CN103788423B - A kind of rubber composition and tire shoulder glue and preparation method thereof - Google Patents
A kind of rubber composition and tire shoulder glue and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of rubber composition and a kind of tire shoulder glue and preparation method thereof, said composition contains dience rubber, vulcanizing agent, vulcanization accelerator, activator and reinforcing agent, wherein, described composition also contains liquid polyisoprene rubber, and described dience rubber contains solution polymerized butadiene styrene rubber and natural rubber. Rubber composition provided by the invention has lower power consumption of polymer processing concurrently, it is good with calendering sizing compound surface quality to extrude, Physical Mechanical is good, especially compression set and resistance to rolling are less, heat-dissipating is lower, better heat stability, can improve durability, the prolongation tyre life of tire, be conducive to tire energy-conservation, simultaneously, because this rubber composition has been avoided at high temperature volatile, shortcoming to environment and man body pollution of common plasticizers, be suitable for preparing high-performance green tire.
Description
Technical field
The present invention relates to a kind of rubber composition and tire shoulder glue and preparation method thereof.
Background technology
Along with the raising of road quality classification and the development of transport service, automobile travels under high speed excess loadQuite general, people are also more and more higher to the performance requirement of tire. Tire is tire shoulder in the process of movingThe stress that bears is concentrated, distortion is large, heat-dissipating is higher, therefore easily occur in the process of moving shoulder empty,Shoulder such as splits at the early stage phenomenon, affects the service life of tire. In addition, in traditional rubber processing process,Conventional low point of seed oil of aromatic hydrocarbons made plasticizer or softening agent, and these plasticizer not only can reduce vulcanizatePhysical property, and at high temperature volatile, majority has contaminative, in use easily migrationExtract out to product surface or by solvent, thereby make that product volume is shunk, distortion and affect service life.Along with the reinforcement of people's environmental consciousness, countries in the world are more and more higher to environmental requirement, and legislation also comesStricter, as the Reach of European Union bill requires to export to after 2010 in the rubber of European Union notCan be containing harmful aromatic hydrocarbon substance, because these materials can be with the wearing and tearing of tire and rubberGrain enters atmosphere and together to environment. This regulation goes out tire manufacture and China's tireMouth industry has caused very large impact.
Adopt reactive plasticizer can give the processing characteristics that rubber is good as liquid rubber. Liquid rubberOften have and the same or analogous chain structure of material of main part, when sulfuration, can participate in the crosslinked sulfuration that becomesPart in glue network, makes vulcanizate have good physical property and chemical stability. This, adopt liquid rubber as plasticizer outward, can also save mixing energy consumption, improve extrusion efficiency and squeezeGo out thing dimensional stability, improve and extrude with calendering sizing compound surface quality and improve the sticky of uncured rubber sheetProperty and reduce permanent deformation and the resistance to rolling of vulcanizate, be conducive to tire energy-conservation, can reduce environmentPollute.
CN102134336A adopts liquid polyisoprene rubber as tyre triangular glue composition, thisBright before ensureing that triangle rubber sizing material Main physical performance, part dimension stability, technique viscosity do not reducePut, reduce extrude heat up high, enhance productivity, reduce process loss. Main body rubber in this inventionGlue is natural rubber, and liquid polyisoprene rubber is the preparation for tyre triangular glue. Tyre triangular glueDifferent with the purposes of tire shoulder glue, completely different to its performance requirement, and this invention triangle rubber formulaMiddle carbon black loading is large, requires sizing material hardness to want large, and processing characteristics will be got well, and compression heat generation is low, but to glueMaterial wearability, resistance to rolling, anti-slippery do not have 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. High owing to containingThe use of aromatics process oil, tire in use still can be to environment.
In JP2000142016A, introduce and a kind ofly improved processing characteristics and with white carbon reinforcementTire tread glue composition, this sizing material is by 100 weight portion dience rubbers, the liquid of 3-40 % by weightThe block copolymer of body isoprene and vinylpyridine (wherein with respect to isoprene, vinylThe content of pyridine is 3%-30%, and number-average molecular weight is 2000-50000) and 20-150 part SiO2Composition, the rubber of this invention has good extrusion performance, and the rubber obtaining after sulfuration has wellWearability and lower resistance to rolling. Although this invention can obtain the tire tread of better performancesGlue composition, but liquid rubber in this invention tread rubber composition need to comprise two kinds of monomers: differentPentadiene and vinylpyridine, the preparation process of this liquid rubber is more complicated, and monomer vinyl pyrroleThe price of pyridine is more expensive, causes the price of this liquid rubber more expensive, and will use in rubber processing processThe SiO that price is relatively expensive2As reinforcing agent, cause the manufacturing cost of tire higher. This inventionIn method, do not mention this tread rubber composition when the tire tread glue to resistance to rolling, anti-slipperyProperty, heat-dissipating and ageing-resistant performance improve result.
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 is providedComposition, the tire shoulder glue that this rubber composition makes can have good physical and mechanical properties and pressureWhen contracting heat-dissipating and dynamic heat build up performance, there is good combination property.
The invention provides a kind of rubber composition, said composition contains main rubber, vulcanizing agent, sulfurationPromoter, activator and reinforcing agent, wherein, described composition also contains liquid polyisoprene rubber,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 above-mentioned rubberComposition carries out mixing, obtains elastomeric compound; And by described elastomeric compound sulfuration, obtain tire shoulder glue.
In addition, the present invention also provides a kind of tire shoulder glue being prepared by said method.
The tire shoulder glue that composition provided by the invention prepares, the tire that this rubber composition makesTire shoulder glue can have good calendering process performance, good physical property, heat endurance and dynamic force concurrentlyLearn performance and environmental protection. 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 naphtha is plasticizer, embodimentThe fissipation factor tan δ (60 DEG C) of the 1 tire shoulder glue preparing is 0.072, vitrification point TgFor-44.15 DEG C, rebound value is 54%, and aging after-drawing intensity is 20.4MPa, and adopts aromatic naphtha to beThe fissipation factor tan δ (60 DEG C) of the tire shoulder glue that the comparative example 1 of plasticizer prepares is 0.0814,Vitrification point Tg is-43.57 DEG C, and rebound value is 48%, and aging after-drawing intensity is 19.1MPa. Study carefullyIts reason may be that liquid polyisoprene rubber is reactive plasticizer, can be to ring in use procedureBorder pollutes and also can not move to product surface, thus can not make product volume shrink, distortion and affectService life; In addition, because the structure of liquid polyisoprene rubber and natural rubber or butadiene-styrene rubber connectsClosely, easily and rubber mix, make plasticizer with general low point of seed oil of aromatic hydrocarbons compared with, the adding of elastomeric compoundWork energy consumption is lower; Moreover, because liquid polyisoprene rubber can be with natural rubber and synthetic rubber at sulphurIn change process, there is co-crosslinking, by the kind of other components and the selection of content of composition, make systemThe standby tire obtaining can have following performance: (1) preferably physical and mechanical properties is as high in intensity, resistance to oldVoltinism can be good, can improve Using Life of Tyre, ensures can not cause this because of heat-dissipating in tire runningPosition properties of rubber declines and affects tire used performance; (2) good, the compression heat generation of the resilience of tire shoulder glueAnd dynamic heat build up is low, permanent deformation is little, can delays tire hot and accumulate the destruction of causing; (3) tire shoulderThe hysteresis loss of glue and heat-dissipating reduce, and can alleviate tire heat history in the process of moving, extend tireLife-span; (4) vitrification point reduces, and can improve the wearability of tire.
Detailed description of the invention
According to the present invention, this rubber composition contains main rubber, vulcanizing agent, vulcanization accelerator, activationAgent and reinforcing agent, wherein, described composition also contains liquid polyisoprene rubber, described main rubberContain solution polymerized butadiene styrene rubber and natural rubber.
According to the present invention, although as long as ensure described rubber contain solution polymerized butadiene styrene rubber and natural rubber andDescribed rubber composition also contains liquid polyisoprene rubber just can realize object of the present invention, to instituteThe kind and the preparation method that state the liquid polyisoprene rubber in rubber composition do not have particular/special requirement. InstituteThe liquid polyisoprene rubber of stating can be commercially available, and also can carry out according to method of the prior artPreparation. For example, liquid polyisoprene rubber can reference literature " elastomer " the 21st volume in 2011Preparation method's preparation of the 2nd phase 32-35 page. But, in order to obtain the rubber that combination property is more excellentComposition, preferably, taking the total amount of described liquid polyisoprene rubber as benchmark, described isopreneThe amount of the construction unit forming by Isosorbide-5-Nitrae-polymerization is more than 96.9 % by mole. Further preferably, liquidThe molecular weight distribution of 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: in anionic polymerisationUnder condition, isoprene is contacted in solvent with water with organic lithium initiator; Wherein, water and instituteThe mol ratio of stating 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 water and instituteThe mol ratio of stating organic lithium initiator is within above-mentioned scope time, the polyisoprene finally obtaining pointSon amount distributes and can reach below 1.10, and in the polyisoprene obtaining, isoprene is with Isosorbide-5-Nitrae-polymerizationThe content of the construction unit that mode forms is high, and can reach 96.9 % by mole above (can under optimum conditionReach 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, taking 100 moles of described organic lithium initiators as benchmark, only there is at the most 0.9-9Mole organic lithium initiator and water react (even if think organic lithium initiator and water to reactThe whole lithium hydroxides that form react and generate lithia, organic lithium initiator with organic lithium initiatorTotal flow be only also 1.8-18 mole). That is, according to the present invention, the organolithium reacting with waterThe amount of initator 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 inventionSet out, 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, Ke YitongIn time, adds water and described organic lithium initiator in the solvent that contains isoprene to; Also can first add waterThen organic lithium initiator is added in the solvent that contains isoprene. Because water is polar substances,Carry out solvent and isoprene monomer polarity that polymerization uses lower, therefore from improving being uniformly dispersed of waterThe angle of property is set out, and preferably first adds water in the solvent that contains isoprene and is uniformly dispersed, thenAdd again described organic lithium initiator.
According to the present invention, can regulate produced according to the present invention by the consumption that changes organic lithium initiatorThe molecular weight of polyisoprene. , the amount of described organic lithium initiator can be according to the poly-isoamyl of expectionThe molecular weight of diene carries out suitable selection. Usually, rubbing of described organic lithium initiator and isopreneYou are than can be 3.5 × 10-4-0.028:1. Preferably, rubbing of described organic lithium initiator and isopreneYou are than being 7 × 10-4-0.013：1。
According to the present invention, described organic lithium initiator can cause isoamyl for conventional various in this areaDiene carries out the organo-lithium compound of anionic polymerisation. For example, described organic lithium initiator can be separatelyCompound shown in formula I,
R1Li（I），
In formula I, R1Can be C1-C10Straight or branched alkyl (comprise C1-C10Straight chained alkyl andC3-C10Branched alkyl) or C6-C20Replacement or unsubstituted aryl.
In the present invention, C1-C10The example of straight or branched alkyl can include but not limited to: methyl,Ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, isoamylBase, tertiary pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl and positive decyl.
In the present invention, C6-C20Replacement or the example of unsubstituted aryl can include but not limited to: benzeneBase, aminomethyl phenyl, ethylphenyl, tert-butyl-phenyl and naphthyl.
According to the present invention, described organic lithium initiator can be ethyl-lithium, n-pro-pyl lithium, isopropyl lithium,N-BuLi, s-butyl lithium, n-pentyl lithium, hexyllithium, cyclohexyl lithium, phenyl lithium, aminomethyl phenylOne or more in lithium and naphthyl lithium.
Preferably, described organic lithium initiator is n-BuLi, s-butyl lithium, isobutyl group lithium and the tert-butyl groupOne or more in lithium.
According to the present invention, be not particularly limited for the monomer concentration of isoprene in solvent, can be thisThe routine in field is selected, for example: taking the total amount of isoprene and described solvent as benchmark, described isoamyl twoThe content of alkene can be more than 5 % by weight. According to the present invention, water and described organic lithium initiator moleThan being 0.9-9:100, not only can make like this liquid polyisoprene finally obtaining there is narrow dividingSon amount distributes, and improves the amount of carrying out the isoprene of polymerization in the mode of Isosorbide-5-Nitrae-polymerization, and at all the otherPart identical (comprising for reducing the service condition of the cooling device of the reaction temperature of polymerization system identical)In situation, also make polymerisation to carry out more stably, reduce and even avoid in polymerization process,The polymerization system temperature causing because local polymerization speed is too high raises. Therefore, according to the present invention, canCarry out polymerization with the monomer concentration with higher, and then make method of the present invention there is higher production effectRate. according to the present invention, taking the total amount of isoprene and described solvent as benchmark, described isopreneContent is preferably 5-60 % by weight, more preferably 10-40 % by weight.
According to the present invention, described solvent can be for the conventional various non-polar solvens in this area, for example variousVarsol is (as C4-C8Straight or branched aliphatic saturated hydrocarbon or C6-C12Replacement or do not replaceAromatic hydrocarbons). In the present invention, the example of described solvent can for but be not limited to: benzene, toluene, cyclohexane,N-hexane, pentane, normal heptane, raffinate oil or hydrogasoline in one or more.
One of the present invention preferred embodiment in, described solvent is that boiling range is more than 55-100 DEG C taking outOil or boiling range are the hydrogasoline of 55-100 DEG C. Adopting boiling range is that 55-100 DEG C raffinating oil or boiling range areWhen the hydrogasoline of 55-100 DEG C, because its solubility parameter is relatively low, to liquid polyisoprene rubberThe dissolubility of glue reduces, and causes polymer molecule in solvent, to be rolled state, makes the polymerization of same concentrationsThe reduced viscosity of thing solution, is conducive to withdrawing from and the steady control of reaction temperature of polymerization reaction heat, like thisNot only under equal conditions, in the liquid polyisoprene of preparation, the knot forming in the mode of Isosorbide-5-Nitrae-polymerizationThe content of structure unit is higher; And even under higher monomer concentration, the liquid of preparation gathers isoamyl twoIn alkene, more than the content of the construction unit forming with Isosorbide-5-Nitrae-polymerization methods still can reach 97 % by weight.And boiling range is that 55-100 DEG C raffinating oil or boiling range are that the source of hydrogasoline of 55-100 DEG C is abundant,Cheap, freezing point is low, while production in the winter time, and can be in order to avoid the pipeline of delivery solvent be carried outHeating, thus the production cost of method of the present invention can further be reduced. Further preferably, described inSolvent is that boiling range is that 55-85 DEG C raffinating oil or boiling range are the hydrogasoline of 55-85 DEG C.
In the present invention, described in to raffinate oil be in petroleum refining process, be rich in the catalytic reformate of aromatic hydrocarbonsRemaining distillate after extraction aromatic hydrocarbons. In the present invention, described hydrogasoline refers in regular gasolineThe gasoline that alkene and diene hydrogenation are saturated, aromatic hydrocarbons partial hydrogenation is saturated and obtain.
According to the present invention, be not particularly limited for described anionic polymerisation condition, can be this areaConventional selection. Usually, described anionic polymerisation condition comprises: temperature can be 20-100 DEG C, preferablyFor 30-80 DEG C; Time can be 10 minutes to 3 hours, is preferably 30 minutes to 2 hours; With tablePress meter, pressure can be 0.01-0.5MPa, is preferably 0.05-0.3MPa. Isoprene and water and organicThe contact of lithium initiator is carried out under inert gas shielding, and described inert gas can be conventional for this areaVarious non-active gas, for example: nitrogen and group 0 element gas (as argon gas).
After polymerization completes, can adopt the conventional method of this area by polymerization activity center according to the present inventionDeactivation. For example, can be by contact the mixture obtaining with organic lithium initiator with water to isopreneIn (, polymerizate), add polymerization terminator, thereby by the polymerization activity in described polymerizateHeart deactivation. Described polymerization terminator can be the conventional various polymerization terminators in this area, for example: described inPolymerization terminator can be water and/or alcohol. Described alcohol can be in methyl alcohol, ethanol, normal propyl alcohol and isopropyl alcoholOne or more. The present invention is not particularly limited for the consumption of described polymerization terminator, as long as described inThe consumption of polymerization terminator can make polymerization activity center loss of activity. Usually, described polymerization eventuallyOnly the mol ratio of agent 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 conventional method of this area to remove the solvent in polymerizate. For example,Can be by the polymerizate that is added with described age resistor in hot-air, steam under decompression or normal pressureSend out, thus desolvation; Also can, under the condition vacuumizing, carry out desolvation by thin film evaporator.
The various reagent that use according to the present invention preferably adopt the conventional method of this area to enter before useRow is refining, 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 carryThe combination property of high described rubber composition, under preferable case, described natural rubber and solution polymerized butylbenzene rubberThe weight ratio of glue 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 composition, in order to obtainThe rubber composition that combination property is more excellent, under preferable case, taking the main rubber of 100 weight portions asBenchmark, the content of described vulcanizing agent is 1-3 weight portion, the content of described vulcanization accelerator is 1-5 weightPart, the content of described reinforcing agent is 40-70 weight portion, the content of described activator is 0.5-8 weight portion,The content of described liquid polyisoprene rubber is 1-10 weight portion, and described natural rubber accounts for main rubber45-95 % by weight, described solution polymerized butadiene styrene rubber accounts for the 5-55 % by weight of main rubber. Further preferablyIn situation, taking the main rubber of 100 weight portions as benchmark, the content of described vulcanizing agent is that 1.5-2.5 is heavyAmount part, the content of described vulcanization accelerator is 1.5-4.5 weight portion, the content of described reinforcing agent is 45-65Weight portion, the content of described activator is 2-5.5 weight portion, the containing of described liquid polyisoprene rubberAmount is for 1.5-9.5 weight portion, and described natural rubber accounts for the 50-90 % by weight of main rubber, described in contain intermingle with fourthBenzene 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 composition, enterAnd obtaining the rubber composition that combination property is more excellent, under preferable case, described composition also containsAge resistor and/or antiscorching agent, taking the main rubber of 100 weight portions as benchmark, the content of described age resistor is2-5 weight portion, the content of described antiscorching agent is 0.05-0.35 weight portion.
According to the present invention, the kind of described age resistor and consumption are conventionally known to one of skill in the art. For example,Described age resistor can be amines antioxidants and/or quinoline type antioxidant; Described amines antioxidants can be selected fromN-isopropyl-N '-diphenyl-para-phenylene diamine, N-(1,3-dimethylbutyl)-N '-diphenyl-para-phenylene diamine (commodityBe called 4020) and N, one or more in N '-bis-(Isosorbide-5-Nitrae-dimethyl amyl group) p-phenylenediamine (PPD), described inQuinoline type antioxidant can be selected from 2,2,4-trimethyl-1,2-dihyaroquinoline condensate, 6-ethyoxyl-2,2,4-Trimethyl-1,2-dihyaroquinoline and 6-dodecyl-2,2,4-trimethyl-1, the one in 2-dihyaroquinolineOr multiple; Wherein, described 2,2,4-trimethyl-1, the polymeric commodity of 2-dihyaroquinoline are called RD, itsStructural formula is as the formula (2):
Formula (2),
It should be noted that, of the present invention 2,2,4-trimethyl-1,2-dihyaroquinoline condensate refers in particular to2,2,4-trimethyl-1, dimer, tripolymer or the tetramer (, n=2,3 or 4) of 2-dihyaroquinoline;And due to described 2,2,4-trimethyl-1, the dimeric anti-old performance of 2-dihyaroquinoline is very excellent, therefore,Described 2,2,4-trimethyl-1,2-dihyaroquinoline condensate is preferably dimer, or dimer and tripolymerAnd/or tetrameric mixture. More preferably, when described 2,2,4-trimethyl-1,2-dihyaroquinoline dimerizationWhen body is dimer and tripolymer and/or tetrameric mixture, taking the gross weight of described mixture as baseStandard, described dimeric content is 25-55 % by weight, described dimer and trimerical total content are45-75 % by weight.
According to the present invention, the kind of described antiscorching agent and consumption are conventionally known to one of skill in the art. For example,Described antiscorching agent can be N-cyclohexylthiophthalimide, N nitrosodiphenyl amine, bigcatkin willowOne or more in acid and phthalic anhydride, are preferably N-cyclohexylthiophthalimide.
According to the present invention, in order to improve wearability and the elasticity of described rubber composition, and then combinedClose the rubber composition that performance is more excellent, under preferable case, the number-average molecular weight of described natural rubberBe 1,000,000-1,000 ten thousand, 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 100,000-40Ten thousand, 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 weight of the vinyl that has neither part nor lot in polymerization in solution polymerized butadiene styrene rubber and contains intermingle withThe ratio of butadiene-styrene rubber gross weight, in other words, it is equivalent to carry out butadiene described in 1,2 additionContent. In addition, it should be noted that, in the present invention, the Mooney viscosity of described solution polymerized butadiene styrene rubber is equalMeasure and obtain according to the disclosed method of GB/T1232.1-2000, wherein, be 1min preheating time, rotatesTime is 4min, and test temperature is 100 DEG C.
According to the present invention, described vulcanizing agent can be the vulcanizing agent of various routines, for example, can be insolubleOne or more in sulphur, two sulfo-morpholines and four sulfuration two morpholines, are preferably insoluble sulfur.Wherein, the allotrope that described insoluble sulfur is sulphur, it is insoluble to sulfur dioxide and other solvent,Also be insoluble to rubber, in rubber, exist with dispersity; When reaching after curing temperature, these are dispersed inInsoluble sulfur in rubber has one " activation stage ", i.e. chain type depolymerisation, makes curingprocess rateAccelerate, reduce sulfur consumption, be conducive to improve the ageing properties of rubber.
According to the present invention, described vulcanization accelerator can be for existingly variously shortening cure time, fallLow curing temperature, minimizing vulcanizing agent consumption also improve the material of the physical and mechanical properties of rubber, but are terribleTo the more excellent rubber composition of environmental-protecting performance, under preferable case, described vulcanization accelerator is time sulphonylAmine vulcanization accelerator and/or guanidine class vulcanization accelerator; Described sulfenamide vulcanization accelerator is preferably selected fromThe N-tert-butyl group-2-[4-morpholinodithio base sulfenamide, N-cyclohexyl-2-[4-morpholinodithio base sulfenamide and N-oxygenOne or more in diethylidene-2-[4-morpholinodithio base sulfenamide; Described guanidine class vulcanization accelerator is twoBenzene guanidine and/or di-o-tolylguanidine. Wherein, the commodity of the described N-tert-butyl group-2-[4-morpholinodithio base sulfenamideTBBS by name or NS, be the vulcanization accelerator that a kind of performance is very excellent, and its structural formula is suc as formula (1)Shown in:
Formula (1).
According to the present invention, the kind of described reinforcing agent and consumption are conventionally known to one of skill in the art, for example,Described reinforcing agent can be carbon black and/or white carbon. Described carbon black can be the existing various rubbers that can be used inThe carbon black of glue composition, for example can be selected from industrial reference black 7#, high abrasion furnace black N330 and in superOne or more in wear-resisting furnace black N220, are preferably middle high abrasion furnace black N330. Described white carbon alsoCan be the existing various white carbons that can improve described rubber composition intensity, and described white carbonAll can be commercially available, for example, can be white for what be 115GR purchased from the trade mark of goldschmidt chemical corporationCarbon black.
According to the present invention, described activator refers to the activity that can increase vulcanization accelerator, and then reduces instituteState the consumption of vulcanization accelerator or the material of shortening cure time; Add a small amount of activating agent to significantly improveThe sulphidity of described rubber and heat resistance. Vulcanizing agent of the present invention can be existing various sulfurationAgent 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 composition is mixed allEven, obtain elastomeric compound, and by described elastomeric compound sulfuration, obtain tire shoulder glue rubber. Described rubber groupIn compound, the kind of each component and content can, according to carrying out choose reasonable above, will be gone to live in the household of one's in-laws on getting married at this no longer one by oneState.
According to the present invention, described mixing method and condition are can be compounding process and the bar of various routinesPart, as a rule, described mixing can carrying out in mill or banbury. Wherein, between each materialMixingly can carry out simultaneously, also can carry out step by step, be preferably substep and carry out. In addition, each in order to makeMaterial can mixingly obtain more even, to obtain the rubber that performance is more excellent, described mixed under preferable caseRefining comprises two stages of carrying out successively, and the mixing of first stage carried out on banbury, mixing condition bagDraw together: temperature is 50-170 DEG C, pressure is 10-15MPa, and the time is 5-15 minute; Mixing of second stageRefining is carried out in mill, and mixing condition comprises: temperature is 40-60 DEG C, and the time is 5-15 minute.
In one embodiment of the invention, described tire shoulder glue can adopt following methods preparation:In banbury, add main rubber 50-70 DEG C to press down the mixing 30-60s of top, then add activator and itsHis small powder, other small powders contain age resistor and/or antiscorching agent is pressed the mixing 60-90s of top, then add reinforcing agentPress the mixing 2-4min of top with liquid isoprene rubber, carry top 1-2min binder removal, dump temperature 150-170DEG C, obtain one section of elastomeric compound, the one section of elastomeric compound obtaining is cooled to room temperature placement overnight; MixingTwo-stage comprises: by one section of elastomeric compound and vulcanizing agent, vulcanization accelerator sheet under thin-pass in mill. ThinLogical number of times can be determined according to the melting effect of elastomeric compound, and preferably, the number of times of thin-pass is for being greater than 2 times,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, and mixing second stage is passableIn mill, carry out, also can on banbury, carry out, in a kind of preferred embodiment of the present invention,The mixing first stage carries out on banbury, and mixing second stage is carried out in mill.
According to the present invention, as a rule, the method that elastomeric compound is vulcanized and condition are art technologyPersonnel are known. For example, described sulfuration can be carried out in vulcanization bed or vulcanizing press; Described sulfurationCondition generally includes temperature, pressure and the time of sulfuration, wherein, the temperature of described sulfuration, pressure and timeAs long as between can ensure described main rubber and vulcanizing agent generation cross-linking reaction, for example, described sulfurationComprise the mixing elastomeric compound obtaining and vulcanizing agent and promoter are added to vulcanizer, the condition of sulfuration comprises sulphurThe temperature of changing is 130-170 DEG C, 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 method of testing 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: do with oxolaneMobile phase, flow velocity 1.0mlmin-125 DEG C of temperature.
The polymer architecture of LIR adopts infrared spectrometer (pressing potassium bromide troche) and NMR (solventFor tritium is for chloroform, probe temperature is 25 DEG C, calibrates with tetramethylsilane) measure.
(2) resistance to rolling
The resistance to rolling of vulcanizate adopts rolling resistance test instrument to measure, test condition: load 15MPa,Rotating speed 400rmin-1。
(3) dynamic mechanical
The dynamic mechanical of vulcanizate adopts DMA to measure, and test condition: frequency 10HZ heats up2 DEG C of min of speed-1, Range of measuring temp-120 DEG C ~ 100 DEG C, sample size (mm) is approximately20.00 × 5.00 × 2.00 (long × wide × thick).
(4) heat endurance
The heat endurance of vulcanizate adopts DSC/TG combined instrument to measure, test condition: heating rate 20℃·min-1, probe temperature 30-1000 DEG C, nitrogen atmosphere, nitrogen flow 50mlmin-1。
(5) Mooney viscosity and mooney scorch
The Mooney viscosity of vulcanizate and mooney scorch adopt Mooney viscosity test instrument to measure, and Mooney viscosity is pressedGB/T1232.1-2000 is equal to ISO289-1:1994 and measures, and test temperature is 100 DEG C, preheatingTime is 1 minute, and rotation time is 4 minutes; Mooney scorch test is undertaken by GB/T1233-1992,Test temperature is 120 DEG C.
(6) vulcanization characteristics
The vulcanization characteristics of vulcanizate is pressed GB/T16584-1996 by MR-C3 type without rotor vulcameter 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, pointSon amount is distributed as 3.5, and Mooney viscosity is 65;
Solution polymerized butadiene styrene rubber Tufprene2000R is purchased from Japanese Asahi company, and weight average molecular weight Mw is16.1 ten thousand, molecular weight distribution 2.6, styrene-content 25%, 1,2-structural content 13%, Mooney viscosity45。
Carbon black is high abrasion furnace black N330, purchased from Guangzhou Li Ben rubber raw materials Co., Ltd;
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 Co., Ltd;
Stearic acid: purchased from the polite Chemical Co., Ltd. in Hong Kong, the trade mark is SA1801;
Antioxidant 4020 (N-(1,3-dimethylbutyl)-N '-diphenyl-para-phenylene diamine): purchased from Shanghai additionChemical Co., Ltd.;
Anti-scorching agent CTP (N-cyclohexylthiophthalimide): purchased from Shandong Boxing section source green woodMaterial Co., Ltd;
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 polymerisation. Paradigmatic system is after high pure nitrogen displacement, successivelyIn polymerization reaction kettle, add 200g isoprene monomer, 1800g is dried cyclohexane, under agitation to poly-Close in reactor and add deionized water, continue stir about 10 minutes and be heated to 40 DEG C, then in this temperatureUnder degree, adding 15.8mL concentration is the hexane solution of the n-BuLi of 0.3M, starts polymerisation, poly-Close in course of reaction, temperature is controlled in the scope of 40-50 DEG C, by the pressure control in polymerization reaction kettleBe made as 0.1-0.3MPa(gauge pressure), carry out the polymerization of 120 minutes. Wherein, deionized water and organolithiumThe mol ratio of initator is 7.5:100. After polymerisation completes, add and organic lithium initiator etc. moleDeionized water continue to stir 10 minutes to stop polymerisation, then adding concentration is 20 % by weightCyclohexane solution (wherein, the BHT consumption of BHTFor 0.6 % by weight of isoprene) stir 5 minutes. Polymerizate is dry in the vacuum drying oven of 80 DEG CDry 2 hours, obtain liquid polyisoprene rubber. Determine by weight method, isoprene conversion ratio is100%. 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, deionizationThe mol ratio of water and organic lithium initiator is 2:100. Determine by weight method, isoprene conversion ratio is100%. 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, deionizationThe mol ratio of water and organic lithium initiator is 4:100. Determine by weight method, isoprene conversion ratio is100%. 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, differentThe content of the construction unit that pentadiene forms in the mode of Isosorbide-5-Nitrae-polymerization is high, can reach 96.9 % by mole withUpper (under optimum condition, can reach more than 97 % by mole); The molecular weight of the liquid polyisoprene of preparationNarrow distribution, 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.
The kind of each component of the tire shoulder glue of embodiment 1-9 and comparative example 1-3 and consumption are as following table 2Shown in, 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 closeIn refining machine, carry out banburying chamber's temperature 60 C, rotor speed 80rmin-1, calendering processEnter rubberRear mixing 1min, then adds activator and optional other small powders, other small powders contain age resistor and/Or mixing 1.5min after antiscorching agent, then add reinforcing agent and the rear mixing 3min of aromatic naphtha (or LIR), carryMixing 1.5min after pressure top, binder removal, dump temperature, not higher than 170 DEG C, obtains one section of elastomeric compound, willTo one section of elastomeric compound be cooled to room temperature placement overnight; Two-stage mixing carries out in mill, calendering processFor: be under 20rpm mixing 8 minutes by one section of elastomeric compound and Sulfur and promoter in roller speed, thin-pass 6 timesLower.
To obtain two-stage mixing glue sizing material and vulcanize on vulcanizing press, conditions of vulcanization is 150 DEG C × 20min.Obtain tire shoulder glue S1-S9.
Comparative example 1
This comparative example is for illustrating the preparation of reference elastomeric compound.
Method according to embodiment 1 is prepared elastomeric compound, different, described liquid polyisoprene rubberWith aromatic naphtha (Ningbo Han Sheng company, N65) replacement, obtain elastomeric compound DH1.
Prepare tire shoulder glue according to the method for embodiment 1, different, described elastomeric compound comparative exampleThe 1 elastomeric compound DH1 preparing replaces, and obtains tire shoulder DS1.
Comparative example 2
This comparative example is for illustrating the preparation of reference elastomeric compound.
Method according to embodiment 1 is prepared elastomeric compound, different, does not add solution polymerized butadiene styrene rubber,To elastomeric compound DH2.
Prepare tire shoulder glue according to the method for embodiment 1, different, described elastomeric compound comparative exampleThe 1 elastomeric compound DH2 preparing replaces, and obtains tire shoulder DS2.
Comparative example 3
This comparative example is for illustrating the preparation of reference elastomeric compound.
Method according to embodiment 1 is prepared elastomeric compound, different, does not add solution polymerized butadiene styrene rubber, andDescribed aromatic naphtha (Ningbo Han Sheng company, N65) replacement for liquid polyisoprene rubber, obtains mixingGlue DH3.
Prepare tire shoulder glue according to the method for embodiment 1, different, described elastomeric compound comparative exampleThe 1 elastomeric compound DH2 preparing replaces, and obtains tire shoulder DS3.
Table 2 embodiment and comparative example formula used
* shown in table, be weight portion, the liquid polyisoprene rubber being purchased in embodiment 4 is that Puyang Linshi Chemical New Materials Co., Ltd. producesLS-IR565, 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 butadiene rubber rear motor, adds small powder electric current to refer to that activator, age resistor and/or antiscorching agent add the electric current of rear motor, adds electricity after reinforcing agent and plasticizerStream refers to the electric current that adds carbon black (or white carbon) and aromatic naphtha (or liquid polyisoprene LIR) rear motor.
Can find out from the data of table 3, adopt isoprene rubber to do plasticizer and contrast embodiment 1Example 1,3 height compare with aromatic naphtha: embodiment 1 than the electric current of mixing process in comparative example 1,3Little, mixer power is little, can reach energy-saving and cost-reducing object; The sizing material smooth surface of extruding is smooth,Outward appearance is better, and component processing process is without distortion; Tire shoulder glue and comparative example that embodiment 1 prepares1, the 3 tire shoulder glue that prepare are compared, and Mooney viscosity is bigger, and Mooney scorch time is suitable, explanationProcessing technology is suitable, can make sizing material have better processing safety; In physical and mechanical properties, remove and pull apart elongationOutside rate 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 stretchIntensity and elongation at break rate of change are little, illustrate that ageing-resistant performance is good, the service life that can improve tire;Rebound value is little compared with large, whole dynamic pressure shrinkage, compression fatigue temperature rise is low, permanent deformation is little, can delay tireAt the heat history of driving process and the damaged tyres causing; Resistance to rolling, dynamically deformation is little, dynamically temperature riseLow, also can alleviate tire heat history in the process of moving, extend tyre life; Tan δ 60 DEG C timeValue reduces, and illustrates that the hysteresis loss of rubber is little, heat-dissipating is little, can alleviate tire in the process of moving equallyHeat history, extend tyre life; Vitrification point reduces, and can improve the wearability of tire. In additionAdopt liquid isoprene rubber reactive plasticizer compared with high aromatic oil plasticizer in comparative example 1,Can from goods, not move out, can be to environment yet.
The embodiment 1-3 of liquid polyisoprene rubber prepared by employing the present invention and employing prior artThe embodiment 4 of the liquid polyisoprene rubber that method prepares compares, and processing characteristics is suitable, physicsMechanical performance is more excellent, and the resilience of the vulcanizate of embodiment 1-3 is larger, whole dynamic pressure shrinkage, temperature rise and foreverFor a long time distortion is all less, and resistance to rolling, dynamically deformation, dynamically the fissipation factor of temperature rise and 60 DEG C is also less.
In addition, in the embodiment of the present invention 1, adopt natural rubber and solution polymerized butadiene styrene rubber composition and comparative example2 only adopt natural rubber to compare, and processing characteristics is better, and physical and mechanical properties quite or more excellent, resistance to oldVoltinism can be better, and rebound value is larger, whole dynamic pressure shrinkage, fatigue temperature rise, permanent deformation, resistance to rolling,Dynamically deformation, dynamically the fissipation factor of temperature rise and 60 DEG C is all slightly little, and vitrification point is slightly low, favourable equallyIn alleviating tire heat history in the process of moving, extend tyre life, improve tire wear.
Claims (15)
1. a rubber composition, said composition contain main rubber, vulcanizing agent, vulcanization accelerator,Activator and reinforcing agent, is characterized in that, described composition also contains liquid polyisoprene rubber, instituteState main rubber and contain solution polymerized butadiene styrene rubber and natural rubber, described natural rubber and solution polymerized butadiene styrene rubberWeight ratio is 0.5-19:1.
2. composition according to claim 1, wherein, with described liquid polyisoprene rubberTotal amount be benchmark, the amount of the construction unit that described isoprene forms by Isosorbide-5-Nitrae-polymerization is 96.9 to rubMore than you %.
3. composition according to claim 1 and 2, wherein, described liquid polyisopreneNumber-average molecular weight is 5000-100000, and molecular weight distribution is 1.01-1.10.
4. composition according to claim 1 and 2, wherein, with the main body rubber of 100 weight portionsGlue is benchmark, and the content of described vulcanizing agent is 1-3 weight portion, and the content of described vulcanization accelerator is 1-5Weight portion, the content of described reinforcing agent is 40-70 weight portion, the content of described activator is that 0.5-8 is heavyAmount part, the content of described liquid polyisoprene rubber is 1-10 weight portion; Described natural rubber accounts for masterThe 45-95 % by weight of body rubber, described solution polymerized butadiene styrene rubber accounts for the 5-55 % by weight of main rubber.
5. composition according to claim 1 and 2, wherein, described composition also contains anti-oldAgent and/or antiscorching agent, taking the main rubber of 100 weight portions as benchmark, the content of described age resistor is 2-5Weight portion, the content of described antiscorching agent is 0.05-0.35 weight portion.
6. composition according to claim 5, wherein, described age resistor be amines antioxidants and/Or quinoline type antioxidant; Described amines antioxidants is selected from N-isopropyl-N '-diphenyl-para-phenylene diamine, N-(1,3-Dimethylbutyl)-N '-diphenyl-para-phenylene diamine and N, in N '-bis-(Isosorbide-5-Nitrae-dimethyl amyl group) p-phenylenediamine (PPD)One or more; Described quinoline type antioxidant is selected from 2,2,4-trimethyl-1,2-dihyaroquinoline condensate,6-ethyoxyl-2,2,4-trimethyl-1,2-dihyaroquinoline and 6-dodecyl-2,2,4-trimethyl-1,2-dihydroOne or more in change quinoline; Described antiscorching agent be selected from N-cyclohexylthiophthalimide,One or more in N nitrosodiphenyl amine, salicylic acid and phthalic anhydride.
7. composition according to claim 6, wherein, described amines antioxidants is N-(1,3-Dimethylbutyl)-N '-diphenyl-para-phenylene diamine.
8. composition according to claim 6, wherein, described quinoline type antioxidant is 2,2,4-Trimethyl-1,2-dihyaroquinoline condensate.
9. composition according to claim 6, wherein, described antiscorching agent is N-cyclohexyl thioPhthalimide.
10. composition according to claim 1 and 2, wherein, the weight average of described natural rubber dividesSon amount is 1,000,000-1,000 ten thousand, and molecular weight distribution is 3-6, and Mooney viscosity is 65-75; The described fourth that contains intermingle withThe number-average molecular weight of benzene rubber is 100,000-400,000, and molecular weight distribution is 1.1-3, with described solution polymerized butylbenzeneThe gross weight of rubber is benchmark, and contents of ethylene is 10-35 % by weight, and Mooney viscosity is 45-65.
11. compositions according to claim 1 and 2, wherein, described vulcanizing agent is selected from insolubleOne or more in sulphur, two sulfo-morpholines and four sulfuration two morpholines; Described vulcanization accelerator choosingFrom the N-tert-butyl group-2-[4-morpholinodithio base sulfenamide, 2,2'-dibenzothiazyl disulfide, the N-tert-butyl group-bis-(2-[4-morpholinodithio) sulfenamide, N-cyclohexyl-bis-(2-mercaptobenzothiazole) sulfenamide and twoOne or more in benzene guanidine; Described activator is zinc oxide and/or stearic acid; Described reinforcing agent is carbon blackAnd/or white carbon.
The preparation method of 12. 1 kinds of tire shoulder glue, the method comprises any in claim 1-11Rubber composition described in one carries out mixing, obtains elastomeric compound; And by described elastomeric compound sulfuration, obtainTire shoulder glue.
13. methods according to claim 12, wherein, described mixing comprise carry out successively twoIn the individual stage, the mixing of first stage carried out on banbury, and mixing condition comprises: temperature is 50-170 DEG C,Pressure is 10-15MPa, and the time is 5-15 minute; The mixing of second stage carried out in mill, mixedRefining condition comprises: temperature is 40-60 DEG C, and the time is 5-15 minute.
14. methods according to claim 12, wherein, described conditions of vulcanization comprises curing temperatureFor 130-170 DEG C, sulfide stress is 10-15MPa, and cure time is 10-50 minute.
15. 1 kinds of tire shoulder glue, is characterized in that, this tire shoulder glue is by claim 12-14The described method of any one prepares.
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| 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 |
| WO2018110409A1 (en) * | 2016-12-15 | 2018-06-21 | 東洋ゴム工業株式会社 | Rubber composition for tire and pneumatic tire using same |
| 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 |
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