature; then adjusting the temperature to 70-75 ℃, rotating speed to 500-600rpm, reacting for 12-14 hours, washing and centrifuging until impurities are removed, and finally obtaining the silica-gel-catalytic repair polymerizing agent double-shell microspheres through natural ventilation drying.
Further, the catalytic repair polymerization agent is nucleophilic reagent tributyl phosphine and/or triethylamine.
Further, the surfactant adopted in the first step is one or a mixture of more than one of octadecyl amine polyoxyethylene ether biquaternary ammonium salt, hexadecyl trimethyl ammonium chloride, didodecyl dimethyl-gamma-biquaternary ammonium salt, polydimethyl diallyl ammonium chloride and N-dodecyl biquaternary ammonium salt, and deionized water and the surfactant are mixed according to the volume ratio of 5.0; styrene monomer, toluene, benzoyl peroxide and catalytic repair polymerization agent are mixed according to the mass ratio of 30.0;
the second step is as follows: the used surfactant is one or a mixture of more of octadecyl amine polyoxyethylene ether biquaternary ammonium salt, hexadecyl trimethyl ammonium chloride, didodecyl dimethyl-gamma-biquaternary ammonium salt, polydimethyl diallyl ammonium chloride and N-dodecyl biquaternary ammonium salt, the surfactant and deionized water are mixed according to the proportion of 1.0, and the gel microsphere of the catalytic repair polymerization agent is coated by toluene, ethyl orthosilicate, (3-aminopropyl) triethoxysilane and crosslinked styrene according to the weight ratio of 1.0:6.0 mass ratio.
Further, hydrochloric acid is adopted to adjust the pH value in the first step and the second step;
further, the product was washed with absolute ethanol in both the first and second steps.
Further, the reverse vulcanized rubber prepolymer is prepared by the following method: weighing 40-45 parts by weight of common sulfur powder, 15-20 parts by weight of polydiene rubber and 25-35 parts by weight of triglyceride, placing the raw materials into a reaction kettle, controlling the temperature of the reaction kettle to be 165-175 ℃, controlling the stirring speed to be 200-300rpm, and reacting for 12-14 min; and obtaining the inverse vulcanized rubber prepolymer after the reaction is finished.
The reverse vulcanized rubber prepolymer is a rubber composition with a self-repairing function, which is prepared by processing a mixture of a polyene rubber material and a triglyceride compound at a certain temperature under the condition that a large amount of sulfur is added, so that sulfur molecules can be subjected to cross-linking polymerization to form a chain polymer, inserting a polyene rubber molecular chain and triglyceride into the sulfur molecular chain to form a cross-linked polymer in the process, and mixing, vulcanizing and curing the mixture by using silica-gel-catalytic repair polymerization agent double-shell microspheres. When the microspheres in the rubber composition are broken, a nucleophilic reagent with a repairing function is released, so that the S-S bond in the rubber composition is triggered to generate a double decomposition reaction, and the purpose of quickly healing the puncture is achieved.
Further, the polydiene hydrocarbon rubber material is at least one of styrene and dicyclopentadiene.
Further, the rubber hydrocarbon content in the liquid isoprene rubber is more than or equal to 95 percent, the weight average molecular weight is 35000-56000, and the flow viscosity is 400-600 Pa.s at 35 ℃;
further, the tackifying resin is at least one of tall oil rosin resin, C5/C9 petroleum resin, dicyclopentadiene (DCPD) resin, coumarone-indene resin and styrene series resin.
Further, the modified white carbon black is prepared by grafting the following groups on the surface of common hydrated silicon dioxide through modification: at least one of vinyl-triethoxysilane, dimethyldichlorosilane, polyethylene glycol-6000 and glycidyl methacrylate, wherein the CTAB specific surface area of the modified white carbon black is 160-220m 2 /g；
Further, the white carbon black dispersing agent is one or a mixture of KYC-913, white carbon black dispersing agent HTS and white carbon black dispersing agent ST;
further, the anti-aging agent is at least one of RD and 264.
The invention also provides a preparation method of the self-repairing rubber composition for the tire, which comprises the following steps:
first-stage mixing:
1) Setting the temperature of the reaction kettle to be 160 ℃ and the stirring speed to be 65-70rpm, adding 90-100 parts by weight of rubber prepolymer and 0-10 parts by weight of liquid isoprene rubber into the reaction kettle, simultaneously adding 2.0-5.0 parts by weight of antioxidant into the reaction kettle, and stirring and mixing for 4-5min;
2) Adding 0-15 parts by weight of modified white carbon black, 0-1.5 parts by weight of white carbon black dispersant and 3.0-5.0 parts by weight of tackifying resin into a reaction kettle, and stirring and mixing for 4-5min to obtain a first-stage mixed rubber composition;
and (3) second-stage mixing:
3) Adding the rubber composition glue prepared in the step 2) into a reaction kettle with the temperature controlled at 100-120 ℃ and the rotating speed of 65-75rpm, adding 3.0-9.0 parts by weight of silica-gel-catalytic repair polymerizer double-shell microspheres, and stirring and mixing for 3.0-5.0min to obtain a second-stage mixed rubber composition;
and (3) vulcanization:
4) Adding the two-stage mixed rubber composition material prepared in the step 3) into a vulcanization mold, controlling the temperature of a vulcanizing machine to be 130-135 ℃, and vulcanizing for 12-14 hours to obtain the self-repairing rubber composition for the tire.
In the mixing process of the rubber composition, the added silica-gel double-shell microspheres are not cracked due to the fact that the pressure of the silica shell in flowing rubber is small, and the pressure of instant puncture of a tire in vulcanized rubber can reach more than 300MPa, so that the double-shell microspheres are cracked by extrusion, and an internal catalytic repair polymerizing agent can flow out to repair and heal the puncture.
The rubber material prepared by adopting the inverse vulcanization technology is used together with the silica-gel double-shell microspheres coated with the catalytic repair polymerizing agent, and meanwhile, the modified white carbon black and the tackifying resin with the adhesion effect are added into the mixture. The prepared rubber composition can be attached to the inner wall of the tire inner liner, when the tire is punctured by a nail or other hard objects in the running process, the silicon dioxide-gel-catalytic repair polymerization agent double-shell microspheres in the cracked rubber composition can be cracked due to instantaneous high pressure, so that the catalytic repair polymerization agent is released, the cracked self-repair rubber composition layer can be crosslinked and healed again in a short time, and the self-sealing effect of stabilizing the tire pressure of the tire is achieved; and the addition of the modified white carbon black and the tackifying resin can ensure that the self-repairing rubber composition keeps certain strength and good bonding performance with the air-tight layer. Meanwhile, the rubber composition with the self-repairing function can be crushed and then secondarily molded, so that the purposes of recycling and saving resources are achieved; the application of the self-repairing rubber composition to the inner wall of the tire can effectively improve the service life of the tire and the life safety of drivers and passengers.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
The liquid isoprene rubber adopted in the following examples has rubber hydrocarbon content of more than or equal to 95%, weight average molecular weight of 35000 and flow viscosity (35 ℃) of 500 Pa.s; the tackifying resin is tall oil rosin resin; modified whiteThe carbon black is vinyl-triethoxysilane modified white carbon black, and the CTAB specific surface area of the carbon black is 190m 2 (iv) g; the white carbon black dispersant is ST; the anti-aging agent is RD.
The following example was prepared using the following procedure for the reverse vulcanized rubber prepolymer:
weighing 45 parts by weight of common sulfur powder, 20 parts by weight of polystyrene rubber and 35 parts by weight of triglyceride, placing the raw materials into a reaction kettle, controlling the temperature of the reaction kettle to be 165-175 ℃, controlling the stirring speed to be 300rpm, and controlling the reaction time to be 12-14 min; and obtaining the inverse vulcanized rubber prepolymer after the reaction is finished.
The silica-gel-catalyzed repair polymerizer microspheres used in the following examples were prepared by the following method:
the first step is as follows: mixing deionized water and octadecyl amine polyoxyethylene ether biquaternary ammonium salt according to the volume ratio of 5.0; mixing and fully stirring styrene monomer, toluene, benzoyl peroxide and catalytic repair polymerization agent triethylamine according to the mass ratio of 30.0; pouring an oil phase dispersing agent into the aqueous phase solution, controlling the temperature to be 40-50 ℃, stirring at the speed of 600-800 rpm, carrying out crosslinking reaction for 12 hours, coating the mixture into balls, washing the balls with absolute ethyl alcohol, centrifuging the balls, and removing unreacted impurities to obtain crosslinked styrene coated catalytic repair polymerization agent gel microspheres;
the second step is that: mixing octadecyl amine polyoxyethylene ether biquaternary ammonium salt with deionized water according to the volume ratio of 1.0; simultaneously mixing toluene, ethyl orthosilicate, (3-aminopropyl) triethoxysilane and crosslinked styrene-coated catalytic repair polymerization agent gel microspheres in a mass ratio of 15; pouring the oil phase mixed solution into the water phase solution, mixing and stirring at the stirring speed of 1000-1200 rpm, and operating at room temperature for 1 hour; then adjusting the temperature to 70 ℃, rotating speed to 500rpm, reacting for 12 hours, washing with absolute ethyl alcohol, centrifuging until impurities are removed, and finally obtaining the silica-gel-catalytic repair polymerization agent double-shell microspheres through natural ventilation drying.
The raw material units "parts" in the following examples are parts by weight unless otherwise specified.
Example 1
90 parts of an inverse vulcanized rubber prepolymer, 10 parts of liquid isoprene rubber, 3.0 parts of silica-gel-catalytic repair polymerizer double-shell microspheres, 2.5 parts of an anti-aging agent, 10 parts of modified white carbon black, 1.0 part of a white carbon black dispersing agent and 4.0 parts of a tackifying resin are adopted. The specific formulation is shown in table 1.
The preparation process of the self-repairing rubber composition comprises the following steps:
first-stage mixing:
1) Setting the temperature of the reaction kettle to be 160 ℃ and the stirring speed to be 70rpm, adding the rubber prepolymer and the liquid isoprene rubber into the reaction kettle, simultaneously adding the anti-aging agent into the reaction kettle, and stirring and mixing for 4min;
2) And putting the modified white carbon black, the white carbon black dispersing agent and the tackifying resin into a reaction kettle, and stirring and mixing for 5min to obtain the first-stage mixed rubber composition.
And (3) second-stage mixing:
3) Adding the rubber composition glue prepared in the step 2) into a reaction kettle with the temperature controlled at 120 ℃ and the rotating speed of 75rpm, adding silica-gel-catalytic repair polymerization agent double-shell microspheres, and stirring and mixing for 3.0min in the second stage to obtain the mixed rubber composition.
And (3) vulcanization:
4) Adding the mixed rubber composition material prepared in the step 3) into a vulcanization mould with a fixed shape, and controlling the temperature of a vulcanizing machine to be 135 ℃ and the time to be 14 hours for vulcanization, fixation and molding to obtain the self-repairing rubber composition.
The prepared self-repairing rubber composition is pasted on the inner wall of the inner liner of the tire, and the sealing effect on the tire is observed.
The apparent sealing effect of the self-healing rubber compositions is shown in table 1.
Example 2
100 parts of an inverse vulcanized rubber prepolymer, 6.0 parts of silica-gel-catalytic repair polymerizer double-shell microspheres, 2.5 parts of an anti-aging agent, 10 parts of modified white carbon black, 1.0 part of a white carbon black dispersing agent and 4.0 parts of tackifying resin are adopted. The specific formulation is shown in table 1.
The preparation process of the self-repairing rubber composition comprises the following steps:
first-stage mixing:
1) Setting the temperature of the reaction kettle to be 160 ℃ and the stirring speed to be 70rpm, adding the inverse vulcanized rubber prepolymer into the reaction kettle, simultaneously adding the anti-aging agent into the reaction kettle, and stirring and mixing for 4min;
2) And putting the modified white carbon black, the white carbon black dispersant and the tackifying resin into a reaction kettle, and stirring and mixing for 5min to obtain the first-stage mixed rubber composition.
And (3) second-stage mixing:
3) Adding the rubber composition glue prepared in the step 2) into a reaction kettle with the temperature controlled at 120 ℃ and the rotating speed of 75rpm, adding silica-gel-catalytic repair polymerization agent double-shell microspheres, and stirring and mixing for 3.0min in the second stage to obtain the mixed rubber composition.
And (3) vulcanizing:
4) Adding the mixed rubber composition material prepared in the step 3) into a vulcanization mould with a fixed shape, and controlling the temperature of a vulcanizing machine to be 135 ℃ and the time to be 14 hours for vulcanization, fixation and molding to obtain the self-repairing rubber composition.
The prepared self-repairing rubber composition is pasted on the inner wall of the inner liner of the tire, and the sealing effect on the tire is observed.
The apparent sealing effect of the self-healing rubber compositions is shown in table 1.
Example 3
90 parts of a reverse vulcanized rubber prepolymer, 10 parts of liquid isoprene rubber, 9.0 parts of silica-gel-catalytic repair polymerizer double-shell microspheres, 2.5 parts of an anti-aging agent, 10 parts of modified white carbon black, 1.0 part of a white carbon black dispersing agent and 4.0 parts of a tackifying resin are adopted. The specific formulation is shown in table 1.
The preparation process of the self-repairing rubber composition comprises the following steps:
first-stage mixing:
1) Setting the temperature of the reaction kettle to be 160 ℃ and the stirring rotation speed to be 70rpm, adding the inverse vulcanized rubber prepolymer and the liquid isoprene rubber into the reaction kettle, simultaneously adding the anti-aging agent into the reaction kettle, and stirring and mixing for 4min;
2) And putting the modified white carbon black, the white carbon black dispersant and the tackifying resin into a reaction kettle, and stirring and mixing for 5min to obtain the first-stage mixed rubber composition.
And (3) second-stage mixing:
3) Adding the rubber composition glue prepared in the step 2) into a reaction kettle with the temperature controlled at 120 ℃ and the rotating speed of 75rpm, adding silica-gel-catalytic repair polymerization agent double-shell microspheres, and stirring and mixing for 3.0min in the second stage to obtain the mixed rubber composition.
And (3) vulcanizing:
4) Adding the mixed rubber composition material prepared in the step 3) into a vulcanization mould with a fixed shape, and controlling the temperature of a vulcanizing machine to be 135 ℃ and the time to be 14 hours for vulcanization, fixation and molding to obtain the self-repairing rubber composition.
The prepared self-repairing rubber composition is pasted on the inner wall of the tire inner liner, and the sealing effect on the tire is observed.
The apparent sealing effect of the self-healing rubber compositions is shown in table 1.
Comparative example 1
40 parts of natural rubber, 30 parts of SBS thermoplastic elastomer, 30 parts of liquid isoprene rubber, 10 parts of modified white carbon black, 2.5 parts of anti-aging agent, 1.0 part of white carbon black dispersing agent and 5.0 parts of tackifying resin.
The specific formulation is shown in table 1.
First-stage mixing:
1) Setting the temperature of the reaction kettle to be 160 ℃ and the stirring rotation speed to be 70rpm, adding the natural rubber, the SBS thermoplastic elastomer and the liquid isoprene rubber into the reaction kettle, simultaneously adding the anti-aging agent into the reaction kettle, and stirring and mixing for 4min;
2) And putting the modified white carbon black, the white carbon black dispersant and the tackifying resin into a reaction kettle, and stirring and mixing for 5min to obtain the first-stage mixed rubber composition.
And (3) second-stage mixing:
3) Adding the rubber composition glue prepared in the step 2) into a reaction kettle with the temperature controlled at 160 ℃ and the rotating speed of 75rpm, and stirring and mixing for 30min in the second stage to obtain the mixed rubber composition.
Molding:
4) Adding the mixed rubber composition material prepared in the step 3) into a vulcanization mould with a fixed shape, controlling the temperature to be 135 ℃ and carrying out compression molding for 30 minutes to obtain a comparative rubber composition.
The prepared comparative rubber composition was applied to the inner wall of the inner liner of the tire, and the sealing effect on the tire was observed.
The apparent sealing effect of the comparative rubber compositions is shown in Table 1.
Comparative example 2
90 parts of brominated butyl rubber, 230 parts of liquid polybutene, 2.5 parts of anti-aging agent, 16 parts of modified white carbon black, 1.0 part of white carbon black dispersant, 10 parts of tackifying resin, 2.0 parts of benzoyl peroxide and 5.0 parts of p-benzoquinone dioxime. The specific formulation is shown in table 1. The preparation process of the self-repairing rubber composition comprises the following steps:
first-stage mixing:
1) Setting the temperature of the reaction kettle to be 160 ℃ and the stirring speed to be 70rpm, adding the brominated butyl rubber and the liquid polybutene into the reaction kettle, simultaneously adding the anti-aging agent into the reaction kettle, and stirring and mixing for 4min;
2) And putting the modified white carbon black, the white carbon black dispersing agent and the tackifying resin into a reaction kettle, and stirring and mixing for 5min to obtain the first-stage mixed rubber composition.
And (3) second-stage mixing:
3) Adding the rubber composition glue prepared in the step 2) into a reaction kettle with the temperature controlled at 120 ℃ and the rotating speed of 75rpm, then adding benzoyl peroxide and p-benzoquinone dioxime, and stirring and mixing for the second time for 3.0min to obtain the mixed rubber composition.
And (3) vulcanization:
4) Adding the mixed rubber composition material prepared in the step 3) into a vulcanization mould with a fixed shape, controlling the temperature of a vulcanizing machine to be 135 ℃ and the time to be 2 hours for vulcanization, fixing and molding, and obtaining the contrast self-repairing rubber composition.
The prepared comparative self-repairing rubber composition is pasted on the inner wall of the tire inner liner, and the sealing effect on the tire is observed.
The apparent sealing effect of the comparative self-healing rubber compositions is shown in table 1.
Comparative example 3
90 parts of reverse vulcanized rubber prepolymer, 10 parts of liquid isoprene rubber, 2.5 parts of anti-aging agent, 10 parts of modified white carbon black, 1.0 part of white carbon black dispersant and 4.0 parts of tackifying resin are adopted. The specific formulation is shown in table 1.
The preparation process of the self-repairing rubber composition comprises the following steps:
first-stage mixing:
1) Setting the temperature of the reaction kettle to be 160 ℃ and the stirring rotation speed to be 70rpm, adding the inverse vulcanized rubber prepolymer and the liquid isoprene rubber into the reaction kettle, simultaneously adding the anti-aging agent into the reaction kettle, and stirring and mixing for 4min;
2) And putting the modified white carbon black, the white carbon black dispersant and the tackifying resin into a reaction kettle, and stirring and mixing for 5min to obtain the first-stage mixed rubber composition.
And (3) second-stage mixing:
3) Adding the rubber composition glue prepared in the step 2) into a reaction kettle with the temperature controlled at 120 ℃ and the rotating speed of 75rpm, and stirring and mixing for 3.0min for the second period to obtain the mixed rubber composition.
And (3) vulcanization:
4) Adding the mixed rubber composition material prepared in the step 3) into a vulcanization mould with a fixed shape, controlling the temperature of a vulcanizing machine to be 135 ℃ and the time to be 14 hours for vulcanization, fixing and molding, and obtaining the contrast self-repairing rubber composition.
The prepared comparative self-repairing rubber composition is pasted on the inner wall of the tire inner liner, and the sealing effect on the tire is observed.
The apparent sealing effect of the comparative self-healing rubber compositions is shown in table 1.
Performance testing
The self-repairing rubber materials prepared in examples 1 to 3 and comparative examples 1 to 3 were applied to the inner liner of the tire for sealing performance test, and the sealing curing property and the sealing effect were measured.
The prepared rubber composition is applied and attached to the inner liner of the tire, then, 5 parallel sample tire treads filled with the same air pressure are punctured by using iron nails with the diameter of 3mm, then the iron nails are removed, and the change of the air pressure of the tire is tested after the tire runs for 150min at the speed of 70Km/h so as to evaluate the sealing effect brought by the self-repairing rubber composition.
And (3) carrying out dynamic balance test on the tested tire, then detaching the tire from the rim, observing the self-repairing healing effect of the punctured part by naked eyes and analyzing the healing condition.
Table 1 shows the raw material composition and the sealing effect of the self-repairing rubber composition prepared in the example and the comparative example
(1) Whether healing occurred was observed by the effect of repairing the puncture with an iron nail after the test (o indicates that healing did not occur; \9679; indicating that healing occurred).
(2) The repairing effect is represented by "tire pressure constant tire number/original normal tire pressure tire number".
It can be understood from the experimental implementation results of the comparative example and the example given in table 1 that, as compared with the flow type sealing material of the comparative example 1 and the cross-linking type sealing material of the comparative example 2, it can be found that the self-repairing rubber composition in the example introduces the inverse vulcanized rubber prepolymer and the silica-gel-catalytic repairing polymerization agent double-shell microspheres with the cross-linking catalytic function, after the tire runs for 150min at the speed of 70Km/h, the sealing material prepared in the comparative examples 1-2 has poor repairing effect, and the dynamic balance performance of the example 1 is far better than that of the comparative examples 1-2. Example 1 compares with comparative example 3 and demonstrates that the addition of silica-gel-catalytic repair polymerizer double-shell microspheres can promote the healing repair of a reverse vulcanized rubber prepolymer. Compared with the comparative examples 1 to 3, the dynamic balance effect and the sealing and healing effects of the self-repairing rubber composition are obviously improved by introducing the silica-gel-catalytic repair polymerization agent double-shell microspheres. Compared with the comparative examples 1 to 3, the content of the silica-gel-catalytic repair polymerization agent double-shell microspheres in the examples 1 to 3 is increased, so that the dynamic balance effect of the tire is obviously improved, the puncture self-repairing effect has the characteristic of being visible to naked eyes, and compared with the repairing effect of the puncture of the comparative examples 1 to 3, the self-repairing rubber composition prepared in the examples has obvious advantages in healing and sealing effects compared with the self-sealing materials of the comparative examples 1 to 3.
Therefore, the introduction of the reverse vulcanized rubber prepolymer and the silica-gel-catalytic repair polymerization agent double-shell microsphere system can effectively generate a self-repair effect; the increase of the content of the silica-gel-catalytic repair polymerization agent double-shell microspheres can enable the tire to have excellent dynamic balance performance after the self-repairing rubber composition is healed. The self-repairing and sealing effects of the examples 2-3 are the best.
As described above, the self-repairing rubber composition used on the inner liner of the automobile tire is characterized in that the self-repairing rubber composition has a characteristic rubber material capable of chemically reacting with a catalytic polymerization material to heal after being pierced by a hard foreign object during the running process of the tire. When the tire is punctured, the puncture hole is healed, so that the tire pressure of the tire is kept at a certain level for stable and continuous running. In addition, the rubber composition has the characteristic of self-healing repair, so that the rubber composition has the characteristic of being capable of being crushed and recycled for molding and utilization. This not only can improve the availability of resources and reduce environmental pollution, but also can contribute to improving the driving safety of the driver and passengers when applied to the sealing material for tires.
The above-mentioned embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solution of the present invention by those skilled in the art should fall within the protection scope defined by the claims of the present invention without departing from the spirit of the present invention.
Claims (7)
1. The self-repairing rubber composition for the tire is characterized by comprising the following components in parts by weight: 90-100 parts of a reverse vulcanized rubber prepolymer, 0-10 parts of liquid isoprene rubber, 3.0-9.0 parts of silica-gel-catalytic repair polymerizer double-shell microspheres, 2.0-5.0 parts of an anti-aging agent, 0-15 parts of modified white carbon black, 0-1.5 parts of a white carbon black dispersing agent and 3.0-5.0 parts of tackifying resin; the core material of the silica-gel-catalytic repair polymerizing agent double-shell layer microsphere is a nucleophilic reagent capable of initiating an S-S cross-linked bond in the reverse vulcanized rubber prepolymer to perform a double decomposition reaction;
the silica-gel-catalytic repair polymerization agent microsphere is prepared by the following method:
the first step is as follows: mixing deionized water and a surfactant according to a volume ratio of 5.0-5.5; mixing and fully stirring styrene monomer, toluene, benzoyl peroxide and catalytic repair polymerization agent according to the mass ratio of (30-35) to (5.0-6.0) to (1.0-1.5) to (2.0-2.5) to prepare an oil phase dispersing agent; pouring the oil phase dispersing agent into the water phase solution, controlling the temperature to be 40-50 ℃, stirring at the speed of 600-800 rpm, carrying out crosslinking reaction for 12-14 hours, coating the mixture into balls, washing, centrifuging, and removing unreacted impurities to obtain crosslinked styrene coated catalytic repair polymerizing agent gel microspheres;
the second step is that: mixing ionic water, a surfactant and water according to a volume ratio of 5.0-5.5; simultaneously mixing toluene, ethyl orthosilicate, (3-aminopropyl) triethoxysilane and crosslinked styrene coated catalytic repair polymerization agent gel microspheres in a mass ratio of (15-18) - (1.0-1.5) - (6.0-7.0) to obtain an oil phase mixed solution; pouring the oil phase mixed solution into the water phase solution, mixing and stirring at the stirring speed of 1000-1200 rpm for 1.0-1.5 hours at room temperature; then adjusting the temperature to 70-75 ℃, rotating speed to 500-600rpm, reacting for 12-14 hours, washing and centrifuging until impurities are removed, and finally obtaining the silica-gel-catalytic repair polymerization agent double-shell microspheres through natural ventilation drying;
the reverse vulcanized rubber prepolymer is prepared by the following method: weighing 40-45 parts of common sulfur powder, 15-20 parts of polydiene rubber and 25-35 parts of triglyceride by weight, placing the raw materials into a reaction kettle, controlling the temperature of the reaction kettle between 165 ℃ and 175 ℃, and stirring at the rotating speed of 200-300rpm for 12-14 min; obtaining a reverse vulcanized rubber prepolymer after the reaction is finished;
the modified white carbon black is prepared by grafting the following groups on the surface of common hydrated silicon dioxide in a modifying way: at least one of vinyl-triethoxysilane, dimethyldichlorosilane, polyethylene glycol-6000 and glycidyl methacrylate, and the CTAB specific surface area of the modified white carbon black is 160-220m 2 (ii)/g; the white carbon black dispersing agent is one or a mixture of KYC-913, white carbon black dispersing agent HTS and white carbon black dispersing agent ST; the anti-aging agent is at least one of RD or 264.
2. The self-repairing rubber composition of claim 1, comprising the following components in parts by weight: 90 parts of a reverse vulcanized rubber prepolymer, 10 parts of liquid isoprene rubber, 9.0 parts of silica-gel-catalytic repair polymerizer double-shell microspheres, 2.5 parts of an anti-aging agent, 10 parts of modified white carbon black, 1.0 part of a white carbon black dispersing agent and 4.0 parts of a tackifying resin.
3. The self-repairing rubber composition of claim 1, wherein the surfactant adopted in the first step is one or more of octadecyl amine polyoxyethylene ether biquaternary ammonium salt, hexadecyl trimethyl ammonium chloride, didodecyl dimethyl-gamma-biquaternary ammonium salt, polydimethyl diallyl ammonium chloride and N-dodecyl biquaternary ammonium salt, and deionized water is mixed with the surfactant according to a volume ratio of 5.0; styrene monomer, toluene, benzoyl peroxide and catalytic repair polymerization agent are mixed according to the mass ratio of 30.0;
the second step is as follows: the used surfactant is one or a mixture of more of octadecyl amine polyoxyethylene ether biquaternary ammonium salt, hexadecyl trimethyl ammonium chloride, didodecyl dimethyl-gamma-biquaternary ammonium salt, polydimethyl diallyl ammonium chloride and N-dodecyl biquaternary ammonium salt, the surfactant is mixed with deionized water according to the volume ratio of 5.0: 6.0 mass ratio.
4. The self-repairing rubber composition of claim 1, wherein the first step and the second step are performed by adjusting the pH value with hydrochloric acid and washing the product with absolute ethanol.
5. The self-repairing rubber composition of claim 1, wherein the polydiene-based rubber material is at least one of styrene and dicyclopentadiene.
6. The self-repairing rubber composition of claim 1, wherein the rubber hydrocarbon content of the liquid isoprene rubber is not less than 95%, the weight average molecular weight is 35000-56000, and the flowing viscosity at 35 ℃ is 400-600 Pa-s; the tackifying resin is at least one of tall oil rosin resin, C5/C9 petroleum resin, dicyclopentadiene resin, coumarone-indene resin and styrene series resin.
7. The preparation method of the self-repairing rubber composition for the tire as claimed in claim 1, characterized by comprising the following steps:
first-stage mixing:
1) Setting the temperature of the reaction kettle to be 150-160 ℃ and the stirring speed to be 65-70rpm, adding 90-100 parts by weight of rubber prepolymer and 0-10 parts by weight of liquid isoprene rubber into the reaction kettle, simultaneously adding 2.0-5.0 parts by weight of antioxidant into the reaction kettle, and stirring and mixing for 4-5min;
2) Adding 0-15 parts by weight of modified white carbon black, 0-1.5 parts by weight of white carbon black dispersant and 3.0-5.0 parts by weight of tackifying resin into a reaction kettle, and stirring and mixing for 4-5min to obtain a first-stage mixed rubber composition;
and (3) second-stage mixing:
3) Adding the rubber composition glue prepared in the step 2) into a reaction kettle with the temperature controlled at 100-120 ℃ and the rotating speed of 65-75rpm, adding 3.0-9.0 parts by weight of silica-gel-catalytic repair polymerizer double-shell microspheres, and stirring and mixing for 3.0-5.0min to obtain a second-stage mixed rubber composition;
and (3) vulcanization:
4) Adding the two-stage mixed rubber composition material prepared in the step 3) into a vulcanization mold, controlling the temperature of a vulcanizing machine to be 130-135 ℃ and the vulcanization time to be 12-14 hours, and obtaining the self-repairing rubber composition for the tire.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105733110A (en) * | 2016-02-25 | 2016-07-06 | 北京石油化工学院 | Method for preparing thermal-reversible cross-linking polyisobutene rubber capable of being processed repeatedly |
| CN110283565A (en) * | 2019-06-12 | 2019-09-27 | 东莞市旭宸环保科技有限公司 | A kind of self-repair material and preparation method thereof for tyre lunge-proof leakage |
| CN111518506A (en) * | 2020-05-21 | 2020-08-11 | 赛轮集团股份有限公司 | Self-repairing high-molecular adhesive for tire and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105733110A (en) * | 2016-02-25 | 2016-07-06 | 北京石油化工学院 | Method for preparing thermal-reversible cross-linking polyisobutene rubber capable of being processed repeatedly |
| CN110283565A (en) * | 2019-06-12 | 2019-09-27 | 东莞市旭宸环保科技有限公司 | A kind of self-repair material and preparation method thereof for tyre lunge-proof leakage |
| CN111518506A (en) * | 2020-05-21 | 2020-08-11 | 赛轮集团股份有限公司 | Self-repairing high-molecular adhesive for tire and preparation method thereof |
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