CN103788423A - Rubber composition, and tire shoulder glue and preparation method - Google Patents
Rubber composition, and tire shoulder glue and preparation method Download PDFInfo
- Publication number
- CN103788423A CN103788423A CN201210425372.XA CN201210425372A CN103788423A CN 103788423 A CN103788423 A CN 103788423A CN 201210425372 A CN201210425372 A CN 201210425372A CN 103788423 A CN103788423 A CN 103788423A
- Authority
- CN
- China
- Prior art keywords
- rubber
- composition
- weight
- tire
- content
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
Abstract
The invention discloses a rubber composition, a tire shoulder glue and a preparation method. The composition contains dialkene rubber, a vulcanizing agent, a sulfuration promoter, an activator and a reinforcing agent, wherein the composition also contains liquid polyisoprene rubber, the dialkene rubber contains solution polymerized styrene-butadiene rubber and natural rubber. The rubber composition has the advantages of low processing energy consumption, good surface quality of an extrusion and calendering rubber compound, excellent physical mechanicalness, little compression permanent deformation and rolling resistance, low heat generation and good heat stability, and is capable of increasing endurance of the tire and prolonging the tire life, and is in favor of energy saving of the tire. The rubber composition can avoid the disadvantages of easy volatilization and environmental pollution of a common plasticizer under high temperature, and is suitable for preparing high performance green tires.
Description
Technical field
The present invention relates to a kind of rubber combination and tire shoulder glue and preparation method thereof.
Background technology
Along with the raising of road quality classification and the development of transport trade, automobile travels quite general under high speed excess load, and people are also more and more higher to the performance requriements of tire.The tire stress concentration that tire shoulder bears in the process of moving, distortion is large, heat-dissipating is higher, and therefore the early stage phenomenons such as shoulder is empty, shoulder splits easily occur in the process of moving, affects the work-ing life of tire.In addition, in traditional Rubber processing process, conventional low point of seed oil of aromatic hydrocarbons made softening agent or tenderizer, these softening agent not only can reduce the physical property of cross-linked rubber, and at high temperature volatile, majority has contaminative, in use easily moves to product surface or is extracted out by solvent, thereby making that product volume is shunk, distortion and affect work-ing life.Along with the reinforcement of people's environmental consciousness, countries in the world are more and more higher to environmental requirement, make laws also more and more stricter, these materials as requiring to export to after 2010 in the rubber item of European Union, the Reach of European Union bill can not contain harmful aromatic hydrocarbon substance, because can enter atmosphere and to environment with the wearing and tearing of tire and rubber grain.This regulation has caused very large impact to tire manufacture and China's tire outlet industry.
Adopt reactive plasticizer can give the processing characteristics that rubber is good as fluid rubber.Fluid rubber often has and the same or analogous chain structure of material of main part, can participate in the crosslinked integral part becoming in cross-linked rubber network when sulfuration, makes cross-linked rubber have good physicals and chemical stability.In addition, adopt fluid rubber as softening agent, can also save mixing energy consumption, improve extrusion efficiency and extrudate dimensional stability, improve and extrude with calendering sizing compound surface quality and improve the viscosity of green compound sheet and tension set and the rolling resistance of reduction cross-linked rubber, be conducive to tire energy-conservation, can reduce environmental pollution.
CN102134336A adopts liquid polyisoprene rubber as tyre triangular glue composition, this invention guaranteeing under the prerequisite that triangle rubber sizing material Main physical performance, part dimension stability, technique viscosity do not reduce, reduce extrude heat up high, enhance productivity, reduce process loss.Main rubber in this invention is natural rubber, and liquid polyisoprene rubber is the preparation for tyre triangular glue.Tyre triangular glue is different with the purposes of tire shoulder glue, completely different to its performance requriements, and in this invention triangle rubber formula, carbon black loading is large, require sizing material hardness to want large, processing characteristics will be got well, and compression heat generation is low, but sizing material wear resistance, rolling resistance, anti-slippery are not had to specific requirement, and main rubber is all natural rubber, in addition, the triangle rubber of this invention also needs to add technical oil and the tackifying resin containing high aromatic hydrocarbons.Due to the use containing high aromatics process oil, tire in use still can be to environment.
In JP2000142016A, introduce a kind of processing characteristics tire tread glue composition with white carbon black reinforcement of improving, this sizing material is by 100 weight part dience rubbers, the liquid isoprene of 3-40 % by weight and the segmented copolymer of vinyl pyridine are (wherein with respect to isoprene, the content of vinyl pyridine is 3%-30%, and number-average molecular weight is 2000-50000) and 20-150 part SiO
2composition, the rubber of this invention has good extrusion performance, and the rubber obtaining after sulfuration has good wear resistance and lower rolling resistance.Although this invention can obtain the tire tread glue composition of better performances, but the fluid rubber in this invention tread rubber composition need to comprise two kinds of monomers: isoprene and vinyl pyridine, the preparation process of this fluid rubber is more complicated, and the price of monomer ethylene yl pyridines is more expensive, cause the price of this fluid rubber more expensive, and will use the SiO that price is relatively expensive in Rubber processing process
2as strengthening agent, cause the manufacturing cost of tire higher.The result of improving to rolling resistance, anti-slippery, heat-dissipating and ageing-resistant performance while not mentioning this tread rubber composition as tire tread glue in this inventive method.
Summary of the invention
The object of the invention is the deficiency existing in order to overcome current tire shoulder glue, a kind of rubber combination is provided, and the tire shoulder glue that this rubber combination makes has good over-all properties when can having good physical and mechanical properties and compression heat generation and dynamic heat build up performance.
The invention provides a kind of rubber combination, said composition contains main rubber, vulcanizing agent, vulcanization accelerator, activator and toughener, wherein, described composition also contains liquid polyisoprene rubber, and described main rubber contains solution polymerized butadiene styrene rubber and natural rubber.
The present invention also provides a kind of preparation method of tire shoulder glue, and the method comprises carries out above-mentioned rubber combination mixing, obtains rubber unvulcanizate; And by described rubber unvulcanizate sulfuration, obtain tire shoulder glue.
In addition, the present invention also provides a kind of tire shoulder glue being prepared by aforesaid method.
The tire shoulder glue that composition provided by the invention prepares, the tire shoulder glue that this rubber combination makes can have good calendering process performance, good physicals, thermostability and dynamic properties and environmental protection concurrently.For example, in embodiments of the invention 1, the electric current of composition mixing process is 10A, be 15A and adopt the electric current of composition mixing process in the comparative example 1 that aromatic hydrocarbon oil is softening agent, the dissipation factor tan δ (60 ℃) of the tire shoulder glue that embodiment 1 prepares is 0.072, second-order transition temperature Tg is-44.15 ℃, rebound value is 54%, aging back draft intensity is 20.4MPa, and the dissipation factor tan δ (60 ℃) of the tire shoulder glue that the comparative example 1 that employing aromatic hydrocarbon oil is softening agent prepares is 0.0814, second-order transition temperature Tg is-43.57 ℃, rebound value is 48%, aging back draft intensity is 19.1MPa.Tracing it to its cause to be, liquid polyisoprene rubber is reactive plasticizer, in use procedure, can also can not move to product surface to environment, thereby can not make that product volume is shunk, distortion and affect work-ing life; In addition, because the structure of liquid polyisoprene rubber and natural rubber or styrene-butadiene rubber(SBR) approaches, easily and rubber mix, make softening agent with general low point of seed oil of aromatic hydrocarbons compared with, the power consumption of polymer processing of rubber unvulcanizate is lower; Moreover, because liquid polyisoprene rubber can co-crosslinking occur in sulfidation with natural rubber and synthetic rubber, by the kind of other components and the selection of content of composition, make the tire preparing can there is following performance: (1) preferably physical and mechanical properties is as high in intensity, ageing-resistant performance is good, can improve Using Life of Tyre, guaranteeing can not affect tire used performance because heat-dissipating causes this position properties of rubber to decline in tire operational process; (2) good, the compression heat generation of the rebound resilience of tire shoulder glue and dynamic heat build up is low, tension set is little, can delay tire hot and accumulate the destruction of causing; (3) hysteresis loss of tire shoulder glue and heat-dissipating reduce, and can alleviate tire heat history in the process of moving, extend tyre life; (4) second-order transition temperature reduces, and can improve the wear resistance of tire.
Embodiment
According to the present invention, this rubber combination contains main rubber, vulcanizing agent, vulcanization accelerator, activator and toughener, and wherein, described composition also contains liquid polyisoprene rubber, and described main rubber contains solution polymerized butadiene styrene rubber and natural rubber.
According to the present invention, although as long as guarantee that described rubber contains solution polymerized butadiene styrene rubber and natural rubber and described rubber combination and also contains liquid polyisoprene rubber and just can realize object of the present invention, kind and preparation method to the liquid polyisoprene rubber in described rubber combination do not have particular requirement.Described liquid polyisoprene rubber can be commercially available, and also can be prepared according to method of the prior art.For example, liquid polyisoprene rubber can reference literature " elastomerics " preparation method's preparation of the 21st volume the 2nd phase 32-35 page in 2011.But in order to obtain the rubber combination that over-all properties is more excellent, preferably, take the total amount of described liquid polyisoprene rubber as benchmark, the amount of the structural unit that described isoprene forms by Isosorbide-5-Nitrae-polymerization is more than 96.9 % by mole.Further preferably, the molecular weight distribution of liquid polyisoprene can be 1.01-1.10, and number-average molecular weight can be 5000-100000.In such cases, the preparation method of described liquid polyisoprene rubber can be: under anionoid polymerization condition, isoprene is contacted in solvent with water with organic lithium initiator; Wherein, the mol ratio of water and described organic lithium initiator is 0.9-9:100.
According to the present invention, the mol ratio of water and described organic lithium initiator is 0.9-9:100.In the time that the mol ratio of water and described organic lithium initiator is within above-mentioned scope, the molecular weight distribution of the polyisoprene finally obtaining can reach below 1.10, and in the polyisoprene obtaining, isoprene is with 1, the content of the structural unit that 4-polymerization methods forms is high, can reach 96.9 % by mole above (under optimum condition, can reach more than 97 % by mole).And, because the mol ratio of water and described organic lithium initiator is only 0.9-9:100, therefore, in theory, take 100 moles of described organic lithium initiators as benchmark, the organic lithium initiator that only has at the most 0.9-9 mole react with water (the whole lithium hydroxides that form even if think organic lithium initiator to react with water and organic lithium initiator react and generate Lithium Oxide 98min, and the total flow of organic lithium initiator is only also 1.8-18 mole).That is, according to the present invention, the amount of the organic lithium initiator reacting with water is few, and therefore, economy according to the present invention is high.
The performance of the polyisoprene finally obtaining from balance and according to the angle of economy of the present invention, the mol ratio of water and described organic lithium initiator is preferably 2-7.5:100.
According to the present invention, be preferably deionized water for the water contacting with described organic lithium initiator.Can adopt the conventional method in this area to prepare described deionized water, repeat no more herein.
According to the present invention, the order of addition of water and described organic lithium initiator is not particularly limited, and can water and described organic lithium initiator be added in the solvent that contains isoprene simultaneously; Also can first add water and then organic lithium initiator be added in the solvent that contains isoprene.Because water is polar material, carry out solvent and isoprene monomer polarity that polymerization uses lower, therefore from improving the angle of dispersing uniformity of water, preferably first add water in the solvent that contains isoprene and be uniformly dispersed, and then add described organic lithium initiator.
According to the present invention, can regulate by changing the consumption of organic lithium initiator the molecular weight of polyisoprene prepared in accordance with the present invention., the amount of described organic lithium initiator can be carried out appropriate selection according to the molecular weight of the polyisoprene of expection.Usually, the mol ratio of described organic lithium initiator and isoprene can be 3.5 × 10
-4-0.028:1.Preferably, the mol ratio of described organic lithium initiator and isoprene is 7 × 10
-4-0.013:1.
According to the present invention, the organolithium compound that described organic lithium initiator can cause isoprene and carries out anionoid polymerization for conventional various in this area.For example, described organic lithium initiator can be the compound shown in formula I separately,
R
1Li （I），
In formula I, R
1can be C
1-C
10straight or branched alkyl (comprise C
1-C
10straight chained alkyl and C
3-C
10branched-chain alkyl) or C
6-C
20replacement or unsubstituted aryl.
In the present invention, C
1-C
10the example of straight or branched alkyl can include but not limited to: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl, neo-pentyl, n-hexyl, n-heptyl, n-octyl and positive decyl.
In the present invention, C
6-C
20replacement or the example of unsubstituted aryl can include but not limited to: phenyl, aminomethyl phenyl, ethylphenyl, tert-butyl-phenyl and naphthyl.
According to the present invention, described organic lithium initiator can be one or more in lithium ethide, n-propyl lithium, isopropyl lithium, n-Butyl Lithium, s-butyl lithium, n-pentyl lithium, hexyllithium, cyclohexyl lithium, phenyl lithium, aminomethyl phenyl lithium and naphthyl lithium.
Preferably, described organic lithium initiator is one or more in n-Butyl Lithium, s-butyl lithium, isobutyl-lithium and tert-butyl lithium.
According to the present invention, be not particularly limited for the monomer concentration of isoprene in solvent, can be that the routine of this area is selected, for example: take the total amount of isoprene and described solvent as benchmark, the content of described isoprene can be more than 5 % by weight.According to the present invention, the mol ratio of water and described organic lithium initiator is 0.9-9:100, not only can make like this liquid polyisoprene finally obtaining there is narrow molecular weight distribution, improve with 1, the mode of 4-polymerization is carried out the amount of the isoprene of polymerization, and in the case of all the other conditions identical (comprising for reducing the operational conditions of the refrigerating unit of the temperature of reaction of polymerization system identical), also make polyreaction to carry out more stably, reduce and even avoid in polymerization process, the polymerization system temperature causing because local polymerization velocity is too high raises.Therefore, according to the present invention, can carry out polymerization with higher monomer concentration, and then make method of the present invention there is higher production efficiency.According to the present invention, take the total amount of isoprene and described solvent as benchmark, the content of described isoprene is preferably 5-60 % by weight, more preferably 10-40 % by weight.
According to the present invention, described solvent can be the conventional various non-polar solvents in this area, and for example various varsols are (as C
4-C
8straight or branched aliphatic saturated hydrocarbon or C
6-C
12replacement or unsubstituted aromatic hydrocarbons).In the present invention, the example of described solvent can for but be not limited to: benzene, toluene, hexanaphthene, normal hexane, Skellysolve A, normal heptane, raffinate oil or hydrogenated gasoline in one or more.
One of the present invention preferred embodiment in, described solvent is that boiling range is that 55-100 ℃ raffinating oil or boiling range are the hydrogenated gasoline of 55-100 ℃.Adopting boiling range is that 55-100 ℃ raffinating oil or boiling range are while being the hydrogenated gasoline of 55-100 ℃, because its solubility parameter is relatively low, the solvability of liquid polyisoprene rubber is reduced, cause polymer molecule in solvent, to be rolled state, make the reduced viscosity of the polymers soln of same concentrations, be conducive to withdrawing from and the steady control of temperature of reaction of polymerization reaction heat, so not only under equal conditions, in the liquid polyisoprene of preparation, the content of the structural unit forming in the mode of Isosorbide-5-Nitrae-polymerization is higher; And, even under higher monomer concentration, in the liquid polyisoprene of preparation, more than the content of the structural unit forming with Isosorbide-5-Nitrae-polymerization methods still can reach 97 % by weight.And boiling range is that 55-100 ℃ raffinating oil or boiling range are that the source of hydrogenated gasoline of 55-100 ℃ is abundant, cheap, zero pour is low, while production in the winter time, can be in order to avoid the pipeline of delivery solvent be heated, thus can further reduce the production cost of method of the present invention.Further preferably, described solvent is that boiling range is that 55-85 ℃ raffinating oil or boiling range are the hydrogenated gasoline of 55-85 ℃.
In the present invention, described in to raffinate oil be in petroleum refining process, be rich in catalytic reformate remaining distillate after extraction aromatic hydrocarbons of aromatic hydrocarbons.In the present invention, described hydrogenated gasoline refer to by saturated to the alkene in regular gasoline and diene hydrogenation, aromatic hydrocarbons partial hydrogenation is saturated and the gasoline that obtains.
According to the present invention, be not particularly limited for described anionoid polymerization condition, can be that the routine of this area is selected.Usually, described anionoid polymerization condition comprises: temperature can be 20-100 ℃, is preferably 30-80 ℃; Time can be 10 minutes to 3 hours, is preferably 30 minutes to 2 hours; In gauge pressure, pressure can be 0.01-0.5MPa, is preferably 0.05-0.3MPa.Isoprene carries out with contacting under protection of inert gas of water and organic lithium initiator, and described rare gas element can be the conventional various non-active gas in this area, for example: nitrogen and neutral element gas (as argon gas).
After polymerization completes, can adopt the ordinary method of this area by the deactivation of polymerization activity center according to the present invention.For example, can in the mixture (, polymerisate) that obtain, add polymerization terminator by contacting with organic lithium initiator with water to isoprene, thereby by the polymerization activity center deactivation in described polymerisate.Described polymerization terminator can be the conventional various polymerization terminators in this area, for example: described polymerization terminator can be water and/or alcohol.Described alcohol can be one or more in methyl alcohol, ethanol, n-propyl alcohol and Virahol.The present invention is not particularly limited for the consumption of described polymerization terminator, as long as the consumption of described polymerization terminator can make polymerization activity center loss of activity.Usually, the mol ratio of described polymerization terminator and organic lithium initiator can be 0.5-2:1, is preferably 0.8-1.2:1.
According to the present invention, can adopt the ordinary method of this area to remove the solvent in polymerisate.For example, can be by the polymerisate that is added with described anti-aging agent in warm air, evaporate under decompression or normal pressure, thereby desolvation; Also can, under the condition vacuumizing, carry out desolvation by thin-film evaporator.
The all ingredients using according to the present invention preferably adopts the ordinary method of this area to refine before use, repeats no more herein.
The present invention is not particularly limited the weight ratio of described natural rubber and solution polymerized butadiene styrene rubber, in order to improve the over-all properties of described rubber combination, under preferable case, the weight ratio of described natural rubber and solution polymerized butadiene styrene rubber can be 0.5-19:1, is preferably 1-9:1.
The present invention does not limit especially to the content of each material in described rubber combination, in order to obtain the rubber combination that over-all properties is more excellent, under preferable case, take the main rubber of 100 weight parts as benchmark, the content of described vulcanizing agent is 1-3 weight part, the content of described vulcanization accelerator is 1-5 weight part, the content of described toughener is 40-70 weight part, the content of described activator is 0.5-8 weight part, the content of described liquid polyisoprene rubber is 1-10 weight part, described natural rubber accounts for the 45-95 % by weight of main rubber, described solution polymerized butadiene styrene rubber accounts for the 5-55 % by weight of main rubber.Further under preferable case, take the main rubber of 100 weight parts as benchmark, the content of described vulcanizing agent is 1.5-2.5 weight part, the content of described vulcanization accelerator is 1.5-4.5 weight part, the content of described toughener is 45-65 weight part, and the content of described activator is 2-5.5 weight part, and the content of described liquid polyisoprene rubber is 1.5-9.5 weight part, described natural rubber accounts for the 50-90 % by weight of main rubber, and described solution polymerized butadiene styrene rubber accounts for the 10-50 % by weight of main rubber.
According to the present invention, in order to improve anti ageing property and the processing characteristics of described rubber combination, and then obtain the rubber combination that over-all properties is more excellent, under preferable case, described composition also contains anti-aging agent and/or scorch retarder, take the main rubber of 100 weight parts as benchmark, the content of described anti-aging agent is 2-5 weight part, and the content of described scorch retarder is 0.05-0.35 weight part.
According to the present invention, the kind of described anti-aging agent and consumption are conventionally known to one of skill in the art.For example, described anti-aging agent can be amines antioxidants and/or quinoline type antioxidant; Described amines antioxidants can be selected from N-sec.-propyl-N '-diphenyl-para-phenylene diamine, N-(1,3-dimethylbutyl)-N '-diphenyl-para-phenylene diamine (commodity by name 4020) and N, N '-bis-(1,4-dimethyl amyl group) one or more in Ursol D, described quinoline type antioxidant can be selected from 2,2,4-trimethylammonium-1,2-dihyaroquinoline polymer, 6-oxyethyl group-2,2,4-trimethylammonium-1,2-dihyaroquinoline and 6-dodecyl-2,2,4-trimethylammonium-1, one or more in 2-dihyaroquinoline; Wherein, described 2,2,4-trimethylammonium-1, the polymeric commodity of 2-dihyaroquinoline are called RD, its structural formula as the formula (2):
Formula (2),
It should be noted that, of the present invention 2,2,4-trimethylammonium-1,2-dihyaroquinoline polymer refers in particular to 2,2,4-trimethylammonium-1, dimer, tripolymer or the tetramer (, n=2,3 or 4) of 2-dihyaroquinoline; And due to described 2,2,4-trimethylammonium-1, the dimeric anti-old performance of 2-dihyaroquinoline is very excellent, therefore, described 2,2,4-trimethylammonium-1,2-dihyaroquinoline polymer is preferably dimer, or dimer and tripolymer and/or tetrameric mixture.More preferably, when described 2,2,4-trimethylammonium-1, when 2-dihyaroquinoline dimer is dimer and tripolymer and/or tetrameric mixture, take the gross weight of described mixture as benchmark, described dimeric content is 25-55 % by weight, and described dimer and trimerical total content are 45-75 % by weight.
According to the present invention, the kind of described scorch retarder and consumption are conventionally known to one of skill in the art.For example, described scorch retarder can be one or more in N-cyclohexylthiophthalimide, N nitrosodiphenyl amine, Whitfield's ointment and Tetra hydro Phthalic anhydride, is preferably N-cyclohexylthiophthalimide.
According to the present invention, in order to improve wear resistance and the elasticity of described rubber combination, and then obtain the rubber combination that over-all properties is more excellent, under preferable case, the number-average molecular weight of described natural rubber is 1,000,000-1,000 ten thousand, and molecular weight distribution is 3-6, and mooney viscosity is 65-75.
According to the present invention, under preferable case, the number-average molecular weight of described solution polymerized butadiene styrene rubber is 100,000-400,000, and molecular weight distribution is 1.1-3, and contents of ethylene is 10-35%, and mooney viscosity is 45-65.Described " contents of ethylene " refers to the ratio of weight and the solution polymerized butadiene styrene rubber gross weight of the vinyl that has neither part nor lot in polymerization in solution polymerized butadiene styrene rubber, and in other words, it is equivalent to carry out the content of divinyl described in 1,2 addition.In addition, it should be noted that, in the present invention, the mooney viscosity of described solution polymerized butadiene styrene rubber is all measured and is obtained according to the disclosed method of GB/T1232.1-2000, and wherein, be 1min warm up time, and rotation time is 4min, and test temperature is 100 ℃.
According to the present invention, described vulcanizing agent can be the vulcanizing agent of various routines, for example, can be one or more in insoluble sulfur, dithio morpholine and four sulfuration two morpholines, is preferably insoluble sulfur.Wherein, the allotropic substance that described insoluble sulfur is sulphur, it is insoluble to sulfurous gas and other solvent, is also insoluble to rubber, in rubber, exists with dispersion state; When reaching after curing temperature, these insoluble sulfurs that are dispersed in rubber have one " activation stage ", i.e. chain type unzipping is accelerated vulcanization rate, reduces sulfur consumption, is conducive to improve the aging resistance of rubber.
According to the present invention, described vulcanization accelerator can be the existing various materials that can shorten curing time, reduction curing temperature, minimizing vulcanizing agent consumption and improve the physical and mechanical properties of rubber, but in order to obtain the more excellent rubber combination of environmental-protecting performance, under preferable case, described vulcanization accelerator is sulfenamide vulcanization accelerator and/or guanidine class vulcanization accelerator; Described sulfenamide vulcanization accelerator is preferably selected from one or more in the N-tertiary butyl-2-[4-morpholinodithio base sulphenamide, N-cyclohexyl-2-[4-morpholinodithio base sulphenamide and N-oxygen diethylidene-2-[4-morpholinodithio base sulphenamide; Described guanidine class vulcanization accelerator is vulkacit D and/or di-o-tolylguanidine.Wherein, the commodity of the described N-tertiary butyl-2-[4-morpholinodithio base sulphenamide TBBS by name or NS, be the vulcanization accelerator that a kind of performance is very excellent, its structural formula as the formula (1):
According to the present invention, the kind of described toughener and consumption are conventionally known to one of skill in the art, and for example, described toughener can be carbon black and/or white carbon black.Described carbon black can be the existing various carbon blacks that can be used in rubber combination, for example, can be selected from one or more in industrial reference black 7#, high abrasion furnace black(HAF) N330 and medium super abrasion furnace black N220, is preferably middle high abrasion furnace black(HAF) N330.Described white carbon black also can be for the existing various white carbon blacks that can improve described rubber combination intensity, and described white carbon black all can be commercially available, and for example, can be the white carbon black that is 115GR purchased from the trade mark of goldschmidt chemical corporation.
According to the present invention, described activator refers to the activity that can increase vulcanization accelerator, and then reduces the consumption of described vulcanization accelerator or the material of shortening curing time; Add a small amount of promoting agent can significantly improve sulphidity and the thermotolerance of described rubber.Vulcanizing agent of the present invention can be existing various vulcanizing agent, for example, can be zinc oxide and/or stearic acid.
According to the present invention, the preparation method of described tire shoulder glue comprises above-mentioned rubber combination is mixed, and obtains rubber unvulcanizate, and by described rubber unvulcanizate sulfuration, obtains tire shoulder glue rubber.In described rubber combination, the kind of each component and content can, according to carrying out choose reasonable above, will repeat at this no longer one by one.
According to the present invention, described mixing method and condition are can be compounding process and the condition of various routines, as a rule, and described mixing can carrying out in mill or Banbury mixer.Wherein, mixing between each material can carry out simultaneously, also can proceed step by step, is preferably proceed step by step.In addition, it is more even for each material can mixingly be obtained, to obtain the rubber that performance is more excellent, described mixing two stages of carrying out successively that comprise under preferable case, the mixing of first stage carried out on Banbury mixer, mixing condition comprises: temperature is 50-170 ℃, and pressure is 10-15MPa, and the time is 5-15 minute; The mixing of subordinate phase carried out in mill, and mixing condition comprises: temperature is 40-60 ℃, and the time is 5-15 minute.
In one embodiment of the invention, described tire shoulder glue can adopt following methods preparation: in Banbury mixer, add main rubber 50-70 ℃ to press down the mixing 30-60s of top, add again activator and other small powders, other small powders contain anti-aging agent and/or scorch retarder is pressed the mixing 60-90s of top, then add toughener and liquid isoprene rubber to press the mixing 2-4min of top, carry top 1-2min binder removal, dump temperature 150-170 ℃, obtain one section of rubber unvulcanizate, the one section of rubber unvulcanizate obtaining is cooled to room temperature placement overnight; Mixing subordinate phase comprises: by one section of rubber unvulcanizate and vulcanizing agent, vulcanization accelerator sheet under thin-pass in mill.The number of times of thin-pass can be determined according to the melting effect of rubber unvulcanizate, and preferably, the number of times of thin-pass is for being greater than 2 times, and more preferably the number of times of thin-pass is 6 times.
In the present invention, the mixing first stage can carry out in Banbury mixer, mixing subordinate phase can be carried out in mill, also can on Banbury mixer, carry out, in a kind of preferred implementation of the present invention, the mixing first stage carries out on Banbury mixer, and mixing subordinate phase is carried out in mill.
According to the present invention, as a rule, the method that rubber unvulcanizate is vulcanized and condition are conventionally known to one of skill in the art.For example, described sulfuration can be carried out in vulcanization bed or vulcanizing press; Described cure conditions generally includes temperature, pressure and the time of sulfuration, wherein, as long as the temperature of described sulfuration, pressure and time can guarantee described main rubber and vulcanizing agent generation crosslinking reaction, for example, described sulfuration comprises the mixing rubber unvulcanizate obtaining and vulcanizing agent and promotor is added to vulcanizer, the condition of sulfuration comprises that the temperature of sulfuration is 130-170 ℃, and the pressure of sulfuration is 10-15MPa, and the time of sulfuration is 10-50 minute.
In addition, the present invention also provides a kind of tire shoulder glue being prepared by method of the present invention.
To be further described in detail the present invention by specific embodiment below.
The testing method relating in following examples is as follows.
(1) relative molecular weight and polymer architecture
The relative molecular weight of LIR and the employing GPC that distributes thereof measure, test condition: make moving phase with tetrahydrofuran (THF), flow velocity 1.0mlmin
-125 ℃ of temperature.
The polymer architecture of LIR adopt infrared spectrometer (pressing potassium bromide troche) and nuclear magnetic resonance analyser (solvent be tritium for chloroform, probe temperature is 25 ℃, calibrates with tetramethylsilane) measure.
(2) rolling resistance
The rolling resistance of cross-linked rubber adopts rolling resistance test instrument to measure, test condition: load 15MPa, rotating speed 400rmin
-1.
(3) dynamic properties
The dynamic properties of cross-linked rubber adopts DMA to measure, test condition: frequency 10HZ, 2 ℃ of min of temperature rise rate
-1, Range of measuring temp-120 ℃ ~ 100 ℃, sample size (mm) approximately 20.00 × 5.00 × 2.00 (long × wide × thick).
(4) thermostability
The thermostability of cross-linked rubber adopts DSC/TG combined instrument to measure, test condition: 20 ℃ of min of temperature rise rate
-1, probe temperature 30-1000 ℃, nitrogen atmosphere, nitrogen flow 50mlmin
-1.
(5) mooney viscosity and mooney scorch
The mooney viscosity of cross-linked rubber and mooney scorch adopt mooney viscosity tester to measure, and mooney viscosity is equal to ISO289-1:1994 by GB/T1232.1-2000 to be measured, and test temperature is 100 ℃, and be 1 minute warm up time, and rotation time is 4 minutes; Mooney scorch test is undertaken by GB/T1233-1992, and test temperature is 120 ℃.
(6) vulcanization characteristics
The vulcanization characteristics of cross-linked rubber is pressed GB/T16584-1996 by MR-C3 type without rotor vulkameter and is measured.
Vulcanizating glue physical performance is all by the national standard test of GB/T528-1998.
In following examples and comparative example:
Natural rubber RSS3 is No. 3 smoke sheet rubbers purchased from Thailand, and number-average molecular weight is 1,000,000, and molecular weight distribution is 3.5, and mooney viscosity is 65;
Solution polymerized butadiene styrene rubber Tufprene 2000R is purchased from Japanese Asahi company, and weight-average molecular weight Mw is 16.1 ten thousand, molecular weight distribution 2.6, styrene content 25%, 1,2-structural content 13%, mooney viscosity 45.
Carbon black is high abrasion furnace black(HAF) N330, purchased from Guangzhou Li Ben rubber raw materials limited liability company;
Anti-aging agent RD: purchased from Jiangsu Sheng'Ao Chemical Technology Co., Ltd;
Sulphur: contain Science and Technology Ltd., S-80 purchased from Jinchang, Guangzhou;
Vulcanization accelerator NS: purchased from Haiyang Chemical Plant, Qingdao;
Zinc oxide: purchased from Liuzhou Xin Pin company limited;
Stearic acid: purchased from the polite Chemical Co., Ltd. in Hong Kong, the trade mark is SA1801;
Antioxidant 4020 (N-(1，3-dimethylbutyl)-N′-phenyl-p-phenylenediamine): purchased from Shanghai addition Chemical Co., Ltd.;
Anti-scorching agent CTP (N-cyclohexylthiophthalimide): purchased from Shandong Boxing Ke Yuan novel material limited liability company;
Insoluble sulfur: contain Science and Technology Ltd., S-80 purchased from Jinchang, Guangzhou.
Preparation example 1
This preparation example is used for explanation according to liquid isoprene of the present invention and preparation method thereof.
In 5L polymerization reaction kettle, carry out polyreaction.Paradigmatic system is after high pure nitrogen displacement, in polymerization reaction kettle, add 200g isoprene monomer successively, 1800g is dried hexanaphthene, under agitation in polymerization reaction kettle, add deionized water, continue stir about 10 minutes and be heated to 40 ℃, then at this temperature, adding 15.8mL concentration is the hexane solution of the n-Butyl Lithium of 0.3M, start polyreaction, in polymerization process, temperature is controlled in the scope of 40-50 ℃, be 0.1-0.3MPa(gauge pressure by the pressure-controlling in polymerization reaction kettle), carry out the polymerization of 120 minutes.Wherein, the mol ratio of deionized water and organic lithium initiator is 7.5:100.After polyreaction completes, add with the equimolar deionized water of organic lithium initiator and continue to stir 10 minutes to stop polyreaction, then adding concentration is 2 of 20 % by weight, the cyclohexane solution of 6-di-tert-butyl methyl phenol (wherein, BHT consumption is 0.6 % by weight of isoprene) stir 5 minutes.Polymerisate is dried to 2 hours in the vacuum drying oven of 80 ℃, obtains liquid polyisoprene rubber.Determine by weighting method, isoprene transformation efficiency is 100%.Liquid polyisoprene to preparation characterizes, and result is shown in table 1.
Preparation example 2
This preparation example is used for explanation according to liquid isoprene of the present invention and preparation method thereof.
Adopt the method identical with preparation example 1 to make isoprene carry out polymerization, different, the mol ratio of deionized water and organic lithium initiator is 2:100.Determine by weighting method, isoprene transformation efficiency is 100%.Liquid polyisoprene to preparation characterizes, and result is shown in table 1.
Preparation example 3
This preparation example is used for explanation according to liquid isoprene of the present invention and its preparation method and application.
Adopt the method identical with preparation example 1 to make isoprene carry out polymerization, different, the mol ratio of deionized water and organic lithium initiator is 4:100.Determine by weighting method, isoprene transformation efficiency is 100%.Liquid polyisoprene to preparation characterizes, and result is shown in table 1.
Table 1
Can be found out by table 1 result, adopt in liquid polyisoprene prepared by method of the present invention, the content of the structural unit that isoprene forms in the mode of Isosorbide-5-Nitrae-polymerization is high, can reach 96.9 % by mole above (under optimum condition, can reach more than 97 % by mole); The molecular weight distribution of the liquid polyisoprene of preparation is narrower, can reach below 1.11 and (under optimum condition, can reach below 1.10).
Embodiment 1-9
Embodiment 1-9 is for illustrating the preparation of tire shoulder glue provided by the invention.
Kind and the consumption of each component of the tire shoulder glue of embodiment 1-9 and comparative example 1-3 are as shown in table 2 below, and concrete preparation method is as follows:
Each component shown in table 2 is carried out to following operation: adopt two-stage process mixing, one section mixing carries out in Banbury mixer, banburying chamber's temperature 60 C, rotor speed 80rmin
-1, calendering process
enter mixing 1min after rubber, then add activator and optional other small powders, other small powders contain mixing 1.5min after anti-aging agent and/or scorch retarder, add again the rear mixing 3min of toughener and aromatic hydrocarbon oil (or LIR), mixing 1.5min after pressure-raising top, binder removal, dump temperature is not higher than 170 ℃, obtain one section of rubber unvulcanizate, the one section of rubber unvulcanizate obtaining is cooled to room temperature placement overnight; Two-stage mixing carries out in mill, and calendering process is: be under 20rpm mixing 8 minutes by one section of rubber unvulcanizate and Sulfur and promotor in roller speed, and 6 lower sheets of thin-pass.
To obtain two-stage mixing glue sizing material and vulcanize on vulcanizing press, cure conditions is 150 ℃ × 20min.Obtain tire shoulder glue S1-S9.
Comparative example 1
This comparative example is for illustrating the preparation of reference rubber unvulcanizate.
Method according to embodiment 1 is prepared rubber unvulcanizate, different, and described aromatic hydrocarbon oil (Ningbo Han Sheng company, N65) replacement for liquid polyisoprene rubber, obtains rubber unvulcanizate DH1.
Prepare tire shoulder glue according to the method for embodiment 1, different, the rubber unvulcanizate DH1 that described rubber unvulcanizate prepares by comparative example 1 replaces, and obtains tire shoulder DS1.
Comparative example 2
This comparative example is for illustrating the preparation of reference rubber unvulcanizate.
Method according to embodiment 1 is prepared rubber unvulcanizate, different, does not add solution polymerized butadiene styrene rubber, obtains rubber unvulcanizate DH2.
Prepare tire shoulder glue according to the method for embodiment 1, different, the rubber unvulcanizate DH2 that described rubber unvulcanizate prepares by comparative example 1 replaces, and obtains tire shoulder DS2.
Comparative example 3
This comparative example is for illustrating the preparation of reference rubber unvulcanizate.
Method according to embodiment 1 is prepared rubber unvulcanizate, different, does not add solution polymerized butadiene styrene rubber, and described aromatic hydrocarbon oil (Ningbo Han Sheng company, N65) replacement for liquid polyisoprene rubber, obtains rubber unvulcanizate DH3.
Prepare tire shoulder glue according to the method for embodiment 1, different, the rubber unvulcanizate DH2 that described rubber unvulcanizate prepares by comparative example 1 replaces, and obtains tire shoulder DS3.
Table 2 embodiment and comparative example formula used
* shown in table, be weight part, the liquid polyisoprene rubber being purchased in embodiment 4 is the LS-IR565 that Puyang Linshi Chemical New Materials Co., Ltd. produces, weight-average molecular weight 47,000-55,000, cis-Isosorbide-5-Nitrae structural content >80%.
Table 3
Note: rubber pugging mullering electric current/A refers to the electric current that adds natural rubber, solution polymerized butylbenzene and cis-1,4-polybutadiene rubber rear motor, add small powder electric current to refer to that activator, anti-aging agent and/or scorch retarder add the electric current of rear motor, add toughener and softening agent after-current to refer to add the electric current of carbon black (or white carbon black) and aromatic hydrocarbon oil (or liquid polyisoprene LIR) rear motor.
Can find out from the data of table 3, adopt synthetic polyisoprene to make softening agent embodiment 1 and comparative example 1,3 height aromatic hydrocarbon oil compare: embodiment 1 is less than the electric current of mixing process in comparative example 1,3, be that mixer power is little, can reach energy-saving and cost-reducing object; The sizing material smooth surface of extruding is smooth, and outward appearance is better, and component processing process is without distortion; Compared with the tire shoulder glue that the tire shoulder glue that embodiment 1 prepares prepares with comparative example 1,3, mooney viscosity is bigger, and Mooney scorch time is suitable, illustrates that complete processing is suitable, can make sizing material have better processing safety; In physical and mechanical properties, except tensile yield is slightly little, all the other are all more excellent or suitable, and good physical and mechanical properties has been described; Aging front and back tensile strength and tensile yield velocity of variation are little, illustrate that ageing-resistant performance is good, the work-ing life that can improve tire; Rebound value is little compared with large, whole dynamic pressure shrinkage, compression fatigue temperature rise is low, tension set is little, can delay the damaged tyres that tire causes at the heat history of driving process; Rolling resistance, dynamically deformation is little, and dynamically temperature rise is low, also can alleviate tire heat history in the process of moving, extends tyre life; Tan δ value 60 ℃ time reduces, and illustrates that the hysteresis loss of rubber is little, heat-dissipating is little, can alleviate equally tire heat history in the process of moving, extends tyre life; Second-order transition temperature reduces, and can improve the wear resistance of tire.Adopt in addition liquid isoprene rubber reactive plasticizer compared with high aromatic oil softening agent in comparative example 1, can from goods, not move out, can be to environment yet.
Compared with the embodiment 4 of the liquid polyisoprene rubber that the method for the embodiment 1-3 of liquid polyisoprene rubber prepared by employing the present invention and employing prior art prepares, processing characteristics is suitable, physical and mechanical properties is more excellent, the rebound resilience of the cross-linked rubber of embodiment 1-3 is larger, whole dynamic pressure shrinkage, temperature rise and tension set are all less, and rolling resistance, dynamically deformation, dynamically the dissipation factor of temperature rise and 60 ℃ is also less.
In addition, in the embodiment of the present invention 1, adopt compared with natural rubber only adopts natural rubber with solution polymerized butadiene styrene rubber composition with comparative example 2, processing characteristics is better, physical and mechanical properties quite or more excellent, ageing-resistant performance is better, rebound value is larger, whole dynamic pressure shrinkage, fatigue temperature rise, tension set, rolling resistance, dynamically deformation, dynamically the dissipation factor of temperature rise and 60 ℃ is all slightly little, second-order transition temperature is slightly low, be conducive to equally alleviate tire heat history in the process of moving, extend tyre life, improve tire wear.
Claims (13)
1. a rubber combination, said composition contains main rubber, vulcanizing agent, vulcanization accelerator, activator and toughener, it is characterized in that, described composition also contains liquid polyisoprene rubber, and described main rubber contains solution polymerized butadiene styrene rubber and natural rubber.
2. composition according to claim 1, wherein, take the total amount of described liquid polyisoprene rubber as benchmark, the amount of the structural unit that described isoprene forms by Isosorbide-5-Nitrae-polymerization is more than 96.9 % by mole.
3. composition according to claim 1 and 2, wherein, the number-average molecular weight of described liquid polyisoprene is 5000-100000, molecular weight distribution is 1.01-1.10.
4. composition according to claim 1, wherein, the weight ratio of described natural rubber and solution polymerized butadiene styrene rubber is 0.5-19:1.
5. according to the composition described in any one in claim 1-4, wherein, take the main rubber of 100 weight parts as benchmark, the content of described vulcanizing agent is 1-3 weight part, the content of described vulcanization accelerator is 1-5 weight part, the content of described toughener is 40-70 weight part, and the content of described activator is 0.5-8 weight part, and the content of described liquid polyisoprene rubber is 1-10 weight part; Described natural rubber accounts for the 45-95 % by weight of main rubber, and described solution polymerized butadiene styrene rubber accounts for the 5-55 % by weight of main rubber.
6. according to the composition described in any one in claim 1-4, wherein, described composition also contains anti-aging agent and/or scorch retarder, take the main rubber of 100 weight parts as benchmark, the content of described anti-aging agent is 2-5 weight part, and the content of described scorch retarder is 0.05-0.35 weight part.
7. composition according to claim 6, wherein, described anti-aging agent is amines antioxidants and/or quinoline type antioxidant; Described amines antioxidants is selected from N-sec.-propyl-N '-diphenyl-para-phenylene diamine, N-(1,3-dimethylbutyl)-N '-diphenyl-para-phenylene diamine and N, one or more in N '-bis-(Isosorbide-5-Nitrae-dimethyl amyl group) Ursol D, be preferably N-(1，3-dimethylbutyl)-N′-phenyl-p-phenylenediamine; Described quinoline type antioxidant is selected from 2,2,4-trimethylammonium-1,2-dihyaroquinoline polymer, 6-oxyethyl group-2,2,4-trimethylammonium-1,2-dihyaroquinoline and 6-dodecyl-2,2,4-trimethylammonium-1, one or more in 2-dihyaroquinoline, be preferably 2,2,4-trimethylammonium-1,2-dihyaroquinoline polymer; Described scorch retarder is selected from one or more in N-cyclohexylthiophthalimide, N nitrosodiphenyl amine, Whitfield's ointment and Tetra hydro Phthalic anhydride, is preferably N-cyclohexylthiophthalimide.
8. according to the composition described in any one in claim 1-4, wherein, the weight-average molecular weight of described natural rubber is 1,000,000-1,000 ten thousand, and molecular weight distribution is 3-6, and mooney viscosity is 65-75; The number-average molecular weight of described solution polymerized butadiene styrene rubber is 100,000-400,000, and molecular weight distribution is 1.1-3, and take the gross weight of described solution polymerized butadiene styrene rubber as benchmark, contents of ethylene is 10-35 % by weight, and mooney viscosity is 45-65.
9. composition according to claim 1 and 2, wherein, described vulcanizing agent is selected from one or more in insoluble sulfur, dithio morpholine and four sulfuration two morpholines; Described vulcanization accelerator is selected from one or more in the N-tertiary butyl-2-[4-morpholinodithio base sulphenamide, 2,2 '-dibenzothiazyl disulfide, the N-tertiary butyl-bis-(2-[4-morpholinodithio) sulfenamide, N-cyclohexyl-bis-(2-mercaptobenzothiazole) sulphenamide and vulkacit D; Described activator is zinc oxide and/or stearic acid; Described toughener is carbon black and/or white carbon black.
10. a preparation method for tire shoulder glue, the method comprises carries out the rubber combination described in any one in claim 1-9 mixing, obtains rubber unvulcanizate; And by described rubber unvulcanizate sulfuration, obtain tire shoulder glue.
11. methods according to claim 10, wherein, in described mixing two stages of carrying out successively that comprise, the mixing of first stage carried out on Banbury mixer, and mixing condition comprises: temperature is 50-170 ℃, and pressure is 10-15MPa, and the time is 5-15 minute; The mixing of subordinate phase carried out in mill, and mixing condition comprises: temperature is 40-60 ℃, and the time is 5-15 minute.
12. methods according to claim 10, wherein, described cure conditions comprises that curing temperature is 130-170 ℃, and sulfide stress is 10-15MPa, and curing time is 10-50 minute.
13. 1 kinds of tire shoulder glue, is characterized in that, this tire shoulder glue is prepared by the described method of any one in claim 10-12.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210425372.XA CN103788423B (en) | 2012-10-30 | 2012-10-30 | A kind of rubber composition and tire shoulder glue and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210425372.XA CN103788423B (en) | 2012-10-30 | 2012-10-30 | A kind of rubber composition and tire shoulder glue and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103788423A true CN103788423A (en) | 2014-05-14 |
| CN103788423B CN103788423B (en) | 2016-05-25 |
Family
ID=50664506
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210425372.XA Active CN103788423B (en) | 2012-10-30 | 2012-10-30 | A kind of rubber composition and tire shoulder glue and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103788423B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105754166A (en) * | 2014-12-17 | 2016-07-13 | 中国石油化工股份有限公司 | Rubber composition and vulcanized rubber and preparation method and application thereof |
| CN106032427A (en) * | 2015-03-18 | 2016-10-19 | 中国石油化工股份有限公司 | Rubber composition, and vulcanized rubber and preparation method thereof |
| CN106032428A (en) * | 2015-03-18 | 2016-10-19 | 中国石油化工股份有限公司 | Rubber composition, and vulcanized rubber and preparation method thereof |
| CN110088191A (en) * | 2016-12-15 | 2019-08-02 | 通伊欧轮胎株式会社 | Rubber composition for tire and the pneumatic tire for having used the rubber composition for tire |
| CN116656020A (en) * | 2023-06-09 | 2023-08-29 | 中策橡胶集团股份有限公司 | Anti-fatigue rubber composition, mixing method and application thereof in preparation of air spring |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20030046541A (en) * | 2001-11-26 | 2003-06-18 | 한국타이어 주식회사 | Tire tread rubber composition |
| CN102030926A (en) * | 2010-11-30 | 2011-04-27 | 江苏通用科技股份有限公司 | High abrasion-resistant tread rubber for middle and long distance highway transportation type radial tire and producing method thereof |
| CN102250393A (en) * | 2011-06-16 | 2011-11-23 | 北京化工大学 | Strengthened and heat-conducting rubber for heavy truck tire shoulder |
-
2012
- 2012-10-30 CN CN201210425372.XA patent/CN103788423B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20030046541A (en) * | 2001-11-26 | 2003-06-18 | 한국타이어 주식회사 | Tire tread rubber composition |
| CN102030926A (en) * | 2010-11-30 | 2011-04-27 | 江苏通用科技股份有限公司 | High abrasion-resistant tread rubber for middle and long distance highway transportation type radial tire and producing method thereof |
| CN102250393A (en) * | 2011-06-16 | 2011-11-23 | 北京化工大学 | Strengthened and heat-conducting rubber for heavy truck tire shoulder |
Non-Patent Citations (1)
| Title |
|---|
| 李传清等: ""液体聚异戊二烯橡胶的研究进展"", 《橡胶工业》, vol. 59, no. 5, 25 May 2012 (2012-05-25), pages 313 - 316 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105754166A (en) * | 2014-12-17 | 2016-07-13 | 中国石油化工股份有限公司 | Rubber composition and vulcanized rubber and preparation method and application thereof |
| CN105754166B (en) * | 2014-12-17 | 2018-02-13 | 中国石油化工股份有限公司 | A kind of rubber composition is with vulcanizing rubber and its preparation method and application |
| CN106032427A (en) * | 2015-03-18 | 2016-10-19 | 中国石油化工股份有限公司 | Rubber composition, and vulcanized rubber and preparation method thereof |
| CN106032428A (en) * | 2015-03-18 | 2016-10-19 | 中国石油化工股份有限公司 | Rubber composition, and vulcanized rubber and preparation method thereof |
| CN106032428B (en) * | 2015-03-18 | 2019-01-18 | 中国石油化工股份有限公司 | A kind of rubber composition and vulcanized rubber and preparation method thereof |
| CN106032427B (en) * | 2015-03-18 | 2019-02-19 | 中国石油化工股份有限公司 | A kind of rubber composition and vulcanized rubber and preparation method thereof |
| CN110088191A (en) * | 2016-12-15 | 2019-08-02 | 通伊欧轮胎株式会社 | Rubber composition for tire and the pneumatic tire for having used the rubber composition for tire |
| CN116656020A (en) * | 2023-06-09 | 2023-08-29 | 中策橡胶集团股份有限公司 | Anti-fatigue rubber composition, mixing method and application thereof in preparation of air spring |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103788423B (en) | 2016-05-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103788422B (en) | A kind of rubber composition and tire tread glue and preparation method thereof | |
| CN109181027B (en) | High-performance tire tread rubber and preparation method thereof | |
| JP6018207B2 (en) | Rubber composition for tread and pneumatic tire | |
| JP5650690B2 (en) | Rubber composition for tread and pneumatic tire | |
| JP5933497B2 (en) | Pneumatic tire | |
| CN102746538B (en) | Rubber composition for tire and pneumatic tyre | |
| CN103788423B (en) | A kind of rubber composition and tire shoulder glue and preparation method thereof | |
| EP2905305B1 (en) | Pneumatic tire | |
| JP2014088544A (en) | Branched conjugated diene copolymer, rubber composition and pneumatic tire | |
| JP5612729B2 (en) | Rubber composition for tire and pneumatic tire | |
| CN107641228B (en) | Use of organosilanes and rubber compositions and vulcanizates and process for their preparation | |
| CN109929160B (en) | Application of organosilane coupling agent, rubber composition, vulcanized rubber and preparation method and application thereof | |
| CN113072750B (en) | High-strength rubber composite material with excellent processability and preparation method thereof | |
| CN107921817B (en) | High-performance tyre | |
| KR20110056238A (en) | Pneumatic tire | |
| CN109929159B (en) | Rubber composition and vulcanized rubber for tire tread as well as preparation method and application of rubber composition and vulcanized rubber | |
| EP2643367B1 (en) | High-performance tyre | |
| US20180051118A1 (en) | High-performance tyre | |
| CN112912258B (en) | Rubber composition and pneumatic tire | |
| JP2019099656A (en) | Tire rubber composition | |
| CN111471221A (en) | High-stiffness low-viscosity tire rubber compound, preparation method thereof and semi-steel radial tire | |
| CN102532613A (en) | Rubber composition | |
| EP2604631A1 (en) | Modified conjugated diene rubber, method and composition thereof | |
| JP6026905B2 (en) | Rubber composition for tire and pneumatic tire | |
| CN105367850A (en) | Tire and method for manufacturing tire |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |