CN116253939A - Preparation method of low-heat-generation tire bead filler for preventing bead void and tire - Google Patents
Preparation method of low-heat-generation tire bead filler for preventing bead void and tire Download PDFInfo
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- CN116253939A CN116253939A CN202310106343.5A CN202310106343A CN116253939A CN 116253939 A CN116253939 A CN 116253939A CN 202310106343 A CN202310106343 A CN 202310106343A CN 116253939 A CN116253939 A CN 116253939A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C15/00—Tyre beads, e.g. ply turn-up or overlap
- B60C15/06—Flipper strips, fillers, or chafing strips and reinforcing layers for the construction of the bead
- B60C15/0603—Flipper strips, fillers, or chafing strips and reinforcing layers for the construction of the bead characterised by features of the bead filler or apex
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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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
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Abstract
The application provides a preparation method of a low-heat-generation tire bead filler for preventing bead void and a tire, and the tire comprises the following components in parts by weight: 20-80 parts of natural rubber, 10-35 parts of styrene-butadiene rubber, 15-45 parts of solution polymerized styrene-butadiene rubber, 1.0-4.0 parts of zinc oxide, 1-4 parts of stearic acid, 1-5 parts of polyethylene glycol, 1.0-3.2 parts of dispersing agent, 1.5-6.0 parts of anti-aging agent, 1.5-3.5 parts of protective wax, 3-9 parts of tackifying resin, 1-8 parts of heat stabilizer, 45-110 parts of carbon black, 3-6 parts of silane coupling agent, 2-6 parts of sulfur, 2-13 parts of accelerator and 0.1-1 part of scorch retarder.
Description
The application is a divisional application, the application number of the original application is 2021111865202, the application date is 2021, 10 and 12 days, and the invention is named as a tire bead filler for preventing bead void and a preparation method and application thereof.
Technical Field
The invention belongs to the technical field of tire manufacturing, and particularly relates to a preparation method of a low-heat-generation tire bead filler for preventing bead void and a tire.
Background
With the development of society, the requirements of people on running safety, high speed, environmental protection and the like are gradually increased, as a tire for the first life of automobile running safety, the safety upgrading of the tire is inadvisable, after meridian and tubeless tire popularization, the tire accident is halved, the tire burst phenomenon is mostly disappeared, the running problem of the tire can be realized without running for hundreds of thousands of kilometers, but the venting and tire burst are still a worry;
as the rim of the tire is directly received by the rim of the automobile, the rim and the rim generate friction, heat accumulation is more and more, and the temperature is higher and higher along with the running of the tire, so that the rim rubber generates vulcanization reversion phenomenon, thereby causing fracture of a rim rubber crosslinking bond, performance reduction and further leading to rim void, the rim crack, rim explosion and other series of early damage quality problems can occur after the rim void reaches a certain degree, the rim void phenomenon easily occurs due to long-term overload phenomenon in the use process of the tire, and the rim is cracked and leaked when the tire continues running under the condition that the rim void is not found by an owner, finally leading to tire burst and great threat to the running safety of the automobile;
therefore, the low heat generating performance and the heat-resistant stability of the bead filler are important, and the improvement of the bead clearance of the tire is to reduce the risk of the bead clearance of the tire, improve the safety performance of the tire and meet the product requirements of people.
Disclosure of Invention
The invention aims to solve the technical problem that the existing tire bead filler is easy to generate bead voids, and provides the low-heat-generation tire bead filler for preventing the bead voids, which can effectively improve the formula rigidity, the tensile strength, the tearing strength, the small permanent deformation, the good flexibility and rebound resilience, can improve the bonding force of each part, enhance the bonding strength with the surface of a contact part, has low heat generation and good heat aging resistance, has cohesive force larger than the destructive force generated by the outside or high-speed movement, can greatly reduce the bead voids, reduce the quality problems of a series of early damages such as bead cracking, bead explosion and the like, and reduce the huge threat to the running safety of vehicles.
In order to solve the technical problems, the application adopts the following technical scheme:
a low-heat-generation tire bead filler for preventing bead void comprises the following components in parts by weight: 20-80 parts of natural rubber, 10-35 parts of styrene-butadiene rubber, 15-45 parts of solution polymerized styrene-butadiene rubber, 1.0-4.0 parts of zinc oxide, 1-4 parts of stearic acid, 1-5 parts of polyethylene glycol, 1.0-3.2 parts of dispersing agent, 1.5-6.0 parts of anti-aging agent, 1.5-3.5 parts of protective wax, 3-9 parts of tackifying resin, 1-8 parts of heat stabilizer, 45-110 parts of carbon black, 3-6 parts of silane coupling agent, 2-6 parts of sulfur, 2-13 parts of accelerator and 0.1-1 part of scorch retarder.
The invention provides a low-heat-generation tire bead filler for preventing bead voids, which uses three types of natural rubber, styrene-butadiene rubber and solution polymerized styrene-butadiene rubber in combination, uses the synergistic effect of an accelerator, sulfur and zinc oxide as a vulcanization system to enable the rubber material to be vulcanized fully, uses carbon black to play a role in reinforcing, uses tackifying resin to increase the adhesion between the rubber and a framework material, is matched with the synergistic effect of stearic acid, polyethylene glycol, a dispersing agent, an anti-aging agent, protective wax, a silane coupling agent, a scorch retarder and the like, and is innovatively added with a heat stabilizer by adjusting the formula, and the optimal use amount of the heat stabilizer and other components is determined after a large number of repeated experiments, so that the formula of the bead filler for preventing the bead voids can be obtained.
Preferably, the weight ratio of the raw materials is as follows:
30-70 parts of natural rubber, 1502 15-35 parts of styrene-butadiene rubber SBR, 2466 15-35 parts of solution polymerized styrene-butadiene rubber SSBR, 1.0-3.0 parts of zinc oxide, 1-3 parts of stearic acid, 1-3 parts of polyethylene glycol, 1.5-2.5 parts of dispersing agent, 1.5-5.5 parts of anti-aging agent, 1.5-2.5 parts of protective wax, 3-8 parts of tackifying resin, 1-6 parts of heat stabilizer, 45-100 parts of carbon black, 3-5 parts of silane coupling agent, 2-6 parts of sulfur, 2-10 parts of accelerator and 0.1-0.5 part of scorch retarder, and the composition has optimal bead gel performance.
Preferably, the heat stabilizer is selected from TCA-90 of the yellow rock eastern sea chemical industry Co., ltd, the melting point is more than or equal to 78.0 ℃ (measured according to GB/T11409 standard 3.1 melting point), ash content is less than or equal to 28.0% (measured according to GB/T11409 standard 3.7 ash content), heating decrement is less than or equal to 4.0% (measured according to GB/T11409 standard 3.4 heating decrement, 60 ℃/2 h), TCA-90 is a bismaleimide derivative, excellent heat stability can be given to rubber products, dynamic performance of rubber products at high temperature is improved, heat generation of rubber vulcanized rubber is reduced, elasticity of the rubber products is improved, TCA-90 and a small amount of zinc oxide are used for crosslinking natural rubber, heat resistance and adhesive force of tire rubber materials can be improved, and flex fatigue and elasticity are excellent, from the viewpoint of tire rubber materials with rubber mouth space are considered, and rubber materials containing TCA-90 do not show the phenomenon of being adhered to natural rubber materials under high temperature vulcanization conditions, no matter that the rubber materials adopt NS, DPG or DTDM as accelerators, the rubber materials can not show the phenomenon of the natural rubber has the phenomenon that the rubber has the free radical has greatly improved activity and the natural rubber has the effect, and the natural rubber has greatly improved heat resistance.
Preferably, the natural rubber is natural rubber SMR20#, and the raw rubber in the formula is natural rubber, so that the natural rubber has excellent tensile strength, elongation, tear strength and elasticity;
the styrene-butadiene rubber is SBR1502 of Fujian rubber chemical industry liability company, which is low-temperature emulsion styrene-butadiene rubber, the volatile component is less than or equal to 0.75%, the total ash content is less than or equal to 0.75%, the organic acid is 5.62%, the soap is less than or equal to 0.50%, the combined styrene is 23.5%, the tensile strength is more than or equal to 23.7mpa35mi n, the elongation is more than or equal to 415%35mi n, and the styrene-butadiene rubber has good tensile strength, abrasion resistance and flexibility;
the solution polymerized styrene-butadiene rubber is solution polymerized styrene-butadiene rubber SSBR2466, the Mooney viscosity ML1+4100 ℃ is 70-80, the styrene is 20-22% in part, the solution polymerized styrene-butadiene rubber has higher Mooney viscosity of the rubber compound, the end of the end group modified SSBR molecular chain enhances the interaction between the end group modified SSBR molecular chain and the carbon black surface group and the coupling agent, the interaction between the molecular chain carbon black and the filler is large, and after the rubber compound is vulcanized, the end group modified SSBR rubber compound participates in the vulcanization reaction due to the functionalized group, so that the crosslinking density is improved, the dynamic property of the rubber compound is obviously improved, the wear resistance is improved, and the rolling resistance is reduced;
the application uses three types of natural rubber, styrene-butadiene rubber and solution polymerized styrene-butadiene rubber in combination, and can endow the rubber product with excellent thermal stability by matching with a heat stabilizer and other raw materials, improve the dynamic performance of the rubber product at high temperature and reduce the heat generation of rubber vulcanized rubber;
preferably, the carbon black consists of three carbon blacks in the following weight portion: 15-45 parts of N326 carbon black, 10-45 parts of N330 carbon black and 10-50 parts of white carbon black. The carbon black with the model number of N326 and N330 is selected from Shanxi Yongdong chemical industry Co., ltd, and the three carbon blacks are matched, so that the optimal dosage finally determined by repeated experiments of the inventor can ensure good comprehensive physical properties of the bead filler, the bead filler is prevented from being improved in empty performance, and meanwhile, the hardness, tear resistance, tensile strength and stretching stress of the rubber material are improved.
Preferably, the accelerator consists of the following three accelerators in parts by weight: 0.5-3 parts of accelerator NS, 0.5-1.5 parts of accelerator DPG and 0.5-2.5 parts of accelerator DTDM, wherein the accelerator is easy to disperse in sizing materials, and sulfur vulcanization can be effectively promoted by combining the accelerator NS, the accelerator DPG and the accelerator DTDM, and meanwhile, the heat stabilizer is used, so that reversion phenomenon can be avoided, and the product stability is improved.
Preferably, the anti-aging agent is at least one selected from N-phenyl-alpha-aniline, N-phenyl-N '-isopropyl-p-phenylenediamine, N-N' -diphenyl-p-phenylenediamine and anti-aging agent 4020, preferably is anti-aging agent 4020, has good compatibility with sizing materials, is not easy to spray frost, is not easy to volatilize, has low toxicity, has excellent anti-oxidation, anti-ozone, anti-flex cracking and sun crack effects, and has strong inhibition effect on harmful metals such as copper and manganese and the like, thereby improving the protection effect.
Preferably, the type of the dispersing agent is KO-311, the compatible dispersing agent KO-311 is a liquid composite modified material, and the heat stabilizer and the carbon black substances can be prevented from being separated out in the mixing process, so that the impact strength of the sizing material is improved.
Preferably, the tackifying resin is styrene-maleic anhydride copolymer resin, is a product with the model of SMA 3000P of the company of gram Lei Weili, the maleic anhydride content is 20-25, the weight average molecular weight is 8000-12000, the melt viscosity is 2000-4000cps, preferably, the styrene/maleic anhydride molar ratio in the styrene-maleic anhydride copolymer resin product is 3/1, the SMA resin can be used as a high-activity maleic anhydride group in an alkali-soluble resin chain segment to chemically react with a functional group in a sizing material to form a firmly-combined covalent bond, and the interfacial bonding of the sizing material is improved, so that the mechanical properties of stretching, bending, toughness and the like of the material are improved, the heat resistance of the sizing material is obviously improved, the bonding strength of each part is improved, the bonding strength with the surface of a contact part is enhanced, the cohesive force is greater than the destructive force generated during external or high-speed movement, the quality problems of early damage such as sub-mouth crack, sub-mouth and sub-mouth are greatly reduced, and the huge threat to the running safety of vehicles is reduced.
The silane coupling agent is selected from coupling agent HP-669 of Jingdezhen macrocypress chemical technology Co., ltd, the chemical name is bis- (3-triethoxysilylpropyl) -tetrasulfide, the crosslinking speed of the polysulfane group of 669 is basically consistent with the reversion speed of sulfur in sulfur vulcanization, the reversion resistance is achieved, the dynamic bending performances such as the heating property, the crack extensibility and the like of rubber are improved, and the multi S atoms can also play a role in vulcanization acceleration.
The sulfur is selected from particle sulfur with sulfur content more than or equal to 95%, preferably high-dispersion insoluble sulfur, and is mainly characterized by high thermal stability and high dispersibility.
The density of the low heat generation tire bead stock prepared by the method is about 1.166-1.169kg/dm 3 ，
The second object of the present invention is to provide a method for preparing a low heat generation tire bead filler for preventing bead void, comprising the steps of:
(1) Mixing: weighing the raw materials according to the weight proportion, transferring the weighed raw materials into an internal mixer, and controlling the pressure to be 45-55N/cm 2 Automatically mixing for 180 seconds at 145-155 ℃ and a rotating speed of 25-45rmp, and then discharging glue;
(2) Extrusion tabletting: extruding the mixture into tablets by double screws after discharging the adhesive, and cooling and stacking after passing through the isolating liquid.
The third object of the invention is to provide an application of the low heat generation tyre bead filler for preventing the bead void in preparing the bead tyre, the prepared tyre bead has excellent performance, the bead void can be greatly reduced, a series of quality problems of early damage such as bead cracking, bead frying and the like can be reduced, and the requirement of the performance of the tyre of a customer can be met.
Compared with the prior art, the invention has the following advantages:
the application provides a low-heat-generation tire bead filler for preventing bead void, which comprises the following components in parts by weight: 20-80 parts of natural rubber, 10-35 parts of styrene-butadiene rubber, 15-45 parts of solution polymerized styrene-butadiene rubber, 1.0-4.0 parts of zinc oxide, 1-4 parts of stearic acid, 1-5 parts of polyethylene glycol, 1.0-3.2 parts of dispersing agent, 1.5-6.0 parts of anti-aging agent, 1.5-3.5 parts of protective wax, 3-9 parts of tackifying resin, 1-8 parts of heat stabilizer, 45-110 parts of carbon black, 3-6 parts of silane coupling agent, 2-6 parts of sulfur, 2-13 parts of accelerator and 0.1-1 part of scorch retarder, the three rubber types of natural rubber, styrene-butadiene rubber and solution polymerized styrene-butadiene rubber are used together, the synergistic effect of the accelerator, sulfur and zinc oxide is used as a vulcanization system to fully vulcanize the rubber material, the reinforcing effect of the carbon black is used, the tackifying resin is used for increasing the adhesion of the rubber and a framework material, and the synergistic effect of the stearic acid, the polyethylene glycol, the dispersing agent, the anti-aging agent, the protective wax, the silane coupling agent, the scorch inhibitor and the like are matched, the invention can effectively improve the rigidity, tensile strength, tearing strength, small permanent deformation, good flexibility and rebound resilience of the prescription, can improve the cohesive force of each part, enhance the cohesive strength with the surface of a contact part, has low heat generation, good heat aging resistance, has cohesive force larger than the destructive force generated by the outside or high-speed movement, can greatly reduce the gap, reduces a series of early damage quality problems such as gap cracking, gap frying and the like, the reduction of the safety of the vehicle causes a great threat to the running safety of the vehicle.
The preparation method of the low-heat-generation tire bead filler for preventing bead core is simple in processing and low in cost, performance of the existing tire bead filler for preventing bead core is upgraded, the technical problem that the existing tire bead filler is prone to bead core is solved, the tire bead core is improved, the risk of bead core occurrence is reduced, the safety performance of the tire is improved, and the product requirements of customers are met.
The invention also discloses the application of the bead filler for preventing the bead void in preparing the bead tire, the bead void can be greatly reduced by the tire prepared from the bead filler, compared with the prior bead filler, the bead void can be reduced by about 90 percent, the performance of a tire endurance test can be improved, the bead performance is excellent, and the requirement of the performance of a customer tire can be met.
Detailed Description
The following describes specific embodiments of the present invention with reference to specific examples 1 to 6 and comparative examples 1 to 6:
example 1
A sub-chewing gum for preventing sub-chewing from being empty comprises the following components in parts by weight:
30 parts of natural rubber (SMR20#) of Jin Mashi, 35 parts of styrene-butadiene rubber (SBR 1502 of Fu rubber chemical industry Co., ltd., fujian), 35 parts of solution polymerized styrene-butadiene rubber (SSBR 2466 of Tai rubber Co., ltd.), 1.0 parts of zinc oxide, 2.0 parts of stearic acid, 1.0 parts of polyethylene glycol-PEG 4000, 1.5 parts of dispersing agent, 1.5 parts of anti-aging agent (4020), 1.5 parts of protective wax, 3.0 parts of tackifying resin (styrene-maleic anhydride copolymer resin SMA 3000P), 1.0 parts of heat stabilizer (heat stabilizer TCA-90 of yellow rock east China Co., ltd.), 15 parts of N326 carbon black (Shanxi Yongdong chemical industry Co., ltd.), 45 parts of N330 carbon black (Shanxi Yongdong chemical Co., ltd.), 30 parts of white carbon black, 3.0 parts of silane coupling agent, 2.0 parts of high-dispersibility insoluble sulfur (sulfur content more than or equal to 95%), 1.0 parts of accelerator NS, 0 parts of accelerator, 0.5 parts of accelerator, DPDM, and 1.0 part of anti-scorch agent.
The child chewing gum for preventing child chewing is prepared by the following steps:
(1) Mixing:
firstly, transporting raw materials into a factory for inspection, and drying, cutting glue or directly feeding and automatically weighing according to the formula amount;
then the weighed raw materials are transferred into an internal mixer at the pressure of 50N/cm 2 And (3) automatically mixing for 180 seconds at the temperature of 150 ℃ and the rotating speed of 25-45rmp, and then discharging the rubber.
(2) Extrusion tabletting:
extruding with double screws, tabletting, passing through spacer fluid (mainly comprising stearic acid soap and talcum powder), cooling, and stacking.
Example 2
The sub-mouth glue for preventing sub-mouth void comprises the following components in parts by weight:
40 parts of natural rubber (SMR20#) of Jin Mashi limited company, 30 parts of styrene-butadiene rubber (SBR 1502 of Fu rubber chemical industry Co., ltd., fujian), 30 parts of solution polymerized styrene-butadiene rubber (SSBR 2466 of Tai rubber Co., ltd.), 1.5 parts of zinc oxide, 1.0 part of stearic acid, 1.5 parts of polyethylene glycol-PEG 4000, 1.5 parts of dispersing agent, 2.5 parts of anti-aging agent (4020), 2.0 parts of protective wax, 4.0 parts of tackifying resin (styrene-maleic anhydride copolymer resin SMA 3000P), 2.0 parts of heat stabilizer (heat stabilizer TCA-90 of yellow rock east China Co., ltd.), 35 parts of N326 carbon black (Shanxi Yongdong chemical industry Co., ltd.), 25 parts of N330 carbon black (Shanxi Yongdong chemical industry Co., ltd.), 20 parts of white carbon black, 2.0 parts of silane coupling agent, 3.0 parts of high-dispersibility insoluble sulfur (sulfur content more than or equal to 95%), 1.5 parts of accelerator NS, 0.8 parts of accelerator, DTDM (DTDM) and 2.0 parts of anti-scorch agent.
The child mouth glue for preventing child mouth void is prepared by the following method: prepared by the method of example 1.
Example 3
The sub-mouth glue for preventing sub-mouth void comprises the following components in parts by weight:
50 parts of natural rubber (SMR20#) of Jin Mashi, 25 parts of styrene-butadiene rubber (SBR 1502 of Fu rubber chemical industry Co., ltd., fujian), 25 parts of solution polymerized styrene-butadiene rubber (SSBR 2466 of Tai rubber Co., ltd.), 2.0 parts of zinc oxide, 1.5 parts of stearic acid, 2.0 parts of polyethylene glycol-PEG 4000, 2.0 parts of dispersing agent, 3.5 parts of anti-aging agent (4020), 1.5 parts of protective wax, 5.0 parts of tackifying resin (styrene-maleic anhydride copolymer resin SMA 3000P), 4.0 parts of heat stabilizer (heat stabilizer TCA-90 of yellow rock east chemical Co., ltd.), 35 parts of N326 carbon black (Shanxi Yongdong chemical Co., ltd.), 10 parts of N330 carbon black (Shanxi Yongdong chemical Co., ltd.), 45 parts of white carbon black, 4.5 parts of silane coupling agent, 4.0 parts of high-dispersibility insoluble sulfur (sulfur content more than or equal to 95%), 2.5 parts of accelerator NS, 0.9 parts of accelerator, 1.5 parts of accelerator DPDM, and 3.3 parts of anti-scorch agent.
The child mouth glue for preventing child mouth void is prepared by the following method: prepared by the method of example 1.
Example 4
The sub-mouth glue for preventing sub-mouth void comprises the following components in parts by weight:
55 parts of natural rubber (SMR20#) of Jin Mashi, 15 parts of styrene-butadiene rubber (SBR 1502 of Fu rubber chemical industry Co., ltd., fujian), 30 parts of solution polymerized styrene-butadiene rubber (SSBR 2466 of Tai rubber Co., ltd.), 2.5 parts of zinc oxide, 2.5 parts of stearic acid, 2.5 parts of polyethylene glycol-PEG 4000, 2.5 parts of dispersing agent, 4.5 parts of anti-aging agent (4020), 2.5 parts of protective wax, 6.0 parts of tackifying resin (styrene-maleic anhydride copolymer resin SMA 3000P), 5.0 parts of heat stabilizer (heat stabilizer TCA-90 of yellow rock east chemical Co., ltd.), 15 parts of N326 carbon black (Shanxi Yongdong chemical Co., ltd.), 25 parts of N330 carbon black (Shanxi Yongdong chemical Co., ltd.), 50 parts of white carbon black, 5.0 parts of silane coupling agent, 5.0 parts of high-dispersibility insoluble sulfur (sulfur content more than or equal to 95%) and 3.0 parts of accelerator NS 1.0 parts of accelerator, 2.5.0 parts of accelerator, and 4.0 parts of anti-scorch agent.
The child mouth glue for preventing child mouth void is prepared by the following method: prepared by the method of example 1.
Example 5
The sub-mouth glue for preventing sub-mouth void comprises the following components in parts by weight:
60 parts of natural rubber (SMR20#) of Jin Mashi, 20 parts of styrene-butadiene rubber (SBR 1502 of Fu rubber chemical industry Co., ltd., fujian), 20 parts of solution polymerized styrene-butadiene rubber (SSBR 2466 of Tai rubber Co., ltd.), 3.0 parts of zinc oxide, 3.0 parts of stearic acid, 3.0 parts of polyethylene glycol-PEG 4000, 2.0 parts of dispersing agent, 5.0 parts of anti-aging agent (4020), 2.0 parts of protective wax, 7.0 parts of tackifying resin (styrene-maleic anhydride copolymer resin SMA 3000P), 6.0 parts of heat stabilizer (heat stabilizer TCA-90 of yellow rock east chemical Co., ltd.), 45 parts of N326 carbon black (Shanxi Yongdong chemical Co., ltd.), 35 parts of N330 carbon black (Shanxi Yongdong chemical Co., ltd.), 10 parts of white carbon black, 1.0 parts of silane coupling agent, 5.5 parts of high-dispersibility sulfur (sulfur content is more than or equal to 95%), 2.0 parts of accelerator NS, 1.5 parts of accelerator, 2.5 parts of accelerator, and 2.0 parts of accelerator DPDM, and CTP.
The child mouth glue for preventing child mouth void is prepared by the following method: prepared by the method of example 1.
Example 6
The sub-mouth glue for preventing sub-mouth void comprises the following components in parts by weight:
70 parts of natural rubber (SMR20#) of Jin Mashi limited company, 15 parts of styrene-butadiene rubber (SBR 1502 of Fu rubber chemical industry Co., ltd., fujian), 15 parts of solution polymerized styrene-butadiene rubber (SSBR 2466 of Tai rubber Co., ltd.), 2.5 parts of zinc oxide, 2.0 parts of stearic acid, 2.0 parts of polyethylene glycol-PEG 4000, 1.5 parts of dispersing agent, 5.5 parts of anti-aging agent (4020), 1.5 parts of protective wax, 8.0 parts of tackifying resin (styrene-maleic anhydride copolymer resin SMA 3000P), 6.0 parts of heat stabilizer (heat stabilizer TCA-90 of yellow rock east China Co., ltd.), 35 parts of N326 carbon black (Shanxi Yongdong chemical industry Co., ltd.), 45 parts of N330 carbon black (Shanxi Yongdong chemical industry Co., ltd.), 20 parts of white carbon black, 2.0 parts of silane coupling agent, 6.0 parts of high-dispersibility insoluble sulfur (sulfur content more than or equal to 95%) and 2.0 parts of accelerator NS 1.2.2 parts of accelerator, 1.2 parts of accelerator, 1.8.0 parts of DTDM and 3.0 parts of anti-scorch agent.
The child mouth glue for preventing child mouth void is prepared by the following method: prepared by the method of example 1.
Comparative example 1
The chewing gum comprises the following components in parts by weight:
40 parts of ethylene propylene diene monomer rubber, 30 parts of natural rubber, 30 parts of solution polymerized styrene-butadiene rubber, 3 parts of zinc oxide, 1.5 parts of stearic acid, 1.5 parts of a life-increasing agent A, 2.5 parts of an anti-aging agent, 2.0 parts of protective wax, 2.0 parts of tackifying resin, 2.5 parts of hardening resin, 40 parts of N339 carbon black, 45 parts of N220 carbon black, 10 parts of white carbon black, 1 part of a silane coupling agent, 2 parts of high-dispersibility insoluble sulfur (sulfur content is more than or equal to 95%), 1 part of an accelerator CBS, 1.5 parts of an accelerator DPG and 3.2 parts of an accelerator MBTS.
The child chewing gum is prepared by the following method: prepared by the method of example 1.
Comparative example 2
The chewing gum comprises the following components in parts by weight:
45 parts of natural rubber, 35 parts of butadiene rubber, 30 parts of styrene-butadiene rubber, 20 parts of ethylene propylene diene monomer, 8 parts of zinc carbonate, 15 parts of superfine calcium carbonate, 2.5 parts of stearic acid, 10 parts of mica powder, 15 parts of white carbon black, 50 parts of high-wear-resistance furnace black, 12 parts of high-grade pottery clay, 5 parts of zinc oxide, 2.8 parts of a life-prolonging agent A, 3.5 parts of dadel oil, 4 parts of an accelerator, 2.5 parts of paraffin mixture, 3.5 parts of RA white powder, 3 parts of insoluble sulfur, 15 parts of carbon black, 3 parts of aluminum hydroxide, 2 parts of magnesium oxide and 2 parts of a silane coupling agent.
The child chewing gum is prepared by the following method: prepared by the method of example 1.
Comparative example 3
The chewing gum comprises the following components in parts by weight:
45 parts of natural rubber, 60 parts of butadiene rubber, 30 parts of styrene-butadiene rubber, 25 parts of ethylene propylene diene monomer rubber, 25 parts of polybutadiene rubber, 8 parts of zinc carbonate, 12 parts of superfine calcium carbonate, 3 parts of stearic acid, 5 parts of talcum powder, 35 parts of white carbon black, 50 parts of low-structure high-wear-resistance furnace black, 35 parts of high-grade pottery clay, 7 parts of 6700 resin, 6 parts of zinc oxide, 3 parts of stearic acid, 3 parts of magnesium oxide, 3.5 parts of RE brown crystals, 2 parts of Darling oil, 1 part of an accelerator, 3.5 parts of paraffin mixture, 3.5 parts of RA white powder, 5.3 parts of insoluble sulfur, 25 parts of carbon black, 2 parts of aluminum hydroxide, 3.5 parts of alkyl phenol disulfide and 3.5 parts of a silane coupling agent.
The child chewing gum is prepared by the following method: prepared by the method of example 1.
Comparative example 4
The chewing gum comprises the following components in parts by weight:
40 parts of natural rubber, 40 parts of butadiene rubber, 20 parts of reclaimed rubber, 58 parts of carbon black, 10 parts of high aromatic oil, 4 parts of 203 resin, 2.5 parts of stearic acid, 3.5 parts of zinc oxide, 3.5 parts of an anti-aging agent 4020.5 part of an anti-aging agent TMQ 1.5 part of an antioxidant 2241 part of microcrystalline wax 2122.5 part of special sulfur 1 part of accelerator DPG 0.4 part of accelerator NS 0.3 part of accelerator CBS 0.15 part of accelerator CBS.
The child chewing gum is prepared by the following method: prepared by the method of example 1.
Comparative example 5
The chewing gum comprises the following components in parts by weight:
40 parts of natural rubber (SMR20#) of Jin Mashi, 30 parts of styrene-butadiene rubber (SBR 1502 of Fu rubber chemical responsibility, fujian, inc.), 30 parts of solution polymerized styrene-butadiene rubber (SSBR 2466 of Tai rubber, inc.), 1.5 parts of zinc oxide, 1.0 part of stearic acid, 1.5 parts of polyethylene glycol-PEG 4000, 1.5 parts of dispersing agent, 2.5 parts of anti-aging agent (4020), 2.0 parts of protective wax, 4.0 parts of cashew nut oil modified phenolic resin, 35 parts of N326 carbon black (Shanxi Yongdong chemical Co., inc.), 25 parts of N330 carbon black (Shanxi Yongdong chemical Co., inc.), 20 parts of white carbon black, 2.0 parts of silane coupling agent, 3.0 parts of high-dispersibility insoluble sulfur (sulfur content is more than or equal to 95%), 1.5 parts of accelerator NS, 0.8 parts of accelerator DPG, 0.9 parts of accelerator DTDM and 0.2 parts of anti-scorch agent CTP.
The child chewing gum is prepared by the following method: prepared by the method of example 1.
Comparative example 6
30 parts of natural rubber (SMR20#) of Jin Mashi limited company, 35 parts of styrene-butadiene rubber (SBR 1502 of Fu rubber chemical industry liability limited company of Fujian province), 35 parts of solution polymerized styrene-butadiene rubber (SSBR 2466 of Tai rubber limited company), 1.0 parts of zinc oxide, 2.0 parts of stearic acid, 1.0 parts of polyethylene glycol-PEG 4000, 1.5 parts of dispersing agent, 1.5 parts of anti-aging agent (4020), 1.5 parts of protective wax, 3.0 parts of 6700 resin, 15 parts of N326 carbon black (Shanxi Yongdong chemical industry Co., ltd.), 45 parts of N330 carbon black (Shanxi Yongdong chemical industry Co., ltd.), 30 parts of white carbon black, 3.0 parts of silane coupling agent, 2.0 parts of high-dispersibility insoluble sulfur (sulfur content is more than or equal to 95 percent), 1.0 parts of accelerator NS, 0.5 parts of accelerator DPG, 0.5 parts of accelerator DT0.5 parts, and 0.1 part of anti-scorching agent CTP.
The child chewing gum is prepared by the following method: prepared by the method of example 1.
Table 1: the weight part ratio of the components of examples 1 to 6
The performances of the gum prepared in the above examples and comparative examples were tested, and the test items and test results are shown in tables 2 to 5.
Table 2 results of test of properties of the rubber prepared from the bead filler of the example
TABLE 3 test results of the properties of the sizes prepared from the sub-gums of the comparative examples
Table 4 the results of the endurance test in the finished tire chambers prepared with the bead filler of the example are shown in the following table:
table 5 comparative example bead fillers prepared finished tire indoor endurance test results are shown in the following table:
from the test results in the above table, it can be seen that:
when the total parts (90 parts) of the carbon black used in examples 1 and 3 are the same, and the parts of the heat stabilizer are different, the finished tires prepared from the bead filler obtained by the method have better tensile strength (27.22 and 29.03 respectively), rebound value (61 and 63 respectively), R97 vulcanization reversion resistance time (46.89 and 48.42 respectively) and compression fatigue test temperature rise (18.2 and 15.9 respectively), and the other physical properties have little change, which indicates that when the carbon black is used in the same amount, the more the parts of the heat stabilizer are used, the tensile strength and rebound value of the bead filler are increased, the vulcanization reversion resistance time is prolonged, the compression heat generation is low, and the obtained bead filler has better heat resistance and endurance test performance and better comprehensive physical properties.
When the total parts of carbon black used in examples 5 and 6 were different (90 parts and 100 parts, respectively), and the parts of the heat stabilizer were the same, the finished tire prepared from the bead filler obtained in example 6 was significantly better than example 5 in terms of tensile strength (29.88, 31.02, respectively), rebound value (62, 65, respectively), R97 anti-reversion time (49.21, 49.87, respectively), and compression fatigue test temperature rise (15.1, 14.3, respectively). The method shows that when the carbon black dosage is reduced, the finished tire prepared from the obtained bead filler has better comprehensive physical properties, and the R97 vulcanization reversion resistance time and the compression fatigue test temperature rise are better.
The R97 anti-reversion times of the finished wheels prepared with the bead fillers obtained in examples 1, 2, 3, 4, 5 and 6, in particular of the bead fillers obtained in examples 4, 5 and 6, were significantly greater than the R97 anti-reversion times of the finished tires prepared with the bead fillers obtained in comparative examples, respectively 46.89, 47.15, 48.42, 48.8, 49.21 and 49.87; meanwhile, the temperature rise of the compression fatigue test is greatly smaller than that of the finished tire prepared by the bead filler obtained in the comparative example, and is 18.2, 17.3, 15.9, 15.3, 15.1 and 14.3 respectively. Therefore, the tire prepared by using the bead filler has higher vulcanization reversion resistance, tensile strength and rebound value, low compression heat generation and improved heat resistance and durability of the finished tire. The method can greatly reduce the gap of the sub-mouth, reduce the quality problems of a series of early damages such as sub-mouth crack, sub-mouth explosion and the like, and reduce the serious threat to the running safety of the vehicle.
Comparative examples 1, 2, 3 and 4 are finished wheels prepared by the existing tire bead filler formulation, and the tensile strength (25.78, 25.36, 26.01 and 25.12 respectively), rebound value (45, 46, 43 and 44 respectively), R97 anti-vulcanization reversion time (30.12, 29.15, 29.78 and 30.14 respectively) and compression fatigue test temperature rise (25.14, 25.89, 26.75 and 26.37 respectively) of the finished wheels are general, and the obtained bead filler is poor in heat resistance and endurance test performance.
The test results show that the finished tires prepared by using no heat stabilizer TCA-90 and no styrene-maleic anhydride copolymer resin in comparative example 5 and comparative example 6 have significantly different tensile strength (26.66 and 26.54 respectively), rebound value (52 and 53 respectively), R97 anti-vulcanization reversion time (32.87 and 30.78 respectively) and compression fatigue test temperature rise (26.79 and 26.98 respectively) than in examples 1-6, the tensile strength and rebound value of the bead compound and the anti-vulcanization reversion time end, the compression heat generation is high, the heat resistance and the durability test performance of the obtained bead compound are general, and the open crack of the endurance test has serious.
The foregoing description of the preferred embodiments of the present application is not intended to be limiting, but is intended to cover any and all modifications, equivalents, and alternatives falling within the spirit and principles of the present application.
Claims (10)
1. The preparation method of the low-heat-generation tire bead filler for preventing bead void is characterized by comprising the following components in parts by weight: 30-70 parts of natural rubber, 1502 15-35 parts of styrene-butadiene rubber SBR, 2466 15-35 parts of solution polymerized styrene-butadiene rubber SSBR, 1.0-3.0 parts of zinc oxide, 1-3 parts of stearic acid, 1-3 parts of polyethylene glycol, 1.5-2.5 parts of dispersing agent, 1.5-5.5 parts of anti-aging agent, 1.5-2.5 parts of protective wax, 3-8 parts of tackifying resin, 1-6 parts of heat stabilizer, 45-100 parts of carbon black, 3-5 parts of silane coupling agent, 2-6 parts of sulfur, 2-10 parts of accelerator and 0.1-0.5 part of scorch retarder;
the styrene-butadiene rubber is SBR1502, which is low-temperature emulsion styrene-butadiene rubber, the volatile component is less than or equal to 0.75%, the total ash content is less than or equal to 0.75%, the organic acid content is 5.62%, the soap content is less than or equal to 0.50%, the combined styrene content is 23.5%, the tensile strength is more than or equal to 23.7MP 35min, and the elongation is more than or equal to 415%35min;
the solution polymerized styrene-butadiene rubber is solution polymerized styrene-butadiene rubber SSBR2466, the Mooney viscosity ML1+4100 ℃ is 70-80, and the styrene is 20-22%;
the heat stabilizer is a heat stabilizer TCA-90, the melting point is more than or equal to 78.0 ℃, the ash content is less than or equal to 28.0%, and the heating decrement is less than or equal to 4.0%;
the preparation method of the low-heat-generation tire bead filler for preventing bead void comprises the following steps of:
(1) Mixing: weighing the raw materials according to the weight proportion, transferring the weighed raw materials into an internal mixer, and controlling the pressure to be 45-55N/cm 2 Automatically mixing for 180 seconds at 145-155 ℃ and a rotating speed of 25-45rmp, and then discharging glue;
(2) Extrusion tabletting: extruding the mixture into tablets by double screws after discharging the adhesive, and cooling and stacking after passing through the isolating liquid.
2. The method for preparing the low heat generation tire bead filler for preventing bead void according to claim 1, wherein the accelerator comprises the following three accelerators in parts by weight: 0.5-3 parts of accelerator NS, 0.5-1.5 parts of accelerator DPG and 0.5-2.5 parts of accelerator DTDM.
3. The method for preparing a low heat generation tire bead filler for preventing bead void according to claim 1, wherein the tackifying resin is a styrene-maleic anhydride copolymer resin, which is a product of the type SMA 3000P of the company g Lei Weili, having a maleic anhydride content of 20 to 25, a weight average molecular weight of 8000 to 12000, a melt viscosity of 2000 to 4000cps, and a styrene/maleic anhydride molar ratio of 3/1.
4. The method for preparing a low heat generation tire bead filler for preventing bead void according to claim 1, wherein the anti-aging agent is at least one selected from the group consisting of N-phenyl- α -aniline, N-phenyl-N '-isopropyl-p-phenylenediamine, N-N' -diphenyl-p-phenylenediamine, and anti-aging agent 4020.
5. The method for preparing a low heat generation tire bead filler for preventing bead void according to claim 1, wherein the dispersant is KO-311.
6. The method for preparing the low heat generation tire bead filler for preventing bead void according to claim 1, wherein the silane coupling agent is a coupling agent HP-669.
7. The method for preparing a low heat generation tire bead filler for preventing bead void according to claim 1, wherein the sulfur is selected from the group consisting of particle sulfur having a sulfur content of 95% or more and is highly dispersed insoluble sulfur.
8. The method for producing a low heat generation tire bead filler for preventing bead void as claimed in claim 1, wherein the density of the tire bead filler is 1.166 to 1.169kg/dm 3 。
9. The method for preparing the low heat generation tire bead filler for preventing bead void according to claim 1, wherein the natural rubber is natural rubber smr20#.
10. Use of a low heat generation tire bead filler for preventing bead void according to any one of claims 1 to 9 in the manufacture of a bead tire.
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| CN202310106343.5A CN116253939A (en) | 2021-10-12 | 2021-10-12 | Preparation method of low-heat-generation tire bead filler for preventing bead void and tire |
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