CN104558416B - A kind of rubber composition and vulcanization rubber - Google Patents
A kind of rubber composition and vulcanization rubber Download PDFInfo
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- CN104558416B CN104558416B CN201310513366.4A CN201310513366A CN104558416B CN 104558416 B CN104558416 B CN 104558416B CN 201310513366 A CN201310513366 A CN 201310513366A CN 104558416 B CN104558416 B CN 104558416B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Abstract
The invention provides a kind of rubber composition and it is well mixed by the rubber composition and is vulcanized obtained vulcanization rubber.Rubber composition described in the rubber composition contains olefinic rubber, vulcanizing agent, vulcanization accelerator, reinforcing agent and activator, wherein, contain modified diene polymer in the olefinic rubber, contain in the strand of the modified diene polymer in monovinylarene construction unit and conjugated diene construction unit, and the strand of the modified diene polymer and also contain formula（Ⅰ）Shown silane coupler construction unit, the number-average molecular weight of the modified diene polymer is 50,000 100 ten thousand；R1‑R4For C1‑C20Straight or branched alkyl or contain heteroatomic C1‑C20Straight or branched alkyl, one or more of the hetero atom in halogen, oxygen, sulphur, silicon and phosphorus.The rubber composition can be between active balance anti-slippery and rolling resistance relation.
Description
Technical field
The present invention relates to a kind of rubber composition and it is well mixed by the rubber composition and is vulcanized obtained vulcanization rubber
Glue.
Background technology
In recent years, with the development of auto industry and climbing up and up for oil price, people to the security of automobile and
Energy saving is paid close attention to further, and this requires tire while with compared with high wet-sliding resistant performance, also with relatively low rolling resistance.But
It is that raising wet-sliding resistant performance is difficult often while taking into account with reduction rolling resistance.Therefore, according to different use requirements, it is necessary to
Seek optimal balance between high wet-sliding resistant performance and low rolling resistance.
For production low rolling resistance tyre, due to anionic solution polymerization can effectively adjust side chain contain it is double
The content and glass transition temperature of the conjugated diene construction unit of key, the solution polymerized butylbenzene of anionic polymerisation have than newborn poly- fourth
Benzene more significant advantage.Relation between wet-sliding resistant performance and rolling resistance of the advantage for balancing tire is favourable.This
Outside, research shows, silane coupler is added in the mixing process of rubber composition, to a certain extent filler can be promoted to exist
The relation between wet-sliding resistant performance and rolling resistance scattered and that improve rubber to a certain extent in rubber, but in rubber
In composition mixing process, influenceed by other additives, the reactivity of silane coupler and rubber and carbon black can be reduced.And
And, addition silane coupler can also produce unpleasant stink in rubber composition mixing process.Being disclosed in EP447066 can
With using with formula（1）The silane of shown structure is hindered as modifying agent with improving the wet-sliding resistant performance of butadiene-styrene rubber and reducing rolling
Power：
USi(OR')jR''4-i-jFormula（1）,
Wherein, U is halogen, and R ＇ and R ＇ ＇ are C1-C20Alkyl, aryl, vinyl or haloalkyl, j be 1-4 integer,
I is 0-2 integer, i and j's and for 2-4.With formula（1）The silane of shown structure can pass through halogen and polymer molecular chain
The catalyst residues of end are reacted and key is connected on polymer molecular chain, however, a usual polymer molecular chain can only key company
A upper silane molecule, is only capable of producing slight influence, it is impossible to effectively improve rubber to the interaction between polymer molecular chain
The anti-slippery of glue simultaneously reduces rolling resistance.
The content of the invention
The invention aims to overcome the wet-sliding resistant performance and the rolling that use existing method not can effectively improve rubber
The defect of relation between dynamic resistance, and provide a kind of rubber composition that can have high anti-lubricity and low-rolling-resistance concurrently and
It is well mixed by the rubber composition and is vulcanized obtained vulcanization rubber.
The invention provides a kind of rubber composition, the rubber composition contains olefinic rubber, vulcanizing agent, vulcanization promotion
Agent, reinforcing agent and activator, wherein, modified diene polymer, the modified diene polymerized hydrocarbon are contained in the olefinic rubber
Contain monovinylarene construction unit and conjugated diene construction unit, and the modified diene polymer in thing strand
Strand in also contain formula（Ⅰ）Shown silane coupler construction unit, the equal molecule of number of the modified diene polymer
Measure as 50,000-100 ten thousand；
Wherein, R1-R4For C1-C20Straight or branched alkyl or contain heteroatomic C1-C20Straight or branched alkyl,
One or more of the hetero atom in halogen, oxygen, sulphur, silicon and phosphorus.
Present invention also offers be well mixed by above-mentioned rubber composition and vulcanized obtained vulcanization rubber.
As described above, in the prior art, silane coupler is just generally added in the mixing process of rubber composition, with
Improve the wet-sliding resistant performance of rubber and reduce its rolling resistance, but the now reactivity of silane coupler and rubber and carbon black
It can reduce, not only be difficult to significantly improve the relation between the wet-sliding resistant performance of rubber and rolling resistance, but also can produce unpleasant
Stink.And the present inventor has found after in-depth study, by the way that silane coupler chemical bond is connected into alkadienes
On polymer, and obtained modified diene polymer can be avoided in rubber integrally as part or all of rubber-based adhesive
The problem of reactivity of silane coupler and rubber and carbon black is reduced caused by composition mixing process, and active balance by
Relation between the anti-slippery and rolling resistance of the tire that the rubber composition is made, while building rubber compound can also be improved
In thing mixing process caused by the use of silane coupler undesirable smell.
Other features and advantages of the present invention will be described in detail in subsequent embodiment part.
Embodiment
The embodiment to the present invention is described in detail below.It should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The rubber composition that the present invention is provided contains olefinic rubber, vulcanizing agent, vulcanization accelerator, reinforcing agent and activator,
Wherein, contain in the olefinic rubber in modified diene polymer, the strand of the modified diene polymer containing single
Also contain in vinyl-arene construction unit and conjugated diene construction unit, and the strand of the modified diene polymer
Formula（Ⅰ）Shown silane coupler construction unit, the number-average molecular weight of the modified diene polymer is 50,000-100 ten thousand；
Wherein, R1-R4For C1-C20Straight or branched alkyl or contain heteroatomic C1-C20Straight or branched alkyl,
One or more of the hetero atom in halogen, oxygen, sulphur, silicon and phosphorus；Preferably, R1-R3For C1-C5Straight or branched
Alkyl or straight or branched alkoxyl, R4For C1-C5Straight or branched alkylidene.
The C1-C5The instantiation of straight or branched alkyl include but is not limited to：Methyl, ethyl, n-propyl, isopropyl
Base, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl and neopentyl；The C1-C5Straight chain or
The instantiation of branched alkoxy includes but is not limited to：It is methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, secondary
Butoxy, isobutoxy, tert-butoxy, n-pentyloxy, isoamoxy, tertiary amoxy and neopentyl oxygen；The C1-C5Straight chain
Or the instantiation of branched alkylidene includes but is not limited to：Methylene, ethylidene, propylidene, butylidene and pentylidene.
The present invention is not particularly limited to the content of the modified olefine polymer, for example, with the olefinic rubber
On the basis of gross weight, the content of modified olefine polymer can be 50-100 weight %, preferably 80-100 in the olefinic rubber
Weight %.
On the strand of the modified diene polymer, monovinylarene construction unit and conjugated diene hydrocarbon structure
The main chain of unit composition polymer, and formula（Ⅰ）Shown silane coupler construction unit key is connected to the conjugated diene on main chain
On construction unit.
It is particularly preferred that formula（Ⅰ）In, R1-R3For methoxyl group, R4For propylidene, now, with formula（Ⅰ）Shown is silane coupled
The corresponding silane coupler of agent construction unit is γ-mercaptopropyl trimethoxysilane；Or, R1-R3For ethyoxyl, R4For Asia
Propyl group, now, with formula（Ⅰ）The corresponding silane coupler of shown silane coupler construction unit is γ-ethoxy of mercapto propyl group three
Base silane；Or, R1-R3For methyl, R4For ethylidene, now, with formula（Ⅰ）Shown silane coupler construction unit is corresponding
Silane coupler be 2- trimethyl silane ethyl mercaptans.
The present invention to the monovinylarene construction unit and conjugated diene construction unit in the modified diene with
The content of silane coupler construction unit is not particularly limited, it is possible to according to monovinylarene in preparation process and conjugation
The consumption of alkadienes and silane coupler is adjusted, but in order that obtaining the modified diene polymer has higher resist
Wet and slippery performance simultaneously has lower rolling resistance, on the basis of the gross weight of the modified diene polymer, single ethene
The total content of base aromatic hydrocarbons construction unit and conjugated diene construction unit is preferably 90-99.99%, more preferably 98-99.8 weights
% is measured, the content of the silane coupler construction unit is preferably 0.01-10 weight %, more preferably 0.2-2 weight %.Further
The weight ratio of ground, the monovinylarene construction unit and conjugated diene construction unit can be 5:95-60:40, preferably
For 20:80-40:60.
The present invention is not particularly limited to the number-average molecular weight and molecular weight distribution of the modified diene polymer, example
Such as, the number-average molecular weight can be 50,000-100 ten thousand, preferably 150,000-20 ten thousand, and molecular weight distribution can be 1-4, preferably 1-
1.5.The number-average molecular weight and molecular weight distribution can use the gel infiltration of the model LC-10AT purchased from Shimadzu Corporation
Chromatograph（GPC）Measure, wherein, using THF as mobile phase, using Narrow distribution polystyrene as standard specimen, test temperature is 25 DEG C.
According to the present invention, the monovinylarene construction unit is the construction unit derived from monovinylarene, i.e.,
It polymerize the construction unit formed by monovinylarene.The monovinylarene can be to be carried on aromatic ring commonly used in the art
The various aromatic monomers of one vinyl substituent, as a rule, the monovinylarene has formula（Ⅲ）Shown structure：
Wherein, R5Can be C6-C20Substituted or unsubstituted aryl, preferably phenyl and by one or more C1-C5
Alkyl-substituted phenyl.
According to the present invention, the C6-C20The instantiation of substituted or unsubstituted aryl include but is not limited to：Phenyl,
Tolyl, ethylbenzene, tert-butyl-phenyl, dodecylphenyl, di-n-butyl phenyl（Including adjacent di-n-butyl phenyl, two just
Butyl phenyl and to di-n-butyl phenyl）, n-propyl phenyl and diethyl phenyl（Including adjacent two positive ethylphenyls, a two positive second
Base phenyl and to two positive ethylphenyls）.
According to the present invention, the monovinylarene be particularly preferably styrene, vinyltoluene, α-methylstyrene,
One or more in 4- t-butyl styrenes and 4- methyl styrenes.
According to the present invention, the conjugated diene construction unit be the construction unit derived from conjugated diene i.e., by altogether
The construction unit of yoke diene polymerization formation.The conjugated diene refers to contain conjugated double bond in molecular structure（That is ,-C=C-C
=C-）Various unsaturated acyclic hydrocarbons.The conjugated diene can be the conventional selection of this area, be not particularly limited, and
Reasonable selection can be carried out according to the application scenario of the modified diene polymer finally given, for example, the conjugated diene
Can be selected from one kind or many in butadiene, isoprene, 1,3- pentadienes, 1,3- hexadienes and 2,3 dimethyl butadiene
Plant, preferably butadiene and/or isoprene.
According to the present invention, the modified diene polymer can be using well known to a person skilled in the art various method systems
It is standby to obtain, for example, the preparation method can include：In an inert atmosphere and in the presence of initiator, single ethene will be contained
The diene polymer of base aromatic hydrocarbons construction unit and conjugated diene construction unit is contacted with silane coupler, the bar of the contact
Part causes the silane coupler chemical bond to be connected on the diene polymer；The number-average molecular weight of the diene polymer
For 50,000-100 ten thousand, and on the basis of the weight of conjugated diene construction unit in the diene polymer, the alkadienes gathers
It is 15-85 weight %, preferably 30-60 weight %, institute that side chain, which contains the content of the conjugated diene construction unit of double bond, in compound
Stating silane coupler has formula（Ⅱ）Shown structure：
Wherein, R1-R4For C1-C20Straight or branched alkyl or contain heteroatomic C1-C20Straight or branched alkyl,
One or more of the hetero atom in halogen, oxygen, sulphur, silicon and phosphorus；Preferably, R1-R3For C1-C5Straight or branched
Alkyl or straight or branched alkoxyl, R4For C1-C5Straight or branched alkylidene.
The content that the side chain contains the conjugated diene construction unit of double bond can use and be purchased from Bruker companies of Switzerland
Model AVANCE DRX400MHz nuclear magnetic resonance chemical analyser be measured, wherein, solvent is deuterochloroform.It is specific to determine
Method is known to the skilled person, and will not be described in great detail herein.
It is particularly preferred that formula（Ⅱ）In, R1-R3For methoxyl group, R4For propylidene, now, corresponding silane coupler is
γ-mercaptopropyl trimethoxysilane；Or, R1-R3For ethyoxyl, R4For propylidene, now, corresponding silane coupler be γ-
Mercaptopropyltriethoxysilane；Or, R1-R3For methyl, R4For ethylidene, now, corresponding silane coupler is 2- trimethyls
Silane ethyl mercaptan.
According to the present invention, the diene polymer can be prepared using existing various methods, for example, it is prepared
Method can include：In an inert atmosphere and in the presence of initiator, by monovinylarene and conjugated diene in solvent
Middle carry out polymerisation, obtains the reaction product containing diene polymer, and the condition of the polymerisation makes obtained diene
The number-average molecular weight of hydrocarbon polymer is 50,000-100 ten thousand, and on the basis of the weight of conjugated diene in the diene polymer,
The content that side chain contains the conjugated diene construction unit of double bond in the diene polymer is 15-85 weight %, is preferably
30-60 weight %.
According to the present invention, the inert atmosphere refers to any one gas not chemically reacted with reactant and product
Or admixture of gas, the one or more in such as nitrogen and periodic table of elements zero group gas.Keep the method for inert atmosphere can be with
To be passed through above-mentioned any one gas or admixture of gas not chemically reacted with reactant and product into reaction system.
According to the present invention, in the preparation process of diene polymer, the initiator can for it is existing it is various can
Trigger the initiator of the monovinylarene and conjugate diene polymerization, for example, can be organic lithium initiator.It is described organic
Lithium initiator for example can be single organic lithium initiator that molecular formula is RLi, wherein, R is the alkyl of straight or branched, cycloalkyl
Or aryl.Specifically, single organic lithium initiator can be selected from ethyl-lithium, propyl lithium, isopropyl lithium, n-BuLi, Zhong Ding
One or more in base lithium, amyl group lithium, hexyl lithium, cyclohexyl lithium, phenyl lithium, aminomethyl phenyl lithium and naphthyl lithium, are preferably just
Butyl lithium and/or s-butyl lithium.In addition, the present invention can also use Dilithium initiator, such as lithium of trimethylene two and/or four methylenes
The lithium of base two.The present invention is not particularly limited to the consumption of the initiator, it is possible to carried out according to the molecular size range of design
Reasonably select.Those skilled in the art are it should be readily understood that working as needs to prepare the larger diene polymer of molecular weight
When, it is possible to reduce the consumption of initiator, but now rate of polymerization also can accordingly reduce；When needing to prepare the less diene of molecular weight
During hydrocarbon polymer, the consumption of initiator can be increased, but now rate of polymerization also can accordingly increase.Therefore, polymerization is considered
Under the molecular size range of speed and obtained diene polymer, preferable case, with 100g monovinylarenes and conjugation two
On the basis of the gross weight of alkene, the consumption of the initiator is 0.15-2.5mmol.
The present invention is not particularly limited to the consumption of the monovinylarene and conjugated diene, it is possible to according to pre-
Phase obtained diene polymer is reasonably selected, for example, the weight of the monovinylarene and conjugated diene
Than that can be 5:95-60:40th, it is preferably 20:80-40:60.
The present invention is not particularly limited to the condition of the polymerisation, generally include polymerization temperature, polymerization pressure and
Polymerization time.Wherein, in order to be more beneficial for the progress of polymerisation, the polymerization temperature is preferably 10-160 DEG C, more preferably
40-80 DEG C, the polymerization pressure is preferably 0.05-0.5MPa, more preferably 0.1-0.3MPa.As a rule, during the polymerization
Between extension be conducive to the raising of reaction-ure conversion-age and reaction product yield, but polymerization time it is long to reaction-ure conversion-age and
The amplitude that reaction product yield is improved is not obvious, therefore, considers polymerization efficiency and effect, the polymerization time is preferably
0.5-10 hours, more preferably 0.5-2 hours.
In the present invention, the pressure refers both to gauge pressure.
According to the present invention, in the preparation process of diene polymer, the solvent can be used as reaction to be various
The material of medium, for example, can be varsol and/or ether solvent.The varsol can be C5-C7Cycloalkane, virtue
One or more in hydrocarbon and isoparaffin.The instantiation of the varsol can include but is not limited to：Benzene, toluene, penta
One or more in alkane, heptane, n-hexane and hexamethylene.The ether solvent can be C4-C15Monoether and/or polyether.
The instantiation of the ether solvent can include but is not limited to：Tert-butoxyethoxy ethane and/or tetrahydrofuran.Wherein,
These solvents can be used alone, can also be used in mixed way.The consumption of the solvent can be closed according to the consumption of monomer
Reason ground selection, for example, the consumption of the solvent can cause the total concentration of the monovinylarene and conjugated diene to be 1-
30 weight %, preferably 5-20 weight %.
, after polymerization was complete, can also be toward adding coupling agent in polymerization system according to the present invention, will at least portion
Diene polymer is divided to be coupled together.The species of the coupling agent is known to the skilled person, for example, can be many second
One or more in alkenyl compound, halide, ether, aldehyde, ketone, ester etc..Specifically, the coupling agent can be selected from divinyl
In base benzene, tetravinyl silane, tetrachloromethane, silicon tetrachloride, butter of tin, dimethyl terephthalate (DMT) and epoxidized soybean oil
One or more in one or more, preferably divinylbenzene, silicon tetrachloride and butter of tin.It should be noted that working as
When the coupling agent is silane compound, the silane compound is with having formula（Ⅱ）The silane coupler of shown structure is different.
The present invention is not particularly limited to the consumption of the coupling agent, can be carried out suitably according to the consumption of initiator
Selection, for example, the mol ratio of the coupling agent and the initiator can be 0.1-2:1, preferably 0.1-1:1.
, according to the invention it is preferred in the case of, structure tune can also be added in the preparation process of the diene polymer
Agent is saved, the microstructure of the diene polymer can be so effectively controlled.The structure regulator can be
The material of the existing various microstructures that can adjust diene polymer, for example, ether, butyl oxide, tetrahydrochysene can be selected from
Furans, glycol dimethyl ether, diethylene glycol dimethyl ether, dioxane, crown ether, tetrahydrofurfuryl alcohol ether, triethylamine, tetramethyl second two
One in amine, HMPA, potassium tert-butoxide, tert-pentyl alcohol potassium, potassium lauryl, alkyl benzene sulphonate potassium and sodium alkyl benzene sulfonate
Plant or a variety of.As a rule, the structure regulator can be with the mol ratio for preparing the initiator used in diene polymer
1-100:1, preferably 80-100:1.
As a rule, anionic polymerisation system does not have obvious terminating reaction and transfer reaction, when ruing out of whole
After monomer, activated centre is still present.Therefore, after completion of the polymerization reaction, obtained polymer solution and terminator should be connect
Touch so that activated centre is inactivated.The consumption of the terminator can be according to used in preparing diene polymer initiator consumption
Reasonably to be selected, as a rule, the terminator can with preparing the mol ratio of the initiator used in diene polymer
Think 0.1-1:1.The terminator can be the existing various reagents that can inactivate anion active center, for example can be with
One or more in water, methanol, ethanol and isopropanol, preferably isopropanol.
The present invention is not particularly limited to the condition for contacting the diene polymer with silane coupler, as long as energy
Enough so that the silane coupler chemical bond is connected on diene polymer, for example, the condition of the contact is generally included
Contact Temperature, contact and time of contact.As a rule, in order to be more beneficial for silane coupler chemical bond be connected to alkadienes gather
On compound, the Contact Temperature is preferably 20-150 DEG C, more preferably 70-90 DEG C, contact is preferably 0.01-1MPa, more
Preferably 0.1-0.5MPa, time of contact is preferably 0.1-24 hours, more preferably 0.5-5 hours.
According to the present invention, when diene polymer is contacted with silane coupler, in order to take into account trigger rate and modification
Under the size of diene polymer molecular weight, preferable case, with the diene polymer and with formula（Ⅱ）Shown structure
On the basis of the gross weight of silane coupler, the consumption of the initiator is 0.01-0.1 weight %, more preferably 0.01-0.08 weights
Measure %.Azo-initiator, peroxide type initiators and the oxidation that the initiator can be known to the skilled person are also
One or more in the radical initiators such as former class initiator.
The azo-initiator can be selected from azo-bis-iso-dimethyl, azo-bis-isobutyrate hydrochloride, azo two
Formamide, azo dicyclohexyl formonitrile HCN hydrochloride, azo isobutyl cyano group formamide, azo diisopropyl imidazoline hydrochloride, azo dicyan
One kind or many in base valeric acid, azo dicyclohexyl formonitrile HCN, azodiisobutyronitrile, AMBN and ABVN
Kind.
The peroxide type initiators can be selected from hydrogen peroxide, ammonium persulfate, sodium peroxydisulfate, potassium peroxydisulfate, peroxide
Change the one or more in benzoyl and the benzoyl peroxide tert-butyl ester.
The redox type initiators can have selected from sulfate-sulphite, persulfate-thiocarbamide, persulfate-
One or more in machine salt and ammonium persulfate-fatty amine.Specifically, the sulfate-sulphite can selected from sodium sulphate-
One or more in sodium sulfite, potassium sulfate-potassium sulfite and ammonium sulfate-ammonium sulfite；Persulfate-thiocarbamide can be selected from
One or more in sodium peroxydisulfate-thiocarbamide, potassium peroxydisulfate-thiocarbamide and ammonium persulfate-thiocarbamide；Persulfate-organic salt can be with
One or more in sodium peroxydisulfate-potassium acetate, potassium peroxydisulfate-potassium acetate and ammonium persulfate-ammonium acetate；Ammonium persulfate-
Fatty amine can be ammonium persulfate-N, N- tetramethylethylenediamine and/or ammonium persulfate-diethylamine.
The present invention is to the diene polymer and with formula（Ⅱ）The consumption of the silane coupler of shown structure is without spy
Do not limit, for example, on the basis of 100g diene polymer, the consumption of the silane coupler can for 0.01-10g,
Preferably 0.1-5g, more preferably 0.2-2g.
According to the present invention, after the modified diene polymer is prepared and completed, it is also an option that property to obtaining
Various additives are added in modified diene polymer.The additive can be for example age resistor, so enable to
Modified diene polymer has good ageing resistace.The species and consumption of the age resistor can be the normal of this area
Rule selection, will not be described in great detail herein.
According to the present invention, after age resistor is added, the modified diene polymer can be by purifying precipitation, centrifugation point
From, filtering, decantation, hot water cohesion etc. method be precipitated out from solution, it would however also be possible to employ air- extraction will be molten in reaction system
Agent is removed, and this those skilled in the art can be known, be will not be described in great detail herein.
According to the present invention, mixed rubber can also be contained in the olefinic rubber.The mixed rubber can be selected from natural
In rubber, polybutadiene rubber, butadiene-styrene rubber, polyisoprene rubber, neoprene, butyl rubber and ethylene propylene diene rubber
It is one or more.The mixed rubber can be commercially available, can also be according to well known to a person skilled in the art various sides
Method is prepared, and will not be described in great detail herein.
The modified diene polymer that contains in the rubber composition, mixed rubber, vulcanizing agent, vulcanization accelerator, increasing
The content of strong agent and activator can be the conventional selection of this area, for example, with the modified diene rubber of 100 parts by weight
On the basis of glue, the content of the mixed rubber can be 10-40 parts by weight, and the content of the vulcanizing agent can be 1-3 parts by weight,
The content of the vulcanization accelerator can be 3-5 parts by weight, and the content of the reinforcing agent can be 70-90 parts by weight, the work
The content of agent can be 3-4 parts by weight.
According to the present invention, the species of the vulcanizing agent can be the conventional selection of this area, for example, can be insoluble sulfur
One or more in sulphur, two thio morpholines and four two morpholines of vulcanization, preferably insoluble sulfur.Wherein, it is described insoluble
Property sulphur be sulphur allotrope, its do not dissolve in sulfur dioxide and other solvents, be also insoluble in rubber, in rubber with point
Bulk state is present；After curing temperature is reached, these insoluble sulfurs being dispersed in rubber have one " activation stage ", i.e.,
Chain type depolymerisation, accelerates curingprocess rate, reduces sulfur consumption, is conducive to improving the ageing properties of rubber.
According to the present invention, the vulcanization accelerator can vulcanize temperature for the existing various cure times, reduction of can shortening
Degree, the material for reducing vulcanizing agent consumption and improving the physical and mechanical properties of rubber, but it is more excellent in order to obtain environmental-protecting performance
Under rubber composition, preferable case, the vulcanization accelerator is that sulfenamide vulcanization accelerator and/or guanidine vulcanization promote
Agent；The sulfenamide vulcanization accelerator is preferably selected from the N- tert-butyl groups -2-[4-morpholinodithio base sulfenamide, N- cyclohexyl -2-
One or more in benzothiazolyl sulfenamide and N- oxygen diethylidene -2-[4-morpholinodithio base sulfenamide；The guanidine
Vulcanization accelerator is preferably diphenylguanidine and/or di-o-tolylguanidine.Wherein, the N- tert-butyl groups -2-[4-morpholinodithio base sulfenamide
Trade name TBBS or NS, be a kind of performance extremely excellent vulcanization accelerator, its structural formula such as formula（Ⅳ）It is shown：
According to the present invention, the species of the reinforcing agent is known to those skilled in the art, for example, the reinforcing agent can be with
For carbon black and/or white carbon.The carbon black can be the existing various carbon blacks that can be used in rubber composition, for example, can select
One or more from industrial reference black 7#, high abrasion furnace black N330 and medium super abrasion furnace black N220.The white carbon
Can for it is existing it is various can improve the white carbon of the rubber composition intensity, and the white carbon can pass through business
Buy, for example, can be purchased from goldschmidt chemical corporation the trade mark be 115GR white carbon.
According to the present invention, the species of the activator can also be the conventional selection of this area, for example, can be stearic acid
And/or zinc oxide.
In addition, the rubber composition of the present invention can also optionally contain age resistor and/or silane according to actual conditions
Coupling agent, to further enhance the anti ageing property and wet-sliding resistant performance of rubber composition and reduce rolling resistance.It is described herein
Age resistor can it is identical from the age resistor species added in modified diene polymer preparation process, can also be different.In addition,
There is formula used in silane coupler described herein and modified diene polymer preparation process（Ⅱ）The silicon of shown structure
Alkane coupling agent is different, usually the silane coupler without sulfydryl, for example, can be double-[γ-(triethoxysilicane) propyl group]-
One or more in tetrasulfide, tetravinyl silane and silicon tetrachloride.Age resistor described herein and silane coupler
Consumption can be the conventional selection of this area, will not be described in great detail herein.
Present invention also offers be well mixed by above-mentioned rubber composition and vulcanized obtained vulcanization rubber.
The main of the present invention is theed improvement is that there is provided a kind of new rubber composition, and rubber composition is mixed into equal
Method that is even and vulcanizing can be the conventional selection of this area, and this those skilled in the art can be known, herein will no longer
Repeat.
The present invention will be described in detail by way of examples below.
In following preparation example and contrast preparation example, sulfydryl conversion ratio is surveyed using Agilent 7890A type gas chromatographs
Fixed, test condition includes：Chromatographic column is SPB-560m × 0.32mm × 1.0um capillary columns, column flow rate 2.0ml/min, column temperature
220 DEG C, gasify 220 DEG C of room temperature, detects 250 DEG C of room temperature, split ratio 50：1, sample size 0.3ul.Side chain contains being total to for double bond
The content of the content of yoke alkadienes construction unit, the content of monovinylarene construction unit and conjugated diene construction unit is adopted
Determined with Bruker companies of Switzerland AVANCE DRX400MHz nuclear magnetic resonance chemical analysers, solvent is deuterochloroform.Number-average molecular weight,
Molecular weight distribution and coupling efficiency are surveyed using the ALLIANCE2690 types gel permeation chromatograph (GPC) of WATERS companies of the U.S.
Fixed, THF is mobile phase, and Narrow distribution polystyrene is standard specimen, and temperature is 25 DEG C.Mooney viscosity uses the SMV- of Japanese Shimadzu Corporation
300 type mooney's viscosimeters method as specified in GB/T1232-92 is determined.The throwing of content=silane coupler of silane coupler
Doses × sulfydryl conversion ratio ÷（The inventory of inventory+silane coupler of inventory+conjugated diene of monovinylarene
× sulfydryl conversion ratio）×100%.
Preparation example 1
The preparation example is used to illustrate modified diene polymer of the invention provided and preparation method thereof.
（1）In 5 liters of stainless steel stirred tanks, under High Purity Nitrogen protection, add 2288g hexamethylenes, 31.20g styrene,
112.30g butadiene and 1.1g tetrahydrofurfuryl alcohol ether, are then heated to after 50 DEG C and add 1.1mmol n-BuLi and by pressure
Initiation reaction 2 hours at 0.2 mpa are controlled, the solution containing diene polymer is obtained.The number of the diene polymer is equal
Molecular weight is 18.2 ten thousand, and on the basis of the weight of conjugated diene construction unit in the diene polymer, the diene
The content that side chain contains the conjugated diene construction unit of double bond in hydrocarbon polymer is 43.02 weight %, styrol structural unit
Content is 21.74 weight %, and the content of butadiene structural units is 78.26 weight %.
（2）Toward step（1）0.8ml is added in obtained product（0.836g）γ-mercaptopropyl trimethoxysilane, and immediately
Sampling carries out sulfydryl test, is then heated to addition 6.7mg azo-bis-isobutyl cyanides after 80 DEG C, and by Stress control at 0.2 mpa
Reaction obtains modified diene polymer after 3 hours, and samples progress sulfydryl test.Add into above-mentioned modified diene polymer
Enter 0.2g age resistor Irganox1520, and the dry 24h in 60 DEG C of vacuum.Wherein, in modified diene polymer, sulfydryl
Conversion ratio is 79%, and Mooney viscosity is 45, and number-average molecular weight is 18.2 ten thousand, and molecular weight distribution is 1.1；With the modified diene
On the basis of the gross weight of polymer, the content of γ-mercaptopropyl trimethoxysilane construction unit is 0.46 weight %.The polymer
There is no undesirable smell.
Preparation example 2
The preparation example is used to illustrate modified diene polymer of the invention provided and preparation method thereof.
（1）In 5 liters of stainless steel stirred tanks, under High Purity Nitrogen protection, 2288g hexamethylenes, 31.20g vinyl first are added
Benzene, 112.32g isoprene and 0.65g tetrahydrofurans, are then heated to the n-BuLi that 1.0mmol is added after 45 DEG C and will press
Power control initiation reaction 2 hours under 0.1MPa, obtain the solution containing diene polymer, then add the four of 0.06mmol
Stannic chloride, and 30min is reacted at 60 DEG C, obtain the polymer that coupling efficiency is 27%.The number of the diene polymer is divided equally
Son amount is 19.4 ten thousand, and on the basis of the weight of conjugated diene construction unit in the diene polymer, the alkadienes
The content that side chain contains the conjugated diene construction unit of double bond in polymer is 33.03 weight %, vinyltoluene construction unit
Content be 21.74 weight %, the content of isoprene structures unit is 78.26 weight %.
（2）Toward step（1）0.6ml is added in obtained product（0.627g）γ-mercaptopropyl trimethoxysilane, and immediately
Sampling carries out sulfydryl test, is then heated to addition 30mg azo-bis-isobutyl cyanides after 80 DEG C, and by Stress control under 0.1MPa
Reaction obtains modified diene polymer after 5 hours, and samples progress sulfydryl test.Add into above-mentioned modified diene polymer
Enter 0.2g age resistor Irganox1520, and the dry 24h in 60 DEG C of vacuum.Wherein, in modified diene polymer, sulfydryl
Conversion ratio is 82%, and Mooney viscosity is 47, and number-average molecular weight is 19.4 ten thousand, and molecular weight distribution is 1.07；With the modified diene
On the basis of the gross weight of polymer, the content of γ-mercaptopropyl trimethoxysilane construction unit is 0.36 weight %.The polymer
There is no undesirable smell.
Preparation example 3
The preparation example is used to illustrate modified diene polymer of the invention provided and preparation method thereof.
（1）In 5 liters of stainless steel stirred tanks, under High Purity Nitrogen protection, add 2288g hexamethylenes, 31.2g styrene,
112.3g butadiene and 0.9g tetrahydrofurfuryl alcohol ether, are then heated to after 80 DEG C and add 1.0mmol n-BuLi and by pressure
Control initiation reaction 0.5 hour under 0.3MPa, obtains the solution containing diene polymer.The number of the diene polymer
Average molecular weight is 19.4 ten thousand, and on the basis of the weight of conjugated diene construction unit in the diene polymer, described two
The content that side chain contains the conjugated diene construction unit of double bond in olefin polymer is 40.02 weight %, styrol structural unit
Content be 21.74 weight %, the content of butadiene structural units is 78.26 weight %.
（2）Toward step（1）3.0ml is added in obtained product（3.135g）γ-mercaptopropyl trimethoxysilane, and immediately
Sampling carries out sulfydryl test, is then heated to addition 30mg azo-bis-isobutyl cyanides after 90 DEG C, and by Stress control under 0.5MPa
Reaction obtains modified diene polymer after 0.5 hour, and samples progress sulfydryl test.Into above-mentioned modified diene polymer
Add 0.2g age resistor Irganox1520, and the dry 24h in 60 DEG C of vacuum.Wherein, in modified diene polymer, mercapto
Base conversion ratio is 89%, and Mooney viscosity is 55, and number-average molecular weight is 19.4 ten thousand, and molecular weight distribution is 1.09；With the modified diene
On the basis of the gross weight of hydrocarbon polymer, the content of γ-mercaptopropyl trimethoxysilane construction unit is 1.91 weight %.The polymerization
Thing does not have undesirable smell.
Preparation example 4
The preparation example is used to illustrate modified diene polymer of the invention provided and preparation method thereof.
（1）In 5 liters of stainless steel stirred tanks, under High Purity Nitrogen protection, add 2288g hexamethylenes, 62.4g styrene,
248.6g butadiene and 1.3g tetrahydrofurfuryl alcohol ether, then add 1.1mmol n-BuLi and by pressure under the conditions of 50 DEG C
Control initiation reaction 1 hour under 0.25MPa, obtains the solution containing diene polymer.The number of the diene polymer
Average molecular weight is 20.5 ten thousand, and on the basis of the weight of conjugated diene construction unit in the diene polymer, described two
The content that side chain contains the conjugated diene construction unit of double bond in olefin polymer is 51.05 weight %, styrol structural unit
Content be 20.06 weight %, the content of butadiene structural units is 79.94 weight %.
（2）Toward step（1）1.9ml is added in obtained product（1.986g）γ-mercaptopropyl trimethoxysilane, and immediately
Sampling carries out sulfydryl test, is then heated to addition 13mg azo-bis-isobutyl cyanides after 80 DEG C, and by Stress control under 0.3MPa
Reaction obtains modified diene polymer after 1 hour, and samples progress sulfydryl test.Add into above-mentioned modified diene polymer
Enter 0.4g age resistor Irganox1520, and the dry 24h in 60 DEG C of vacuum.Wherein, in modified diene polymer, sulfydryl
Conversion ratio is 78%, and Mooney viscosity is 59, and number-average molecular weight is 20.5 ten thousand, and molecular weight distribution is 1.1；With the modified diene
On the basis of the gross weight of polymer, the content of γ-mercaptopropyl trimethoxysilane construction unit is 0.50 weight %.The polymer
There is no undesirable smell.
Preparation example 5
The preparation example is used to illustrate modified diene polymer of the invention provided and preparation method thereof.
（1）In 5 liters of stainless steel stirred tanks, under High Purity Nitrogen protection, add 2288g hexanes, 62.4g styrene,
248.5g butadiene and 1.3g tetrahydrofurfuryl butyl ether, are then heated to after 70 DEG C and add 1.1mmol n-BuLi and by pressure
Initiation reaction 1.2 hours at 0.2 mpa are controlled, the solution containing diene polymer is obtained.The number of the diene polymer
Average molecular weight is 19.0 ten thousand, and on the basis of the weight of conjugated diene construction unit in the diene polymer, described two
The content that side chain contains the conjugated diene construction unit of double bond in olefin polymer is 46.80 weight %, styrol structural unit
Content be 20.07 weight %, the content of butadiene structural units is 79.93 weight %.
（2）Toward step（1）2.02ml is added in obtained product（1.990g）Gamma-mercaptopropyltriethoxysilane, exists side by side
I.e. sampling carries out sulfydryl test, is then heated to addition 30mg azo-bis-isobutyl cyanides after 75 DEG C, and by Stress control in 0.25MPa
Lower reaction obtains modified diene polymer after 1.2 hours, and samples progress sulfydryl test.Toward above-mentioned modified diene polymer
Middle addition 0.2g age resistor Irganox1520, and the dry 24h in 60 DEG C of vacuum.Wherein, in modified diene polymer,
Sulfydryl conversion ratio is 82%, and Mooney viscosity is 50, and number-average molecular weight is 19.0 ten thousand, and molecular weight distribution is 1.1；With the modification two
On the basis of the gross weight of olefin polymer, the content of gamma-mercaptopropyltriethoxysilane construction unit is 0.52 weight %.This gathers
Compound does not have undesirable smell.
Preparation example 6
The preparation example is used to illustrate modified diene polymer of the invention provided and preparation method thereof.
Method according to preparation example 4 prepares modified diene polymer, unlike, the γ-mercapto propyl trimethoxy
The addition of silane is 7.3ml（7.629g）, obtain modified diene polymer.Wherein, in modified diene polymer, mercapto
Base conversion ratio is 63%, and Mooney viscosity is 54, and number-average molecular weight is 20.7 ten thousand, and molecular weight distribution is 1.1；With the modified diene
On the basis of the gross weight of hydrocarbon polymer, the content of γ-mercaptopropyl trimethoxysilane construction unit is 1.52 weight %.The polymerization
Thing does not have undesirable smell.
Preparation example 7
The preparation example is used to illustrate modified diene polymer of the invention provided and preparation method thereof.
Method according to preparation example 4 prepares modified diene polymer, unlike, the γ-mercapto propyl trimethoxy
Silane is substituted with the 2- trimethyl silanes ethyl mercaptan of identical weight part, obtains modified diene polymer.Wherein, in modified diene
In hydrocarbon polymer, sulfydryl conversion ratio is 65%, and Mooney viscosity is 52, and number-average molecular weight is 20.3 ten thousand, and molecular weight distribution is 1.1；With
On the basis of the gross weight of the modified diene polymer, the content of 2- trimethyl silane ethyl mercaptan construction units is 0.41 weight
Measure %.The polymer does not have undesirable smell.
Contrast preparation example 1
The contrast preparation example is used to illustrate reference diene polymer and preparation method thereof.
Method according to preparation example 4 prepares diene polymer, unlike, not including step（2）, obtain alkadienes and gather
Compound.Wherein, in diene polymer, Mooney viscosity is 48, and number-average molecular weight is 190,000, and molecular weight distribution is 1.1.With institute
On the basis of the gross weight for stating diene polymer, the content of styrol structural unit is 20.06 weight %, butadiene structural units
Content be 79.94 weight %.
Contrast preparation example 2
The contrast preparation example is used to illustrate reference diene polymer and preparation method thereof.
（1）In 5 liters of stainless steel stirred tanks, under High Purity Nitrogen protection, 1500g hexamethylenes, 20g butadiene and 2.7g are added
Tetrahydrofurfuryl alcohol ether, is then heated to the n-BuLi that 12mmol is added after 40 DEG C and Stress control is triggered into anti-under 0.4MPa
Answer 1 hour, obtain the solution containing diene polymer.The number-average molecular weight of the diene polymer is 1000, and with institute
State in diene polymer on the basis of the weight of conjugated diene construction unit, side chain contains double bond in the diene polymer
Conjugated diene construction unit content be 67 weight %.
（2）Toward step（1）20g γ-mercaptopropyl trimethoxysilane is added in obtained product, and sampling carries out mercapto immediately
Base is tested, and is then heated to after 100 DEG C addition 1g dilauroyl peroxides, and after Stress control is reacted 5 hours under 0.4MPa
Modified diene polymer is obtained, and samples progress sulfydryl test.24h is finally dried in 80 DEG C of vacuum.Wherein, modified diene
The sulfydryl conversion ratio of hydrocarbon polymer is 80%, and number-average molecular weight is 1788.Using the gross weight of the modified diene polymer as base
Standard, the content of γ-mercaptopropyl trimethoxysilane construction unit is 44.4 weight %.
Embodiment 1-6
Embodiment 1-6 is used to illustrate vulcanization rubber of the invention provided and preparation method thereof.
（1）The preparation of elastomeric compound：
Modified diene polymer, the stearic acid of 1 parts by weight that 100 parts by weight are prepared by preparation example 1-6 respectively
（The polite Chemical Co., Ltd. in Hong Kong, SA1801）, 10 parts by weight high abrasion furnace black N330（The Tianjin gold autumn limited public affairs of reality carbon black chemical industry
Department）, 60 parts by weight white carbon 115GR（Goldschmidt chemical corporation）It is well mixed and uses Haake to be heat-treated, wherein, heat treatment temperature
For 150 DEG C, rotating speed is 30rpm/min, and the time is 7min.After the completion of heat treatment, said mixture is added in mill, and added
Enter the zinc oxide of 2.5 parts by weight（Liuzhou Xin Pin Co., Ltds）, 1 parts by weight stearic acid（The polite Chemical Co., Ltd. in Hong Kong,
SA1801）, 2 parts by weight antioxidant 4020, the N- cyclohexyl -2- benzothiazole sulfonamides of 1.4 parts by weight（Join purchased from Hebi
Vast and boundless Chemical Co., Ltd., CZ）, 0.75 parts by weight diphenylguanidine（Guangzhou Li great rubber raw materials trade Co., Ltd, DPG）With 6 weights
Measure part silane coupler Si69（Goldschmidt chemical corporation）, kneaded 60 minutes at 50 ± 5 DEG C, obtain elastomeric compound H1-H6.
（2）Vulcanization：
Under 150 DEG C, 12MPa, by step（1）Obtained elastomeric compound H1-H6 is vulcanized on vulcanizing press respectively
Processing 40 minutes, obtains vulcanization rubber S1-S6.
Embodiment 7
The embodiment is used to illustrate vulcanization rubber of the invention provided and preparation method thereof.
Method according to embodiment 1-6 prepares vulcanization rubber, unlike, 100 parts by weight are prepared into by embodiment 1-6
To 80 parts by weight of modified diene polymer the modified diene polymer prepared by preparation example 7 and 20 parts by weight
Natural rubber（Shanghai Yun Tai limited rubbers company）Mixture replacing, obtain vulcanization rubber S7.
Comparative example 1
The comparative example is used for the preparation method for illustrating that reference vulcanizes rubber.
Method according to embodiment 1 prepares vulcanization rubber, unlike, the modified diene that will be prepared by preparation example 1
Hydrocarbon polymer is substituted with the diene polymer prepared by contrast preparation example 1, and the addition of diene polymer is
99.54 parts by weight, in addition, in the preparation process of elastomeric compound, being also added into γ-mercapto propyl trimethoxy silicon of 0.46 parts by weight
Alkane, obtains reference vulcanization rubber DS1.
Comparative example 2
The comparative example is used for the preparation method for illustrating that reference vulcanizes rubber.
Method according to embodiment 1 prepares vulcanization rubber, unlike, the modified diene that will be prepared by preparation example 1
The hydrocarbon polymer diene polymer obtained by contrast preparation example 1 of 98.96 parts by weight and being made by contrast for 1.04 parts by weight
The mixture replacing for the modified diene polymer that standby example 2 is obtained, obtains reference vulcanization rubber DS2.
Test case 1-7
Test case 1-7 is used for the test for vulcanizing rubber S1-S7 performances for illustrating to provide containing the present invention.
（1）Glass transition temperature（Tg）Test：
Using the model MDSC2910 of TA companies of U.S. differential scanning calorimetry（DSC）Instrument is measured, wherein, adjust
Cycle processed is 60s, and modulated amplitude is ± 1.5 DEG C, and heating rate is 10 DEG C/min, and nitrogen is protected, and flow velocity is 50mL/min.Gained
As a result it is as shown in table 1.
（2）The test of mechanical property：
Rubber S1-S7 will be vulcanized respectively the thick vulcanization sheet rubbers of 2mm are made, and according to specified in GB/T528-1998 1
Obtained vulcanization sheet rubber is cut into dumbbell shaped standard film by type dumbbell shaped cut-off knife, using rubber puller system（Japanese Shimadzu Corporation's life
Production, model AG-20KNG）Mechanical property to the vulcanization sheet rubber is tested, wherein, test temperature is 25 DEG C, traction
Speed is 500 mm/mins, obtains vulcanizing the breaking strength and elongation at break of rubber, and acquired results are as shown in table 1.
（3）The test of shore a hardness：
Method is tested according to specified in GB/T531-1999, and acquired results are as shown in table 1；
（4）Anti- deformation nature test：
Dumbbell shaped standard film is cut into by rubber S1-S7 is vulcanized according to 1 type dumbbell shaped cut-off knife specified in GB/T528-92,
Test temperature be 25 DEG C, hauling speed be 500 mm/mins under conditions of sample is broken.Sample after tension failure is put
3min is put, then two parts of fracture are coincide together, the distance after measurement coincide between two parallel lines is calculated as follows and pulled apart
Permanent deformation value：
Sb=100（Lt-L0）/L0, wherein, SbTo pull apart permanent deformation, %；LtAfter being coincide for sample between two parallel lines away from
From mm；L0For initial trial length, mm.Acquired results are as shown in table 1.
（5）Thermogenesis performance is tested：
It is measured using the Y3000E type compression heat generation test machines of Beijing You Shen Electronic Instrument, Limiteds, wherein, test temperature
Spend for 55 DEG C, the testing time is 25 minutes, compression frequency is 30 times/second.Acquired results are as shown in table 1.
（6）The test of wet-sliding resistant performance and rolling resistance：
Using wet-sliding resistant performance and rolling resistance of U.S.'s TA companies DMA-2980 types viscoelastic spectrometer to vulcanization rubber S1-S7
It is measured, wherein, test frequency is 2Hz, and heating rate is 5 DEG C/min, and test temperature is 100 DEG C, and sample size is 40mm
×5mm×1mm.Represent to vulcanize the wet-sliding resistant performance of rubber with tan δ at 0 DEG C, tan δ are bigger, represent that vulcanization rubber is anti-slippery
Performance is better；Represent to vulcanize the rolling resistance of rubber with tan δ at 60 DEG C, tan δ are smaller, represent that vulcanization rubber rolling resistance is got over
It is small；Scattered in rubber of filler uses Tan δ（0℃）/Tanδ（60℃）Value characterize, its value is higher show that filler is scattered must be more
It is good.Acquired results are as shown in table 1.
Contrast test example 1-2
Contrast test example 1-2 is used for the test for illustrating the performance containing reference rubber.
Vulcanize rubber DS1 and DS2 property to the reference obtained by comparative example 1 and comparative example 2 according to test case 1-7 method
It can be tested, acquired results are as shown in table 1.
Table 1
As can be seen from the above results, the rubber composition that the present invention is provided can effectively improve anti-slippery and rolling
Relation between resistance.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (22)
1. a kind of rubber composition, the rubber composition contains olefinic rubber, vulcanizing agent, vulcanization accelerator, reinforcing agent and work
Agent, it is characterised in that contain modified diene polymer, the molecule of the modified diene polymer in the olefinic rubber
Contain monovinylarene construction unit and conjugated diene construction unit, and the molecule of the modified diene polymer in chain
Also containing the silane coupler construction unit shown in formula (I), on the strand of the modified diene polymer, Dan Yi in chain
The main chain of alkenyl arene construction unit and conjugated diene construction unit composition polymer, and the silane coupler shown in formula (I)
Construction unit key is connected on the conjugated diene construction unit on main chain, and the number-average molecular weight of the modified diene polymer is
50000-100 ten thousand；On the basis of the gross weight of the modified diene polymer, the content of the silane coupler construction unit is
0.36-2 weight %；
Wherein, R1-R4For C1-C20Straight or branched alkyl or contain heteroatomic C1-C20Straight or branched alkyl, it is described
One or more of the hetero atom in halogen, oxygen, sulphur, silicon and phosphorus.
2. rubber composition according to claim 1, wherein, R1-R3For C1-C5Straight or branched alkyl or straight chain or branch
Chain alkoxy, R4For C1-C5Straight or branched alkylidene.
3. rubber composition according to claim 1, wherein, on the basis of the gross weight of the olefinic rubber, the alkene
The content of modified olefine polymer is 50-100 weight % in hydrocarbon rubbers.
4. rubber composition according to claim 3, wherein, on the basis of the gross weight of the olefinic rubber, the alkene
The content of modified olefine polymer is 80-100 weight % in hydrocarbon rubbers.
5. the rubber composition according to any one in claim 1-4, wherein, also containing mixing in the olefinic rubber
Rubber, the mixed rubber be selected from natural rubber, polybutadiene rubber, butadiene-styrene rubber, polyisoprene rubber, neoprene,
One or more in butyl rubber and ethylene propylene diene rubber.
6. rubber composition according to claim 5, wherein, using the modified diene polymer of 100 parts by weight as
Benchmark, the content of the mixed rubber is 10-40 parts by weight, and the content of the vulcanizing agent is 1-3 parts by weight, and the vulcanization promotes
The content of agent is 3-5 parts by weight, and the content of the reinforcing agent is 70-90 parts by weight, and the content of the activator is 3-4 weight
Part.
7. rubber composition according to claim 1, wherein, using the gross weight of the modified diene polymer as base
Standard, the total content of the monovinylarene construction unit and conjugated diene construction unit is 98-99.64 weight %, described
The content of silane coupler construction unit is 0.36-2 weight %.
8. rubber composition according to claim 1, wherein, the monovinylarene construction unit and conjugated diene
The weight ratio of construction unit is 5:95-60:40.
9. rubber composition according to claim 8, wherein, the monovinylarene construction unit and conjugated diene
The weight ratio of construction unit is 20:80-40:60.
10. the rubber composition according to any one in claim 1-4, wherein, in formula (I),
R1-R3For methoxyl group, R4For propylidene；Or,
R1-R3For ethyoxyl, R4For propylidene；
R1-R3For methyl, R4For ethylidene.
11. the rubber composition according to any one in claim 1-4, wherein, the modified diene polymer
Number-average molecular weight is 150,000-20 ten thousand, and molecular weight distribution is 1-4.
12. rubber composition according to claim 11, wherein, the molecular weight distribution of the modified diene polymer is
1-1.5。
13. rubber composition according to claim 1, wherein, the modified diene polymer is made by the following method
It is standby to obtain：In an inert atmosphere and in the presence of initiator, monovinylarene construction unit and conjugated diene will be contained
The diene polymer of construction unit is contacted with silane coupler, and the condition of the contact causes the silane coupler chemical bond
It is connected on the diene polymer；The number-average molecular weight of the diene polymer is 50,000-100 ten thousand, and with the alkadienes
In polymer on the basis of the weight of conjugated diene construction unit, side chain contains the conjugation two of double bond in the diene polymer
The content of olefin unit is 15-85 weight %, and the silane coupler has the structure shown in formula (II)；The silane is even
Connection agent consumption cause on the basis of the gross weight of the modified diene polymer, the silicon derived by the silane coupler
The content of alkane coupling agent construction unit is 0.36-2 weight %；
Wherein, R1-R4For C1-C20Straight or branched alkyl or contain heteroatomic C1-C20Straight or branched alkyl, it is described
One or more of the hetero atom in halogen, oxygen, sulphur, silicon and phosphorus.
14. rubber composition according to claim 13, wherein, R1-R3For C1-C5Straight or branched alkyl or straight chain or
Branched alkoxy, R4For C1-C5Straight or branched alkylidene.
15. rubber composition according to claim 13, wherein, side chain contains being total to for double bond in the diene polymer
The content of yoke alkadienes construction unit is 30-60 weight %.
16. the rubber composition according to any one in claim 13-15, wherein, the diene polymer passes through
Following methods are prepared：In an inert atmosphere and in the presence of initiator, monovinylarene and conjugated diene are existed
Polymerisation is carried out in solvent, the reaction product containing diene polymer is obtained, the condition of the polymerisation makes what is obtained
The number-average molecular weight of diene polymer is 50,000-100 ten thousand, and with conjugated diene construction unit in the diene polymer
Weight on the basis of, in the diene polymer side chain contain the conjugated diene construction unit of double bond content be 15-85
Weight %.
17. rubber composition according to claim 16, wherein, side chain contains being total to for double bond in the diene polymer
The content of yoke alkadienes construction unit is 30-60 weight %.
18. rubber composition according to claim 16, wherein, the condition of the polymerisation is including polymerization temperature
10-160 DEG C, polymerization pressure is 0.05-0.5MPa, and polymerization time is 0.5-10 hours.
19. rubber composition according to claim 18, wherein, the condition of the polymerisation is including polymerization temperature
40-80 DEG C, polymerization pressure is 0.1-0.3MPa, and polymerization time is 0.5-2 hours.
20. the rubber composition according to any one in claim 13-15, wherein, by the diene polymer with
It is 20-150 DEG C that the condition of silane coupler contact, which includes Contact Temperature, and contact is 0.01-1MPa, and time of contact is 0.1-
24 hours.
21. rubber composition according to claim 20, wherein, the diene polymer is contacted with silane coupler
Condition to include Contact Temperature be 70-90 DEG C, contact is 0.1-0.5MPa, and time of contact is 0.5-5 hours.
22. it is well mixed as the rubber composition described in any one in claim 1-21 and is vulcanized obtained vulcanization rubber.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310513366.4A CN104558416B (en) | 2013-10-25 | 2013-10-25 | A kind of rubber composition and vulcanization rubber |
| DE201410221690 DE102014221690A1 (en) | 2013-10-25 | 2014-10-24 | FUNCTIONAL DIENPOLYMER, MANUFACTURING METHOD AND RUBBER COMPOSITION THEREOF CONTAINING THIS |
| RU2014142923/04A RU2599641C2 (en) | 2013-10-25 | 2014-10-24 | Functional polydiene, method for production thereof and rubber composition containing same |
| US14/523,113 US9296840B2 (en) | 2013-10-25 | 2014-10-24 | Functional diene polymer, preparation method thereof, and rubber composition comprising the same |
| FR1460262A FR3012455B1 (en) | 2013-10-25 | 2014-10-24 | FUNCTIONAL DIENE POLYMER, PROCESS FOR PREPARING THE SAME, AND RUBBER COMPOSITION COMPRISING SAME |
| BE2014/0796A BE1022183B1 (en) | 2013-10-25 | 2014-10-24 | FUNCTIONAL DIENPOLYMER, MANUFACTURING METHOD AND RUBBER COMPOSITION THEREOF CONTAINING THIS |
| KR1020140146390A KR101660856B1 (en) | 2013-10-25 | 2014-10-27 | Functional diene polymer, preparation method thereof, and rubber composition comprising the same |
| SG10201407122YA SG10201407122YA (en) | 2013-10-25 | 2014-10-31 | Functional diene polymer, preparation method thereof, and rubber composition comprising the same |
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|---|---|---|---|
| CN201310513366.4A CN104558416B (en) | 2013-10-25 | 2013-10-25 | A kind of rubber composition and vulcanization rubber |
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| Publication Number | Publication Date |
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| CN104558416A CN104558416A (en) | 2015-04-29 |
| CN104558416B true CN104558416B (en) | 2017-07-28 |
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| CN102731723A (en) * | 2011-04-13 | 2012-10-17 | 住友橡胶工业株式会社 | Diene polymer and production method thereof |
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| CN102731723A (en) * | 2011-04-13 | 2012-10-17 | 住友橡胶工业株式会社 | Diene polymer and production method thereof |
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