CN106700159A - Rubber composition and vulcanized rubber, and preparation method therefor and application thereof - Google Patents
Rubber composition and vulcanized rubber, and preparation method therefor and application thereof Download PDFInfo
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- CN106700159A CN106700159A CN201510781222.6A CN201510781222A CN106700159A CN 106700159 A CN106700159 A CN 106700159A CN 201510781222 A CN201510781222 A CN 201510781222A CN 106700159 A CN106700159 A CN 106700159A
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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
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- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
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Abstract
The invention relates to the rubber field and discloses a rubber composition. The composition contains diolefine rubber, fluid rubber, fortifier, vulcanization agent, vulcanization accelerator, activating agent and first coupling agent. The composition is characterized in that the fluid rubber is a silicone atoms containing fluid rubber, and the silicone atoms containing fluid rubber is a star-shaped styrene-butadiene polymer with silicone modification on both ends. The invention also discloses the method for preparing vulcanized rubber by using the rubber composition, the vulcanized rubber obtained from the method, and the application of the vulcanized rubber as a tire tread material. The rubber composition provided by the invention successfully solves the problems of colour change and quality fluctuation of the finished tire product, which is due to the moving of processing oil to the surface of the finished tire product during the storage process. The vulcanized rubber prepared by the provided rubber composition has lower rolling resistance, better wet skid resistance and superior overall performance.
Description
Technical field
The present invention relates to rubber materials, in particular it relates to a kind of rubber composition, a kind of vulcanized rubber and
Its preparation method and application.
Background technology
With becoming increasingly popular for automobile, the consumption of oil and the discharge capacity of carbon dioxide are also therewith increasingly
Height, and consequently leads to the in short supply and global climate of petroleum resources and warm.Therefore, a reduction oil consumption
Auto industry revolution directly triggered automaker to reduce tire drag requirement.Hindering
In the resistance that automobile advances, rolling resistance accounts for 18-30%, and rolling resistance energy consumption accounts for fuel consumption
14.4%, it means that rolling resistance reduction by 30%, then can fuel-economizing 4.5-6%.Reducing rolling resistance
While, tire should could also meet the demand of commercial Application with preferable wet-sliding resistant performance.
Under normal circumstances, anti-slippery and rolling resistance can be respectively by vulcanized rubber in 0 DEG C and 60 DEG C
Fissipation factor tan δ values are characterized.Tan δ values at 0 DEG C are bigger, and anti-slippery is better；Tan δ at 60 DEG C
Value is smaller, and rolling resistance is lower.Sizing material is obtained good combination property, should try one's best when increasing 0 DEG C
Tan δ values, reduce 60 DEG C when tan δ values.
In terms of rolling resistance is reduced, the direction of research is more at present, including rubber structure design, rubber
The many aspects such as modified, processing technology improvement, Design of Tire Structure, tyre tread design.
US6184296 is using the crosslinking being modified by surface along fourth and butylbenzene powdered rubber (swelling index
4~5,60~450nm of particle diameter), the rolling resistance of natural rubber (NR) formula system vulcanizate drops
It is low, but strength property is uninfluenced.1-chloro-4-methyl-benzene is grafted to crosslinking butylbenzene powder by US6133364
On rubber surface, then use it in NR formula systems, making the rolling resistance of vulcanizate reduces, and
Anti-slippery is improved.The modified crosslinking butylbenzene powdered rubber of US6207757 1-chloro-4-methyl-benzenes reaches
The effect of NR formula system vulcanizate rollings resistance is reduced, while improve the hauling ability of tire and resistance to
The property used.
Polar group is introduced in above-mentioned patent document, but all there is complex process, and cannot be simultaneously
Play a part of the defect of processing oil.It is well known that need to add in rubber preparation process processing
Oil improves the processing characteristics and reduces cost of sizing material.In tire art, as " green tire " is general
The proposition of thought, formula design is varied.Because the filling system of green tire is based on white carbon, in vain
Carbon black is highly polar material, the difficulties in dispersion in rubber matrix, it is therefore desirable to add polyethylene glycol etc. to help
Dispersant solves the scattering problem of white carbon.It can be seen that, both need to introduce in green tire formula to process
Oil needs to introduce dispersion aids again, and the packing variety of addition is more.At present the processing oil that uses be aromatic naphtha,
The apolar substances such as naphthenic oil, and molecular weight is relatively low, is readily migrate into during tire products storage
Product surface, makes product that color change to occur and produces quality fluctuation.
Also have and replace the research of processing oil using liquid rubber, but liquid rubber used is still for nonpolar,
White carbon is can do nothing to help uniformly to disperse in rubber.Such as CN101792545B discloses a kind of isoamyl
Diene liquid rubber, in order to reduce the high wet-sliding resistant of rubber, but this liquid rubber is only applicable
In carbon black system, act on unobvious in white carbon system.
The content of the invention
Tire finished surface is readily migrate into order to solve tire finished product processing oil during storage, makes wheel
There is color change and produce the problem of quality fluctuation in tire finished product, the invention provides a kind of new rubber
Composition, vulcanized rubber and its preparation method and application.
The present inventor has found after research, dience rubber and liquid rubber interworking used, its
Middle liquid rubber is the liquid rubber of silicon atoms, can well solve tire finished product during storage
Processing oil is readily migrate into tire finished surface, makes tire finished product that color change to occur and produces quality ripple
Dynamic problem, and white carbon difficulties in dispersion in rubber matrix can also be solved the problems, such as, so as to complete
The present invention.
In a first aspect, the present invention provides a kind of rubber composition, said composition contains dience rubber, liquid
Body rubber, reinforcing agent, vulcanizing agent, vulcanization accelerator, activator and the first coupling agent, the liquid rubber
Glue is the star-like styrene-butadiene polymer of both-end Si modification, benzene second in the star-like styrene-butadiene polymer of the both-end Si modification
The content of alkene construction unit is 10-30 weight %, and the content of 1,2 structure is 0-80 weight %, described double
The number-average molecular weight for holding the star-like styrene-butadiene polymer of Si modification is 1000-30000.
Second aspect, the present invention provides a kind of preparation method of vulcanized rubber, and the method includes will be according to this
Each component in the rubber composition that the first aspect of invention is provided is kneaded, and obtains elastomeric compound, then
The elastomeric compound is vulcanized.
The third aspect, the present invention provides the vulcanized rubber prepared by the method for the second aspect invented.
Fourth aspect, the present invention provides application of the vulcanized rubber as tire tread material.
Due to introducing the liquid rubber of silicon atoms in the rubber composition that the present invention is provided, serve and replace
The multi-function action of generation filling oil and dispersion aids, so as to solve white carbon well in rubber matrix
Difficulties in dispersion, and tire finished product processing oil during storage is readily migrate into tire finished surface, makes
There is color change and produce the problem of quality fluctuation in tire finished product.
The vulcanized rubber that the rubber composition provided using the present invention is prepared has relatively low rolling resistance
With preferable wet-sliding resistant performance, excellent combination property.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific embodiment
Specific embodiment of the invention is described in detail below.It should be appreciated that this place is retouched
The specific embodiment stated is merely to illustrate and explain the present invention, and is not intended to limit the invention.
According to the first aspect of the invention, the invention provides a kind of rubber composition, said composition contains
Dience rubber, liquid rubber, reinforcing agent, vulcanizing agent, vulcanization accelerator, activator and the first coupling
Agent, the liquid rubber is the star-like styrene-butadiene polymer of both-end Si modification, the star-like fourth of the both-end Si modification
The content of styrol structural unit is 10-30 weight % in benzene polymer, and the content of 1,2 structure is 0-80
Weight %, the number-average molecular weight of the star-like styrene-butadiene polymer of the both-end Si modification is 1000-30000.
Preferably, the content of styrol structural unit is in the star-like styrene-butadiene polymer of the both-end Si modification
15-25 weight %, the content of 1,2 structure is 40-70 weight %, the star-like butylbenzene of the both-end Si modification
The number-average molecular weight of polymer is 3000-15000.
Preferably, the molecular weight distributing index of the star-like styrene-butadiene polymer of the both-end Si modification is
1.01-1.20；More preferably molecular weight distributing index is 1.06-1.15.
In the present invention, number-average molecular weight and molecular weight distributing index are according to gel permeation chromatography (GPC)
Detection.
Preferably, the star-like styrene-butadiene polymer of the both-end Si modification is by by styrene monomer and butadiene
Monomer is contacted and is obtained with initiator, the second coupling agent, end-capping reagent successively, wherein, the initiation
Agent has the structure as shown in following formula (I)：
Wherein, R1、R2And R3It is each independently selected from alkyl, the monoolefine of C2~C20 of C1~C20
The aralkyl of base or C6~C20, R4Selected from the alkylidene of C1~C20.
Preferably, the preparation method of the initiator with the structure shown in formula (I) is as follows：
Under the protection of inert gas, the halogenated silanes shown in formula (II) is connect in organic solvent with lithium
Touch, siliceous organic lithium initiator is then obtained from the contact mixture for obtaining, and (as formula (I) is shown
Structure the initiator),
Wherein, R1、R2、R3And R4Same as described above, X is Cl or Br.
Preferably, the straight chained alkyl of the alkyl of the C1~C20 of the invention including C1-C20 and
The branched alkyl of C3-C20 and the cycloalkyl of C3-C20, its instantiation can be included but is not limited to：
Methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl,
Isopentyl, tertiary pentyl, neopentyl, n-hexyl, cyclopropyl, cyclopenta, cyclohexyl, 4- methyl cyclohexanes
Base, 4- ethylcyclohexyls, 4- n-propyls cyclohexyl, 4- normal-butyls cyclohexyl, cyclooctyl and 2- ethyl rings
Dodecyl.
Preferably, the monoene alkyl of the C2~C20 of the invention includes the straight chain mono-olefins of C2-C20
The branched monoolefins base of base and C4-C20, its instantiation can be included but is not limited to：Vinyl, third
Alkenyl, 2- methyl -2- pentenyls, 2- methyl -3- ethyls-laurylene base.
Preferably, the instantiation of the aralkyl of the C6~C20 of the invention can be included but is not limited to：
Phenyl, naphthyl, 4- aminomethyl phenyls, 4- ethylphenyls, 2- isobutyl phenenyls and 4,5 ,-dimethyl naphthyl.
Preferably, in the structure shown in formula (I) and formula (II), R1、R2And R3Independently of one another
Selected from the alkyl of C1~C20, the more preferably alkyl of C1~C12.R4Preferably C1~C20's
The alkylidene of alkylidene, more preferably C2~C5.
It is further preferred that in the structure shown in formula (I) and formula (II), R1、R2And R3Each
Independently selected from methyl, ethyl, n-propyl and isopropyl, R4It is ethylidene or propylidene.
Preferably, the halogenated silanes and the mol ratio of lithium are 1:(2~10), more preferably 1:
(2.5~5.0).
Preferably, the halogenated silanes is including temperature with the condition that lithium is contacted in organic solvent
- 30~30 DEG C, preferably -5~15 DEG C, the time is 5~100h, preferably 15~50h.Preferably, it is described
Halogenated silanes includes with the mode that lithium is contacted in organic solvent：By halogenated silanes and the organic solvent with
Volume ratio is 1：After the ratio mixing of (2-6), with 0.5~10mL/h, the preferably speed of 1.5~3.5mL/h
Rate is added in the organic solvent containing lithium and is contacted.Preferably, the hair of side reaction is reduced to try one's best
Raw, the contact is carried out under agitation.
The inert gas refers to not sent out with reactant, reaction product and solvent under the contacting conditions
The gas of biochemical interaction, for example：Group 0 element gas.The preferred argon gas of inert gas.
The process that siliceous organic lithium initiator is obtained from the contact mixture for obtaining can be in inertia
Carried out under the protection of gas.The inert gas is preferably same as above.It is described from the contact mixture for obtaining
The middle operation for obtaining siliceous organic lithium initiator can for example include：Under the protection of inert gas, by institute
Stating contact mixture carries out sedimentation acquisition supernatant, and supernatant is filtered with core filter bulb then.Institute
Stating the condition of sedimentation can include standing 1-10 hours.Sedimentation can make the lithium halide (chlorine that reaction is generated
Change lithium or lithium bromide) and lithia precipitate.The aperture of the core filter bulb can be 3~4 μm.
Core filter bulb can filter remaining lithium in contact mixture, the lithium halide of reaction generation and lithia etc.
Inorganic matter, so as to obtain more pure siliceous organic lithium initiator.
Preferably, second coupling agent is p-divinyl benzene, m-divinyl benzene and adjacent divinyl
At least one in benzene；It is further preferred that second coupling agent is p-divinyl benzene and/or a diethyl
Alkenyl benzene.
Preferably, the end-capping reagent is the alkoxy silane containing monochloro or single bromine；It is further preferred that described
End-capping reagent is selected from trimethoxy chlorosilane, the ethyoxyl chlorosilane of dimethoxy one, the methoxyl group of diethoxy one
Chlorosilane, triethoxychlorosilane, the ethyoxyl bromo-silicane of dimethoxy one, the methoxy bromide of diethoxy one
Silane, trimethoxy bromo-silicane, triethoxy bromo-silicane, r-chloropropyl trimethoxyl silane, chloropropyl three
Ethoxysilane, the methoxy silane of chloropropyl diethoxy one, bromopropyl trimethoxy silane, bromopropyl
At least one in triethoxysilane and the methoxy silane of bromopropyl diethoxy one.
According to a kind of preferred embodiment, the star-like styrene-butadiene polymer of the both-end Si modification according to
Following method is prepared：
(1) in a solvent, in the presence of structure regulator, by styrene monomer and divinylic monomer
Contacted with initiator, carry out polymerisation in solution, obtain styrene butadiene random copolymer；The initiation
Agent has the structure as shown in following formula (I)：
Wherein, R1、R2And R3It is each independently selected from alkyl, the monoolefine of C2~C20 of C1~C20
The aralkyl of base or C6~C20, R4Selected from the alkylidene of C1~C20；
(2) styrene butadiene random copolymer and the second coupling agent for obtaining step (1)
Contact to carry out coupling reaction, the styrene butadiene random copolymer being coupled；
(3) styrene butadiene random copolymer of the coupling for obtaining step (2) and end-blocking
Agent contact is blocked with the styrene butadiene random copolymer to the coupling.
Preferably, in step (1), the styrene monomer accounts for the 15-45 weights of reaction monomers total amount
Amount %.The reaction monomers total amount is the weight summation of styrene monomer and divinylic monomer.In step (1)
In, the solvent can be the common solvent for polymerisation in solution, as long as the solvent is in polymerisation bar
It is in a liquid state under part, and cannot participate in polymerisation, the polymer that will not be also obtained with reaction reacts
.Preferably, the solvent is at least one in cycloalkane, aromatic hydrocarbons and isoparaffin.Specifically,
The solvent can for benzene, toluene, ethylbenzene, dimethylbenzene, mixed xylenes, n-hexane, hexamethylene,
Pentane, heptane, octane and at least one in raffinating oil.It is described raffinate oil be in petroleum refining process,
Catalytic reformate rich in aromatic hydrocarbons remaining distillate after extracting aromatic hydrocarbons.Preferably, the solvent is
The mixed solvent of hexamethylene and n-hexane, wherein, the weight of hexamethylene and n-hexane is than being preferably (4-9)：
1.The consumption of the solvent can be selected according to the amount of polymerized monomer.Usually, the solvent
Consumption cause step (1) in monomer concentration in the range of 5-30 weight %, preferably in 10-20 weight %
In the range of.Preferably, in step (1), during the structure regulator is used to make step (1)
Styrene monomer and divinylic monomer realize copolymerization, can be that common various can realize above-mentioned functions
Compound.Usually, the structure regulator can in molecular structure containing oxygen atom, nitrogen-atoms,
The compound of sulphur atom or phosphorus atoms.Specifically, the structure regulator can selected from ether, butyl oxide,
Tetrahydrofuran (THF), glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofurfuryl alcohol ether, tetrahydrochysene chaff
Alcohol butyl ether, dioxane, crown ether, triethylamine, tetramethylethylenediamine, HMPA, tertiary fourth
At least one in potassium alcoholate, tert-pentyl alcohol potassium, potassium lauryl, alkyl benzene sulphonate potassium and sodium alkyl benzene sulfonate,
It is preferred that tetrahydrofurfuryl alcohol ether.Consumption to the structure regulator is not particularly limited, people in the art
Member can carry out appropriate selection according to the general knowledge of this area with reference to specific polymerizing condition.For example when
During from tetrahydrofurfuryl alcohol ether as structure regulator, on the basis of all solvents and monomer gross mass, knot
The addition of structure conditioning agent can be 50-500ppm, preferably 200-400ppm.Preferably, in step
(1) in, the solution polymerization condition includes that temperature is 30-70 DEG C, and the time is 10-100 minutes.
Preferably, the initiator is in terms of elemental lithium, the consumption of the initiator and second coupling agent
Mol ratio is 1：(1.5-10), more preferably 1：(3-5).Preferably, in step (2), institute
Stating the condition of coupling reaction includes that temperature is 40-100 DEG C, and the time is 10-60 minutes.
Preferably, in step (3), the condition for being blocked includes that temperature is 20-100 DEG C,
Time is 5-40 minutes.
In the composition that the present invention is provided, the dience rubber can be selected from polybutadiene rubber, fill
At least one in oily solution polymerized butadiene styrene rubber and non-oil-filled solution polymerized butadiene styrene rubber.Preferably, the alkadienes
At least contain oil-filled solution polymerized butadiene styrene rubber in rubber.For example, the dience rubber is oil-filled solution polymerized butylbenzene
Rubber, or oil-filled solution polymerized butadiene styrene rubber and polybutadiene rubber combination, or oil-filled solution polymerized butylbenzene rubber
The combination of glue and non-oil-filled solution polymerized butadiene styrene rubber, or oil-filled solution polymerized butadiene styrene rubber and polybutadiene rubber and
The combination of non-oil-filled solution polymerized butadiene styrene rubber.
Preferably, the described oil-filled solution polymerized butylbenzene rubber containing 0.1-100 weight % in the dience rubber
Glue；It is further preferred that containing the described oil-filled solution polymerized butylbenzene of 50-100 weight % in the dience rubber
Rubber；It is further preferred that being contained intermingle with containing the described oil-filled of 70-100 weight % in the dience rubber
Butadiene-styrene rubber.
Under preferable case, the content of styrol structural unit is 10-30 in the oil-filled solution polymerized butadiene styrene rubber
Weight %, the content of 1,2 structure is 40-70 weight %, and Mooney viscosity is 50-70, and oil-filled number is 20-50
Part；In the case of more preferably, the content of styrol structural unit is in the oil-filled solution polymerized butadiene styrene rubber
15-25 weight %, the content of 1,2 structure is 50-65 weight %, and Mooney viscosity is 55-65, oil-filled number
It is 30-40 parts.The oil-filled number refers to be calculated with the rubber of 100 weight portions, fills the weight portion of oil
Number.
In the present invention, it is necessary to illustrate, unless stated otherwise, relevant oil-filled solution polymerized butylbenzene rubber
The metering of glue is calculated on the basis of butt, that is to say, that relevant oil-filled solution polymerized butylbenzene of the invention
Do not include the number of filling oil in the metering of rubber.
Preferably, the polybutadiene rubber is butadiene rubber.It is further preferred that in the butadiene rubber
Cis-structure content be more than or equal to 95 weight %.
In the composition that the present invention is provided, it is preferable that the dience rubber with 100 weight portions is
Benchmark, the content of the liquid rubber is 5-35 weight portions, and the content of the reinforcing agent is 50-95 weight
Part, the content of the vulcanizing agent is 0.5-5 weight portions, and the content of the vulcanization accelerator is 1-6 weight
Part, the content of the activator is 3-8 weight portions, and the content of first coupling agent is 3-10 weight portions.
In the case of more preferably, on the basis of the dience rubber of 100 weight portions, the liquid rubber
The content of glue is 8-30 weight portions, and the content of the reinforcing agent is 60-85 weight portions, the vulcanizing agent
Content is 1-3.5 weight portions, and the content of the vulcanization accelerator is 2-4 weight portions, the activator
Content is 4-6 weight portions, and the content of first coupling agent is 5-8 weight portions.
Preferably, containing more than 50 weight % white carbons in the reinforcing agent；The more preferred enhancing
Contain the white carbon of 80-100 weight % in agent.
Under preferable case, carbon black is also contained in the reinforcing agent, it is preferable that in the reinforcing agent, institute
The content for stating carbon black is 0.001-20 weight %, more preferably 5-15 weight %.
According to a kind of preferred embodiment, the reinforcing agent of the invention is by white carbon and carbon black group
Into.
Preferably, the vulcanizing agent is insoluble oil-filled sulphur, two thio morpholines and four two morphines of vulcanization
At least one in quinoline.
Preferably, the vulcanization accelerator is that sulfenamide vulcanization accelerator and/or guanidine vulcanization promote
Agent.The more preferred sulfenamide vulcanization accelerator is the N- tert-butyl groups -2-[4-morpholinodithio base time sulphonyl
Amine (accelerator TBBS), N- cyclohexyl -2-[4-morpholinodithio base sulfenamide and N- oxygen diethylidene -2- benzene
At least one in benzothiazolyl sulfenamide.The more preferred guanidine vulcanization accelerator is diphenylguanidine
(diphenylguanidine) and/or di-o-tolylguanidine.It is particularly preferred that the vulcanization accelerator is sulfenamide
Vulcanization accelerator and guanidine vulcanization accelerator.
Preferably, the activator is zinc oxide and/or stearic acid.
Preferably, first coupling agent is the silane coupler of sulfur atom-containing and alkoxy.It is further excellent
Selection of land, first coupling agent is double-[γ-(triethoxysilicane) propyl group] tetrasulfide (Si69) and/or double
- (γ-triethoxy silicon substrate propyl group) disulphide (Si75).
Preferably, the composition that the present invention is provided further contains age resistor and/or microwax.
Preferably, the microwax is main by C20-60Cycloalkane and it is a small amount of just, isoparaffin composition,
Fusing point is 60-95 DEG C, and molecular weight is 580-700.
Preferably, when age resistor is contained in the composition, the dience rubber with 100 weight portions is
Benchmark, the content of the age resistor is 1-5 weight portions, is preferably 2-4 weight portions.
Preferably, when microwax is contained in the composition, the dience rubber with 100 weight portions is
Benchmark, the content of the microwax is 0.1-2 weight portions, is preferably 0.5-1.5 weight portions.
Preferably, the age resistor is amines antioxidants and/or quinoline type antioxidant.The more preferred amine
Class age resistor is N- isopropyls-N '-diphenyl-para-phenylene diamine, N- (1,3 dimethylbutyl)-N '-phenyl to benzene two
At least one in amine and N, N '-bis- (1,4- dimethyl amyl groups) p-phenylenediamine.The more preferred quinolines
Age resistor is 2,2,4- trimethyl -1,2- dihyaroquinolines condensate, 6- ethyoxyl -2,2,4- trimethyl -1,2-
At least one in dihyaroquinoline and 6- dodecyl -2,2,4- trimethyl -1,2- dihyaroquinolines.
According to the second aspect of the invention, it is described the invention provides a kind of preparation method of vulcanized rubber
Method includes being kneaded each component in above-mentioned composition, elastomeric compound is obtained, then by the mixing
Glue is vulcanized.
In the preparation method of the vulcanized rubber that the present invention is provided, the rubber composition (also referred to as group
Compound) in the species and content of each component be able to will not be repeated herein according to reasonable selection is carried out above.
In the preparation method of the vulcanized rubber that the present invention is provided, the method and condition of the mixing can be
The conventional selection of this area.For example, the mixing can be carried out in mill or banbury.
Preferably, the condition of the vulcanization includes that the temperature of vulcanization is 140-160 DEG C, and the pressure of vulcanization is
5-15MPa, the time of vulcanization is 10-50 minutes.
A kind of preferred embodiment of the invention, the method for preparing vulcanized rubber can be with
Carry out as follows：
(1) in banbury, dience rubber and liquid rubber are added, and in 50-80 DEG C of initial temperature
Lower mixing 30-60s；
(2) reinforcing agent of the weight of the 1/2-3/4 of whole reinforcing agents and the activator of whole are added
2-3min is kneaded with whole silane couplers；
(3) remaining reinforcing agent, the whole components in addition to vulcanizing agent and vulcanization accelerator are added,
Treat sizing material temperature to reach 150-160 DEG C that mixing time reaches 5-7min or sizing material temperature reaches 170 DEG C afterwards
When unload sizing material；
(4) sizing material is passed through three times in the mill that roll spacing is 3-7mm, roller temperature is 50 ± 5 DEG C,
The batch mixing glue of acquisition is parked into 3-5h；
(5) batch mixing glue, vulcanizing agent and the vulcanization accelerator for obtaining step (4) are in initial temperature 40
Kneaded at ± 5 DEG C, glue is unloaded when sizing material temperature reaches 100-120 DEG C or mixing time reaches 2-4min
Material；
(6) sizing material for obtaining step (5) is that 0.4-0.6mm, roller temperature are 50 ± 5 DEG C in roll spacing
Pass through once in mill, roll spacing is then adjusted to 2-4mm, then by twice；The elastomeric compound that will be obtained
Park 18-30h；
(7) sizing material that will be processed by step (6) vulcanizes under 140-160 DEG C, 5-15MPa pressure
10-50 minutes, obtain vulcanized rubber.
According to the third aspect of the invention we, present invention also offers the vulcanization rubber prepared by the above method
Glue.
According to the fourth aspect of the invention, present invention also offers above-mentioned vulcanized rubber as tire facestock
The application of material.
Below will the present invention will be described in detail by specific embodiment.
Disclosure used below is as follows：
Oil-filled solution polymerized butadiene styrene rubber is the business for SSBR2535E purchased from the sinopec Yanshan Petrochemical company trade mark
Product, wherein, the content of styrol structural unit is 25 weight %, and the content of 1,2 structure is 62 weight %,
Mooney viscosity is 57, and oil-filled number is 37.5 parts.
Non- oil-filled solution polymerized butadiene styrene rubber is the business for SSBR2506 purchased from the sinopec Yanshan Petrochemical company trade mark
Product, wherein, the content of styrol structural unit is 25 weight %, and the content of 1,2 structure is 60 weight %,
Mooney viscosity is 65.
Polybutadiene rubber is the commodity for BR9000 purchased from the sinopec Yanshan Petrochemical company trade mark, and its is suitable
The content of formula structure is 97 weight %.
White carbon (reinforcing agent) is the business for 165GR purchased from Luo Diya (Qingdao) Co., Ltd trade mark
Product.
Carbon black (reinforcing agent) is the commodity for N330 purchased from the Bo Rui Chemical Co., Ltd.s trade mark of Tianjin hundred million.
Si69, Si75 (the first coupling agent) are the commodity purchased from Shanghai Rui Shi Chemical Industry Science Co., Ltd.
SA (stearic acid) (activator) is purchased from the commodity of Chemical Reagent Co., Ltd., Sinopharm Group.
Antioxidant 4010 (age resistor) is the commodity purchased from Gaoyi County profit and Chemical Co., Ltd..
Microwax is the commodity for W-445, carbon purchased from the Tianjin Heng Shengxin sources International Trading Company Ltd trade mark
Atom number is 20-50.
Diphenylguanidine (vulcanization accelerator) is the commodity purchased from Shijiazhuang City first rays of the morning sun Chemical Co., Ltd..
Accelerator TBBS (vulcanization accelerator) is the business purchased from Guangdong Du Ba new materials Science and Technology Ltd.
Product.
Vulcanizing agent used below is two thio morpholines, purchased from Hangzhou Hai Rui Chemical Co., Ltd.s.
Banbury is U.S. law Lai Er BR1600 types, and mold cavity volume is 1.5L.
Vulcanizing press is the production of huge rock oil pressure industry (Anhui) Co., Ltd, model P-50-PCD-3L.
TDAE (Treated Distillate Aromatic Extract) (filling oil) is purchased from Qingzhou City Ostwald-Folin
The commodity of profit limited rubber company.
PEG4000 (polyethylene glycol) is the commodity purchased from Nanjing Run Bang Chemical Co., Ltd.s.
Preparation example 1-6 is used to provide initiator.
Preparation example 1a-6a is used to provide the star-like styrene-butadiene polymer of both-end Si modification.
Embodiment 1-13 is used to prepare vulcanized rubber of the present invention, the rubber composition being below related to
Total amount it is identical, be 1200g.
Preparation example 1
Under argon gas protection, in three neck round bottom flask, hexamethylene/n-hexane mixed solvent is added (by China
The factory of petrochemical industry Beijing Yanshan Mountain branch company synthetic rubber one provides, and the mass ratio of its cyclohexane and n-hexane is 5：
1, similarly hereinafter) and 1.05g lithiums sand (0.15mol containing lithium, the average grain diameter of lithium sand is 0.8mm).Then
Sucked by 40mL hexamethylenes/n-hexane mixed solvent and 0.059mol chloropropyl trimethyl silicanes with syringe
The mixture of alkane composition, connects syringe and there-necked flask, and the liquid in syringe is with 1.67mL/h
Speed be added drop-wise in flask, reacted 40 hours under 0 DEG C and stirring condition.
Then stop stirring, stand 5 hours, the lithium chloride and lithia of reaction generation is precipitated.
Again under argon gas protection, supernatant is transferred in a new flask, is 3 μm with average pore size
Core filter bulb filters the inorganic matters such as lithium sand, lithium chloride and the lithia of residual in supernatant, is triggered
Agent Y1.
Preparation example 2
Under argon gas protection, in three neck round bottom flask, hexamethylene/n-hexane mixed solvent is added (by China
The factory of petrochemical industry Beijing Yanshan Mountain branch company synthetic rubber one provides, and the mass ratio of its cyclohexane and n-hexane is 5：
1, similarly hereinafter) and 1.05g lithiums sand (0.15mol containing lithium, the average grain diameter of lithium sand is 0.8mm).Then
Sucked by 50mL hexamethylenes/n-hexane mixed solvent and 0.03mol chloroethyl -1,2- dimethyl with syringe
The mixture of -3- ethylsilanes composition, syringe and there-necked flask connection, liquid in syringe with
The speed of 2.0mL/h is added drop-wise in flask, is reacted 24 hours under 15 DEG C and stirring condition.
Then stop stirring, stand 2 hours, the lithium chloride and lithia of reaction generation is precipitated.
Again under argon gas protection, supernatant is transferred in a new flask, is 3 μm with average pore size
Core filter bulb filters the inorganic matters such as lithium sand, lithium chloride and the lithia of residual in supernatant, is drawn
Hair agent Y2.
Preparation example 3
Under argon gas protection, in three neck round bottom flask, hexamethylene/n-hexane mixed solvent is added (by China
The factory of petrochemical industry Beijing Yanshan Mountain branch company synthetic rubber one provides, and the mass ratio of its cyclohexane and n-hexane is 5：
1, similarly hereinafter) and 1.05g lithiums sand (0.15mol containing lithium, the average grain diameter of lithium sand is 0.8mm).Then
Sucked by 40mL hexamethylenes/n-hexane mixed solvent and 0.041mol bromoethyl -1- methyl with syringe
The mixture of -2,3- diethylsilane composition, connects syringe and there-necked flask, the liquid in syringe
It is added drop-wise in flask with the speed of 2.12mL/h, is reacted 50 hours under subzero 5 DEG C and stirring condition.
Then stop stirring, stand 8 hours, the lithium bromide and lithia of reaction generation is precipitated.
Again under argon gas protection, supernatant is transferred in a new flask, is 3 μm with average pore size
Core filter bulb filters the inorganic matters such as lithium sand, lithium chloride and the lithia of residual in supernatant, is drawn
Hair agent Y3.
Preparation example 4
Initiator Y4 is prepared using the method similar to preparation example 1, except that：
The halogenated silanes used in this preparation example is chloroethyl -1,2,3- triethyl silicanes, and chloroethyl
The consumption mol ratio of -1,2,3- triethyl silicanes and lithium is 1：3.
Remaining is identical with preparation example 1.
Obtain initiator Y4.
Preparation example 5
Initiator Y5 is prepared using the method similar to preparation example 2, except that：
The halogenated silanes used in this preparation example is chloropropyl -1- methyl -2- ethyl -3- propyl silanes, and chlorine
The consumption mol ratio of propyl group -1- methyl -2- ethyl -3- propyl silanes and lithium is 1：4.
Remaining is identical with preparation example 2.
Obtain initiator Y5.
Preparation example 6
Initiator Y6 is prepared using the method similar to preparation example 3, except that：
The halogenated silanes used in this preparation example is chloropropyl -1,2- diethyl -3- propyl silanes, and chloropropyl
The consumption mol ratio of -1,2- diethyl -3- propyl silanes and lithium is 1：3.5.
Remaining is identical with preparation example 3.
Obtain initiator Y6.
Preparation example 1a
To 2350g hexamethylenes/n-hexane mixed solvent is added in 5L stainless steel polymeric kettles, it is subsequently adding
1.08g tetrahydrofurfuryl alcohols ether, 52.5g styrene and 297.5g butadiene.System temperature to be polymerized reaches
At 50 DEG C, the initiator Y1 for adding 116.7mmol to be prepared by above-mentioned preparation example 1；20 points of reaction
System temperature, is brought up to 80 DEG C by Zhong Hou, adds 350mmol divinylbenzenes (by divinyl
Base benzene and m-divinyl benzene are according to 1：1 mixed in molar ratio is formed)；After coupling 30 minutes, addition γ-
R-chloropropyl trimethoxyl silane, reacts 20 minutes, obtains the star-like styrene-butadiene polymer X1 of both-end Si modification.
In the star-like styrene-butadiene polymer X1 of both-end Si modification for being obtained, the content of styrene is 15 weight %,
The content of 1,2 structure is 50 weight %, and number-average molecular weight is 3000, and molecular weight distribution is 1.06.
Preparation example 2a
To 2350g hexamethylenes/n-hexane mixed solvent is added in 5L stainless steel polymeric kettles, it is subsequently adding
1.21g tetrahydrofurfuryl alcohols butyl ether, 70g styrene and 280g butadiene.System temperature to be polymerized reaches 70 DEG C
When, the initiator Y2 for adding 116.7mmol to be prepared by above-mentioned preparation example 2；After reaction 20 minutes,
System temperature is brought up to 85 DEG C, 460mmol p-divinyl benzenes are added；After coupling 40 minutes,
Triethoxychlorosilane is added, is reacted 30 minutes, obtain the star-like styrene-butadiene polymer X2 of both-end Si modification.
In the star-like styrene-butadiene polymer X2 of both-end Si modification for being obtained, the content of styrene is 18 weight %,
The content of 1,2 structure is 59 weight %, and number-average molecular weight is 3700, and molecular weight distribution is 1.08.
Preparation example 3a
To 2350g hexamethylenes/n-hexane mixed solvent is added in 5L stainless steel polymeric kettles, it is subsequently adding
1.08g tetrahydrofurfuryl alcohols ether, 105g styrene and 245g butadiene.System temperature to be polymerized reaches 40 DEG C
When, the initiator Y3 for adding 116.7mmol to be prepared by above-mentioned preparation example 3；After reaction 20 minutes,
System temperature is brought up to 85 DEG C, 525mmol m-divinyl benzenes are added；After coupling 30 minutes,
Trimethoxy chlorosilane is added, is reacted 25 minutes, obtain the star-like styrene-butadiene polymer X3 of both-end Si modification.
In the star-like styrene-butadiene polymer X3 of both-end Si modification for being obtained, the content of styrene is 22 weight %,
The content of 1,2 structure is 55 weight %, and number-average molecular weight is 4500, and molecular weight distribution is 1.07.
Preparation example 4a
This preparation example is carried out using the method similar to preparation example 1a, except that：
The initiator used in this preparation example is the initiator Y4 prepared in preparation example 4, is used
End-capping reagent is γ-bromopropyl trimethoxy silane, and the consumption of the second coupling agent is 400mmol.
Remaining is identical with preparation example 1a, obtains the star-like styrene-butadiene polymer X4 of both-end Si modification.
As a result：In the star-like styrene-butadiene polymer X4 of both-end Si modification, the content of styrene is 20 weight %,
The content of 1,2 structure is 55 weight %, and number-average molecular weight is 3300, and molecular weight distribution is 1.06.
Preparation example 5a
This preparation example is carried out using the method similar to preparation example 2a, except that：
The initiator used in this preparation example is the initiator Y5 prepared in preparation example 5, is used
End-capping reagent is γ-chloropropyl triethoxysilane.
Remaining is identical with preparation example 2a, obtains the star-like styrene-butadiene polymer X5 of both-end Si modification.
As a result：In the star-like styrene-butadiene polymer X5 of both-end Si modification, the content of styrene is 19 weight %,
The content of 1,2 structure is 61 weight %, and number-average molecular weight is 3700, and molecular weight distribution is 1.08.
Preparation example 6a
This preparation example is carried out using the method similar to preparation example 3a, except that：
The initiator used in this preparation example is the initiator Y6 prepared in preparation example 6, is used
End-capping reagent is the methoxyl group chlorosilane of diethoxy one.
Remaining is identical with preparation example 3a, obtains the star-like styrene-butadiene polymer X6 of both-end Si modification.
As a result：In the star-like styrene-butadiene polymer X6 of both-end Si modification, the content of styrene is 23 weight %,
The content of 1,2 structure is 55 weight %, and number-average molecular weight is 4400, and molecular weight distribution is 1.07.
Embodiment 1
The preparation method of the vulcanized rubber SX1 of the present embodiment is carried out as follows：
(1) in banbury, under 90rpm rotating speeds, by dience rubber and liquid rubber initial
30s is kneaded at 80 DEG C of temperature；
(2) the 3/4 of the weight for accounting for total reinforcing agent reinforcing agent, whole activator and complete is added
The first coupling agent Si69 mixings 2.5min in portion；
(3) remaining reinforcing agent, the rubber composition in addition to vulcanizing agent and vulcanization accelerator are added
Remaining ingredient in Z1, glue is unloaded after kneading 6min at this temperature after sizing material temperature reaches 150 DEG C
Material；
(4) sizing material is passed through three times in the mill that roll spacing is 5mm, roller temperature is 50 ± 5 DEG C, will
The batch mixing glue of acquisition parks 4h；
(5) the batch mixing glue and vulcanizing agent and vulcanization accelerator for obtaining step (4) are in initial temperature 40
Kneaded at ± 5 DEG C, the time to be mixed unloads sizing material when reaching 4min；
(6) sizing material for obtaining step (5) is in the mill that roll spacing is 0.5mm, roller temperature is 50 ± 5 DEG C
Pass through once on machine, roll spacing is then adjusted to 3mm, then by twice；The elastomeric compound of acquisition is parked
24h；
(7) sizing material that will be processed by step (6) vulcanizes 35 points under 160 DEG C, 15MPa pressure
Clock, obtains vulcanized rubber SX1.
The relevant parameter of the dience rubber T1 in the present embodiment is as shown in table 1；The rubber of the present embodiment
The composition and consumption (weight portion) of composition Z1 are as shown in table 2.
Embodiment 2
The preparation method of the vulcanized rubber SX2 of the present embodiment is carried out as follows：
(1) in banbury, under 90rpm rotating speeds, by dience rubber and liquid rubber initial
45s is kneaded under temperature 60 C；
(2) the 3/5 of the weight for accounting for total reinforcing agent reinforcing agent, whole activator and complete is added
The first coupling agent Si69 mixings 2min in portion；
(3) remaining reinforcing agent, the rubber composition in addition to vulcanizing agent and vulcanization accelerator are added
Remaining ingredient in Z2, sizing material is unloaded when sizing material temperature reaches 170 DEG C；
(4) sizing material is passed through three times in the mill that roll spacing is 5mm, roller temperature is 50 ± 5 DEG C, will
The batch mixing glue of acquisition parks 5h；
(5) the batch mixing glue and vulcanizing agent and vulcanization accelerator for obtaining step (4) are in initial temperature 40
Kneaded at ± 5 DEG C, sizing material is unloaded when sizing material temperature reaches 110 DEG C；
(6) sizing material for obtaining step (5) is in the mill that roll spacing is 0.5mm, roller temperature is 50 ± 5 DEG C
Pass through once on machine, roll spacing is then adjusted to 3mm, then by twice；The elastomeric compound of acquisition is parked
18h；
(7) sizing material that will be processed by step (6) vulcanizes 40 points under 150 DEG C, 15MPa pressure
Clock, obtains vulcanized rubber SX2.
The relevant parameter of the dience rubber T2 in the present embodiment is as shown in table 1；The rubber of the present embodiment
The composition and consumption (weight portion) of composition Z2 are as shown in table 2.
Embodiment 3
The preparation method of the vulcanized rubber SX3 of the present embodiment is carried out as follows：
(1) in banbury, under 90rpm rotating speeds, by dience rubber and liquid rubber initial
45s is kneaded under temperature 50 C；
(2) the 1/2 of the weight for accounting for total reinforcing agent reinforcing agent, whole activator and complete is added
The silane coupler Si75 mixings 3min in portion；
(3) remaining reinforcing agent, the rubber composition in addition to vulcanizing agent and vulcanization accelerator are added
Remaining ingredient in Z3, glue is unloaded after kneading 5min at this temperature after sizing material temperature reaches 155 DEG C
Material；
(4) sizing material is passed through three times in the mill that roll spacing is 5mm, roller temperature is 50 ± 5 DEG C, will
The batch mixing glue of acquisition parks 5h；
(5) the batch mixing glue and vulcanizing agent and vulcanization accelerator for obtaining step (4) are in initial temperature 40
Kneaded at ± 5 DEG C, sizing material is unloaded when sizing material temperature reaches 115 DEG C；
(6) sizing material for obtaining step (5) is in the mill that roll spacing is 0.5mm, roller temperature is 50 ± 5 DEG C
Pass through once on machine, roll spacing is then adjusted to 3mm, then by twice；The elastomeric compound of acquisition is parked
30h；
(7) sizing material that will be processed by step (6) vulcanizes 50 points under 140 DEG C, 14MPa pressure
Clock, obtains vulcanized rubber SX3.
The relevant parameter of the dience rubber T3 in the present embodiment is as shown in table 1；The rubber of the present embodiment
The composition and consumption (weight portion) of composition Z3 are as shown in table 2.
Embodiment 4
The present embodiment prepares vulcanized rubber SX4 using method similar to Example 1, except that,
The rubber composition used in the present embodiment be rubber composition Z4, and the composition of rubber composition Z4 and
Consumption (weight portion) is as shown in table 2.
Remaining is in the same manner as in Example 1, obtains vulcanized rubber SX4.
Embodiment 5
The present embodiment prepares vulcanized rubber SX5 using method similar to Example 2, except that,
The rubber composition used in the present embodiment be rubber composition Z5, and the composition of rubber composition Z5 and
Consumption (weight portion) is as shown in table 2.
Remaining is in the same manner as in Example 2, obtains vulcanized rubber SX5.
Embodiment 6
The present embodiment prepares vulcanized rubber SX6 using method similar to Example 3, except that,
The rubber composition used in the present embodiment be rubber composition Z6, and the composition of rubber composition Z6 and
Consumption (weight portion) is as shown in table 2.
Remaining is in the same manner as in Example 3, obtains vulcanized rubber SX6.
Embodiment 7
The present embodiment prepares vulcanized rubber SX7 using method similar to Example 1, except that,
The dience rubber used in the present embodiment is T4, and the relevant parameter of T4 is as shown in table 1, this implementation
The rubber composition used in example is rubber composition Z7, and the composition and consumption of rubber composition Z7 are (heavy
Amount part) as shown in table 2.
Remaining is in the same manner as in Example 1, obtains vulcanized rubber SX7.
Embodiment 8
The present embodiment prepares vulcanized rubber SX8 using method similar to Example 1, except that,
The dience rubber used in the present embodiment is T5, and the relevant parameter of T5 is as shown in table 1, this implementation
The rubber composition used in example is rubber composition Z8, and the composition and consumption of rubber composition Z8 are (heavy
Amount part) as shown in table 2.
Remaining is in the same manner as in Example 1, obtains vulcanized rubber SX8.
Embodiment 9
The present embodiment prepares vulcanized rubber SX9 using method similar to Example 1, except that,
The dience rubber used in the present embodiment is T6, and the relevant parameter of T6 is as shown in table 1, this implementation
The rubber composition used in example is rubber composition Z9, and the composition and consumption of rubber composition Z9 are (heavy
Amount part) as shown in table 2.
Remaining is in the same manner as in Example 1, obtains vulcanized rubber SX9.
Embodiment 10
The present embodiment prepares vulcanized rubber SX10 using method similar to Example 2, except that,
The rubber composition used in the present embodiment be rubber composition Z10, and rubber composition Z10 composition
And consumption (weight portion) is as shown in table 2.
Remaining is in the same manner as in Example 2, obtains vulcanized rubber SX10.
Embodiment 11
The present embodiment prepares vulcanized rubber SX11 using method similar to Example 3, except that,
The rubber composition used in the present embodiment be rubber composition Z11, and rubber composition Z11 composition
And consumption (weight portion) is as shown in table 2.
Remaining is in the same manner as in Example 3, obtains vulcanized rubber SX11.
Embodiment 12
The present embodiment prepares vulcanized rubber SX12 using method similar to Example 1, except that,
The rubber composition used in the present embodiment be rubber composition Z12, and rubber composition Z12 composition
And consumption (weight portion) is as shown in table 2.
Remaining is in the same manner as in Example 1, obtains vulcanized rubber SX12.
Embodiment 13
The present embodiment prepares vulcanized rubber SX13 using method similar to Example 1, except that,
The dience rubber used in the present embodiment is T7, and the relevant parameter of T7 is as shown in table 1, this implementation
The rubber composition that uses is rubber composition Z13 in example, and rubber composition Z13 composition and consumption
(weight portion) is as shown in table 2.
Remaining is in the same manner as in Example 1, obtains vulcanized rubber SX13.
Comparative example 1
This comparative example prepares vulcanized rubber DSX1 using method similar to Example 1, except that,
The rubber composition used in this comparative example be rubber composition DZ1, and rubber composition DZ1 group
Into and consumption (weight portion) as shown in table 2.
Remaining is in the same manner as in Example 1, obtains vulcanized rubber DSX1.
Comparative example 2
This comparative example prepares vulcanized rubber DSX2 using method similar to Example 1, except that,
The rubber composition used in this comparative example be rubber composition DZ2, and rubber composition DZ2 group
Into and consumption (weight portion) as shown in table 2.
Remaining is in the same manner as in Example 1, obtains vulcanized rubber DSX2.
Table 1
| SSBR2535E/ weight % | SSBR2506/ weight % | Polybutadiene rubber/weight % | |
| T1 | 75 | - | 25 |
| T2 | - | 100 | - |
| T3 | 70 | 10 | 20 |
| T4 | 85 | - | 15 |
| T5 | 60 | 20 | 20 |
| T6 | 45 | 30 | 25 |
| T7 | 100 | - | - |
Table 2
Test case
The performance of the vulcanized rubber that above-described embodiment and comparative example are prepared is tested as follows.
(1) Mooney viscosity：
According to GB/T 1232.1-2000 standard testings.
Preheated 1 minute at 100 ± 0.5 DEG C, tested 4 minutes.
(2) tensile property test：
According to GB《GB/T 528-1998 vulcanized rubbers or thermoplastic elastomer tensile stress-strain performance
Determine》In method test.
The AG-20KNG of puller system model Shimadzu Corporation production；Tear resistance is tested according to GB
《GB/T 529-1999 vulcanized rubbers or thermoplastic elastomer tearing strength measure (trousers shape, square and
Crescent sample)》In method test, puller system model Shimadzu Corporation production AG-20KNG.
Acquired results are as shown in table 3.
(" tensile strength/MPa ", " elongation/% ", " tearing strength/(kN/m) ", " 100% in table 3
Surely/MPa is stretched " and " 300% stretches/MPa surely " data).
(3) dynamic mechanical：
Temperature scanning is on German GABO companies EPLEXOR-500N dynamic thermomechanical analysis apparatus to sample
The viscoelastic behavior of product is tested.
Sample length is 35mm, and width is 8mm, and thickness is 1.0mm.Test uses stretch mode,
Test frequency be 11Hz, temperature range be -80~80 DEG C, heating rate be 3 DEG C/min, static strain 1%,
Dynamic strain 0.25%.
Acquired results are as shown in table 3 (" tan δ (0 DEG C) ", " tan δ (60 DEG C) " and " Tg/ DEG C " in table 3
Data).
Table 3
From the results shown in Table 3, the vulcanization that the rubber composition that the present invention is provided is prepared
The property of rubber is substantially better than the property of the vulcanized rubber that comparative example is prepared, and liquid of the invention
Body rubber can substitute processing oil and dispersion aids, while be applied in combination with dience rubber interworking, not only
Can be very good to solve white carbon difficulties in dispersion in rubber matrix, and tire finished product is during storage
Processing oil is readily migrate into tire finished surface, makes tire finished product that color change to occur and produces quality ripple
Dynamic problem, moreover it is possible to the performance of vulcanizate is significantly lifted, so as to obtain the tire of excellent combination property
Face glue material.Comparing between comparative example 1 and comparative example 2 can with it is further seen that, even if increasing
The consumption of polyethylene glycol, the lifting effect to the performance of the vulcanized rubber for obtaining also still is not so good as by rubber
The liquid rubber of silicon atoms is introduced in composition.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
The detail in mode is applied, in range of the technology design of the invention, can be to technical side of the invention
Case carries out various simple variants, and these simple variants belong to protection scope of the present invention.
Additionally, can also be combined between a variety of implementation methods of the invention, as long as its
Without prejudice to thought of the invention, it should equally be considered as content disclosed in this invention.
Claims (13)
1. a kind of rubber composition, said composition contain dience rubber, liquid rubber, reinforcing agent,
Vulcanizing agent, vulcanization accelerator, activator and the first coupling agent, it is characterised in that the liquid rubber is
The star-like styrene-butadiene polymer of both-end Si modification, styrene knot in the star-like styrene-butadiene polymer of the both-end Si modification
The content of structure unit is 10-30 weight %, and the content of 1,2 structure is 0-80 weight %, the both-end silicon
The number-average molecular weight of modified star-like styrene-butadiene polymer is 1000-30000.
2. composition according to claim 1, wherein, the star-like butylbenzene of the both-end Si modification
The content of styrol structural unit is 15-25 weight % in polymer, and the content of 1,2 structure is 40-70 weights
Amount %, the number-average molecular weight of the star-like styrene-butadiene polymer of the both-end Si modification is 3000-15000.
3. composition according to claim 1, wherein, the star-like butylbenzene of the both-end Si modification
Polymer by by styrene monomer and divinylic monomer successively with initiator, the second coupling agent, end-capping reagent
Contacted and be obtained, wherein, the initiator has the structure as shown in following formula (I)：
Wherein, R1、R2And R3It is each independently selected from alkyl, the monoolefine of C2~C20 of C1~C20
The aralkyl of base or C6~C20, R4Selected from the alkylidene of C1~C20, it is preferable that R1、R2And R3
It is each independently selected from the alkyl of C1~C12, R4Selected from the alkylidene of C2~C5；
Second coupling agent be in p-divinyl benzene, m-divinyl benzene and adjacent divinylbenzene extremely
Few one kind, it is preferable that second coupling agent is p-divinyl benzene and/or m-divinyl benzene；And
The end-capping reagent is the alkoxy silane containing monochloro or single bromine, it is preferable that the end-capping reagent is selected from three
Methoxyl group chlorosilane, the ethyoxyl chlorosilane of dimethoxy one, the methoxyl group chlorosilane of diethoxy one, three second
Epoxide chlorosilane, the ethyoxyl bromo-silicane of dimethoxy one, the methoxyl group bromo-silicane of diethoxy one, trimethoxy
Bromide silane, triethoxy bromo-silicane, r-chloropropyl trimethoxyl silane, chloropropyl triethoxysilane,
The methoxy silane of chloropropyl diethoxy one, bromopropyl trimethoxy silane, bromopropyl triethoxysilane
With at least one in the methoxy silane of bromopropyl diethoxy one.
4. the composition according to any one in claim 1-3, wherein, the alkadienes rubber
Glue is selected from least in polybutadiene rubber, oil-filled solution polymerized butadiene styrene rubber and non-oil-filled solution polymerized butadiene styrene rubber
Kind；Preferably
In the dience rubber containing 0.1-100 weight %, preferably 50-100 weight %, further it is excellent
Select the described oil-filled solution polymerized butadiene styrene rubber of 70-100 weight %.
5. composition according to claim 4, wherein, benzene in the oil-filled solution polymerized butadiene styrene rubber
The content of ethylene unit unit is 10-30 weight %, and the content of 1,2 structure is 40-70 weight %, Mooney
Viscosity is 50-70, and oil-filled number is 20-50 parts；Preferably
The content of styrol structural unit is 15-25 weight %, 1,2 in the oil-filled solution polymerized butadiene styrene rubber
The content of structure is 50-65 weight %, and Mooney viscosity is 55-65, and oil-filled number is 30-40 parts.
6. composition according to claim 4, wherein, the polybutadiene rubber is along fourth rubber
Glue；Cis-structure content in preferably described butadiene rubber is more than or equal to 95 weight %.
7. the composition according to any one in claim 1-3, wherein, with 100 weight portions
The dience rubber on the basis of, the content of the liquid rubber is 5-35 weight portions, the enhancing
The content of agent is 50-95 weight portions, and the content of the vulcanizing agent is 0.5-5 weight portions, and the vulcanization promotees
Enter the content of agent for 1-6 weight portions, the content of the activator is 3-8 weight portions, first coupling
The content of agent is 3-10 weight portions；Preferably
On the basis of the dience rubber of 100 weight portions, the content of the liquid rubber is 8-30
Weight portion, the content of the reinforcing agent is 60-85 weight portions, and the content of the vulcanizing agent is 1-3.5 weights
Amount part, the content of the vulcanization accelerator is 2-4 weight portions, and the content of the activator is 4-6 weight
Part, the content of first coupling agent is 5-8 weight portions.
8. the composition according to any one in claim 1-3, wherein, in the reinforcing agent
Containing more than 50 weight % white carbons；Preferably
Contain the white carbon of 80-100 weight % in the reinforcing agent；Further preferably
Also contain carbon black in the reinforcing agent.
9. the composition according to any one in claim 1-3, wherein,
The vulcanizing agent be insoluble oil-filled sulphur, two thio morpholines and four vulcanization two morpholines in extremely
Few one kind；
The vulcanization accelerator is sulfenamide vulcanization accelerator and/or guanidine vulcanization accelerator；
The activator is zinc oxide and/or stearic acid；
First coupling agent is the silane coupler of sulfur atom-containing and alkoxy.
10. the composition according to any one in claim 1-3, wherein, in the composition
Further contain age resistor and/or microwax；Preferably
On the basis of the dience rubber of 100 weight portions, the content of the age resistor is 1-5 weight portions,
The content of the microwax is 0.1-2 weight portions.
A kind of 11. preparation methods of vulcanized rubber, methods described includes will be any in claim 1-10
The each component in composition described in one is kneaded, and obtains elastomeric compound, then enters the elastomeric compound
Row vulcanization；Preferably
The condition of the vulcanization includes that the temperature of vulcanization is 140-160 DEG C, and the pressure of vulcanization is 5-15MPa,
The time of vulcanization is 10-50 minutes.
12. vulcanized rubbers prepared as the method described in claim 11.
Vulcanized rubber described in 13. claims 12 as tire tread material application.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN109369998A (en) * | 2018-09-30 | 2019-02-22 | 安徽佳通乘用子午线轮胎有限公司 | A kind of high humidity grabs the Tire tread rubber composition of performance and low rolling resistance |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109575387A (en) * | 2017-09-29 | 2019-04-05 | 中国石油化工股份有限公司 | Tire tread rubber composition and vulcanized rubber and its preparation method and application |
| CN107698831A (en) * | 2017-10-18 | 2018-02-16 | 正新橡胶（中国）有限公司 | Tire tread rubber composition |
| CN107698831B (en) * | 2017-10-18 | 2020-07-28 | 正新橡胶（中国）有限公司 | Tire tread rubber composition |
| CN109929160A (en) * | 2017-12-15 | 2019-06-25 | 中国石油化工股份有限公司 | The application of organo silane coupling agent and rubber composition and vulcanized rubber and its preparation method and application |
| CN109929160B (en) * | 2017-12-15 | 2021-08-03 | 中国石油化工股份有限公司 | Application of organosilane coupling agent, rubber composition, vulcanized rubber and preparation method and application thereof |
| CN109369998A (en) * | 2018-09-30 | 2019-02-22 | 安徽佳通乘用子午线轮胎有限公司 | A kind of high humidity grabs the Tire tread rubber composition of performance and low rolling resistance |
| CN114479217A (en) * | 2020-10-23 | 2022-05-13 | 北京化工大学 | Low rolling resistance and high wet-skid resistance solution-polymerized styrene-butadiene rubber composite material as well as preparation method and application thereof |
| CN114479217B (en) * | 2020-10-23 | 2023-02-28 | 北京化工大学 | Low rolling resistance and high wet-skid resistance solution-polymerized styrene-butadiene rubber composite material as well as preparation method and application thereof |
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