CN106700159B - Rubber composition and vulcanized rubber and its preparation method and application - Google Patents
Rubber composition and vulcanized rubber and its preparation method and application Download PDFInfo
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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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- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
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Abstract
The present invention relates to rubber materials, disclose a kind of rubber composition, the composition contains dience rubber, liquid rubber, reinforcing agent, vulcanizing agent, vulcanization accelerator, activator and the first coupling agent, it is characterized in that, the liquid rubber is the liquid rubber of silicon atoms, and the liquid rubber of the silicon atoms is the star-like styrene-butadiene polymer of both-end Si modification.The invention also discloses the methods for using rubber composition preparation vulcanized rubber and obtained vulcanized rubber and the vulcanized rubber as the application in tire tread material.Rubber composition provided by the invention has well solved tire finished product processing oil during storage and has been readily migrate into tire finished surface, makes tire finished product that color change occur and leads to the problem of quality fluctuation.There is lower rolling resistance and preferable wet-sliding resistant performance, excellent combination property using the vulcanized rubber that rubber composition provided by the invention is prepared.
Description
Technical field
The present invention relates to rubber materials, and in particular, to a kind of rubber composition, a kind of vulcanized rubber and preparation method thereof
And application.
Background technique
With becoming increasingly popular for automobile, the dosage of petroleum and the discharge amount of carbon dioxide are also higher and higher therewith, and by
This results in warming for the in short supply and global climate of petroleum resources.Therefore, the auto industry revolution of a reduction oil consumption is directly drawn
Requirement of the automaker to tire drag is reduced is sent out.In the resistance for hindering automobile to advance, rolling resistance accounts for 18-
30%, rolling resistance energy consumption accounts for about the 14.4% of fuel consumption, it means that rolling resistance reduces by 30%, then can fuel-economizing 4.5-6%.
While reducing rolling resistance, demand that tire should also have preferable wet-sliding resistant performance to be just able to satisfy industrial application.
Under normal conditions, the fissipation factor that anti-slippery and rolling resistance can respectively by vulcanized rubber in 0 DEG C and 60 DEG C
Tan δ value characterizes.Tan δ value at 0 DEG C is bigger, and anti-slippery is better；Tan δ value at 60 DEG C is smaller, and rolling resistance is lower.
Sizing material is set to obtain good comprehensive performance, tan δ value when should increase 0 DEG C as far as possible, tan δ value when reducing 60 DEG C.
In terms of reducing rolling resistance, the direction studied at present is more, including the design of raw rubber structure, raw rubber are modified, processing
The many aspects such as process modification, Design of Tire Structure, tyre tread design.
US6184296 is used by the modified crosslinking in surface along fourth and butylbenzene powdered rubber (swelling index 4~5, partial size 60
~450nm), reduce the rolling resistance of natural rubber (NR) formula system vulcanizate, but strength property is uninfluenced.
US6133364 is grafted to 1-chloro-4-methyl-benzene on crosslinking butylbenzene powdered rubber surface, is then used in NR formula system,
Making the rolling resistance of vulcanizate reduces, and anti-slippery improves.Crosslinking butylbenzene powder US6207757 modified with 1-chloro-4-methyl-benzene
Last rubber haved the function that reduce NR formula system vulcanizate rolling resistance, while improving the hauling ability of tire and durable
Property.
Polar group is introduced in above patent document, but all there is complex process, and can not play processing simultaneously
The defect of the effect of oil.It is well known that needing to be added processability of the processing oil to improve sizing material in rubber product preparation process
It can and reduce cost.In tire art, with the proposition of " green tire " concept, formula design is varied.Because green
For the filling system of tire based on white carbon black, white carbon black is highly polar substance, the difficulties in dispersion in rubber matrix, it is therefore desirable to
The dispersion aids such as polyethylene glycol are added to solve the dispersion of white carbon black.As it can be seen that both needing to introduce in green tire formula
Processing oil needs to introduce dispersion aids again, and the packing variety of addition is more.Processing oil used at present is aromatic naphtha, naphthenic oil etc.
Apolar substance, and molecular weight is relatively low, is readily migrate into product surface during tire products storage, makes product that face occur
Color change and generation quality fluctuation.
Also there is the research that processing oil is replaced using liquid rubber, but liquid rubber used is still nonpolarity, be can do nothing to help
White carbon black uniformly disperses in rubber.Such as CN101792545B discloses a kind of isoprene liquid rubber, it is therefore an objective to be
The high wet-sliding resistant of rubber is reduced, but this liquid rubber is only applicable to carbon black system, act in white carbon black system unknown
It is aobvious.
Summary of the invention
It is readily migrate into tire finished surface in order to solve tire finished product processing oil during storage, sends out tire finished product
Raw color change and leads to the problem of quality fluctuation, the present invention provides the new rubber composition of one kind, vulcanized rubber and its
Preparation method and application.
The present inventor has found after studying, and dience rubber and liquid rubber interworking is used, wherein liquid rubber
Glue is the liquid rubber of silicon atoms, can well solve tire finished product processing oil during storage and be readily migrate into tire
Finished surface makes tire finished product that color change occur and lead to the problem of quality fluctuation, but also can solve white carbon black in rubber
In matrix body the problem of difficulties in dispersion, so as to complete the present invention.
In a first aspect, the present invention provides a kind of rubber composition, the composition contains dience rubber, liquid rubber, increasing
Strong agent, vulcanizing agent, vulcanization accelerator, activator and the first coupling agent, the liquid rubber are the star-like butylbenzene of both-end Si modification
Polymer, the content of styrol structural unit is 10-30 weight %, 1,2 knot in the star-like styrene-butadiene polymer of the both-end Si modification
The content of structure is 0-80 weight %, and the number-average molecular weight of the star-like styrene-butadiene polymer of the both-end Si modification is 1000-30000.
Second aspect, the present invention provide a kind of preparation method of vulcanized rubber, and this method includes by according to the present invention the
On the one hand each component in rubber composition provided is kneaded, and is obtained rubber compound, is then vulcanized the rubber compound.
The third aspect, the present invention provide the vulcanized rubber being prepared by the method for the second aspect invented.
Fourth aspect, the present invention provide application of the vulcanized rubber as tire tread material.
Due to introducing the liquid rubbers of silicon atoms in rubber composition provided by the invention, substitution filling oil is played
With the multi-function action of dispersion aids, thus well solved white carbon black in rubber matrix difficulties in dispersion and tire at
Product processing oil during storage is readily migrate into tire finished surface, makes tire finished product that color change occur and generates quality
The problem of fluctuation.
The vulcanized rubber being prepared using rubber composition provided by the invention is with lower rolling resistance and preferably
Wet-sliding resistant performance, excellent combination property.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
According to the first aspect of the invention, the present invention provides a kind of rubber composition, the composition contains alkadienes rubber
Glue, liquid rubber, reinforcing agent, vulcanizing agent, vulcanization accelerator, activator and the first coupling agent, the liquid rubber are both-end silicon
Modified star-like styrene-butadiene polymer, the content of styrol structural unit is 10- in the star-like styrene-butadiene polymer of the both-end Si modification
30 weight %, the content of 1,2 structure are 0-80 weight %, the number-average molecular weight of the star-like styrene-butadiene polymer of the both-end Si modification
For 1000-30000.
Preferably, the content of styrol structural unit is 15-25 weight in the star-like styrene-butadiene polymer of the both-end Si modification
% is measured, the content of 1,2 structure is 40-70 weight %, and the number-average molecular weight of the star-like styrene-butadiene polymer of the both-end Si modification 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；It is more excellent
Selection of land molecular weight distributing index is 1.06-1.15.
In the present invention, number-average molecular weight and molecular weight distributing index are detected according to gel permeation chromatography (GPC).
Preferably, the star-like styrene-butadiene polymer of the both-end Si modification by by styrene monomer and divinylic monomer successively
It is contacted and is made with initiator, the second coupling agent, end-capping reagent, wherein the initiator has to be tied as shown in following formula (I)
Structure:
Wherein, R1、R2And R3It is each independently selected from the alkyl of C1~C20, the monoene alkyl of C2~C20 or C6~C20
Aralkyl, R4Alkylidene selected from C1~C20.
Preferably, the initiator with structure shown in formula (I) the preparation method is as follows:
Under the protection of inert gas, halogenated silanes shown in formula (II) is contacted in organic solvent with lithium, then from
Siliceous organic lithium initiator (the as initiator of structure shown in formula (I)) is obtained in obtained contact mixture,
Wherein, R1、R2、R3And R4Same as described above, X is Cl or Br.
Preferably, the alkyl of the C1~C20 of the invention includes the straight chained alkyl of C1-C20 and the branched alkane of C3-C20
The naphthenic base of base and C3-C20, specific example can include but is not limited to: methyl, ethyl, n-propyl, isopropyl, positive fourth
Base, sec-butyl, isobutyl group, tert-butyl, n-pentyl, isopentyl, tertiary pentyl, neopentyl, n-hexyl, cyclopropyl, cyclopenta, hexamethylene
Base, 4- methylcyclohexyl, 4- ethylcyclohexyl, 4- n-propyl cyclohexyl, 4- normal-butyl cyclohexyl, cyclooctyl and 2- ethyl ring ten
Diyl.
Preferably, the monoene alkyl of the C2~C20 of the invention includes the straight monoene alkyl and C4-C20 of C2-C20
Branched monoolefins base, specific example can include but is not limited to: vinyl, acrylic, 2- methyl -2- pentenyl, 2- first
Base -3- ethyl-laurylene base.
Preferably, the specific example of the aralkyl of the C6~C20 of the invention can include but is not limited to: phenyl, naphthalene
Base, 4- aminomethyl phenyl, 4- ethylphenyl, 2- isobutyl phenenyl and 4,5 ,-dimethyl naphthalene.
Preferably, in the structure shown in formula (I) and formula (II), R1、R2And R3It is each independently selected from the alkane of C1~C20
Base, the further preferably alkyl of C1~C12.R4The preferably alkylidene of C1~C20, the further preferably alkylene of C2~C5
Base.
It is further preferred that in the structure shown in formula (I) and formula (II), R1、R2And R3Be each independently selected from methyl,
Ethyl, n-propyl and isopropyl, R4For ethylidene or propylidene.
Preferably, the molar ratio of the halogenated silanes and lithium is 1:(2~10), more preferably 1:(2.5~5.0).
Preferably, it is -30~30 DEG C that the halogenated silanes, which includes temperature with the condition that lithium contacts in organic solvent, preferably
It is -5~15 DEG C, the time is 5~100h, preferably 15~50h.Preferably, the halogenated silanes connects in organic solvent with lithium
The mode of touching includes: after the ratio by halogenated silanes and the organic solvent with volume ratio for 1:(2-6) mixes, with 0.5~
10mL/h, the preferably rate of 1.5~3.5mL/h are added in the organic solvent containing lithium and are contacted.Preferably, in order to as far as possible
The generation of side reaction is reduced, the contact carries out under agitation.
The inert gas, which refers to, does not occur chemical phase with reactant, reaction product and solvent under the contacting conditions
The gas of interaction, such as: group 0 element gas.The preferred argon gas of inert gas.
The process that siliceous organic lithium initiator is obtained from obtained contact mixture can be in the guarantor of inert gas
Shield is lower to be carried out.The inert gas is preferably same as above.It is described that siliceous organolithium initiation is obtained from obtained contact mixture
The operation of agent for example may include: that the contact mixture is carried out sedimentation and obtains supernatant, so under the protection of inert gas
Supernatant is filtered with sand core filter bulb afterwards.The condition of the sedimentation may include standing 1-10 hours.Sedimentation can make anti-
The lithium halide (lithium chloride or lithium bromide) and lithia that should be generated precipitate.The aperture of the sand core filter bulb can be 3~4
μm.Sand core filter bulb can filter out the inorganic matters such as remaining lithium in contact mixture, the lithium halide that reaction generates and lithia, from
And obtain more pure siliceous organic lithium initiator.
Preferably, second coupling agent be in p-divinyl benzene, m-divinyl benzene and adjacent divinylbenzene extremely
Few one kind；It is further preferred that second coupling agent is p-divinyl benzene and/or m-divinyl benzene.
Preferably, the end-capping reagent is the alkoxy silane containing monochloro or single bromine；It is further preferred that the end-capping reagent is selected from
Trimethoxy chlorosilane, one ethyoxyl chlorosilane of dimethoxy, one methoxyl group chlorosilane of diethoxy, triethoxychlorosilane,
One ethyoxyl bromo-silicane of dimethoxy, one methoxyl group bromo-silicane of diethoxy, trimethoxy bromo-silicane, triethoxy bromo-silicane,
R-chloropropyl trimethoxyl silane, chloropropyl triethoxysilane, one methoxy silane of chloropropyl diethoxy, bromopropyl trimethoxy
At least one of one methoxy silane of base silane, bromopropyl triethoxysilane and bromopropyl diethoxy.
According to a kind of preferred embodiment, the star-like styrene-butadiene polymer of the both-end Si modification is as follows
It is prepared:
(1) in a solvent, in the presence of structure regulator, styrene monomer and divinylic monomer are connect with initiator
Touching carries out polymerisation in solution, obtains styrene butadiene random copolymer；The initiator has to be tied as shown in following formula (I)
Structure:
Wherein, R1、R2And R3It is each independently selected from the alkyl of C1~C20, the monoene alkyl of C2~C20 or C6~C20
Aralkyl, R4Alkylidene selected from C1~C20；
(2) styrene butadiene random copolymer that step (1) obtains is contacted with the second coupling agent to carry out idol
Connection reaction, the styrene butadiene random copolymer being coupled；
(3) styrene butadiene random copolymer for the coupling that step (2) obtains is contacted with end-capping reagent to institute
The styrene butadiene random copolymer for stating coupling is blocked.
Preferably, in step (1), the styrene monomer accounts for the 15-45 weight % of reaction monomers total amount.The reaction
Monomer total amount is the weight summation of styrene monomer and divinylic monomer.In step (1), the solvent can be for for solution
The common solvent of polymerization as long as the solvent is in a liquid state under the polymerization conditions, and cannot participate in polymerization reaction, will not
It reacts with the polymer reacted.Preferably, the solvent be cycloalkane, aromatic hydrocarbons and isoparaffin at least
It is a kind of.Specifically, the solvent can for benzene, toluene, ethylbenzene, dimethylbenzene, mixed xylenes, n-hexane, hexamethylene, pentane,
It heptane, octane and at least one of raffinates oil.Described raffinate oil is catalytic reforming in petroleum refining process, rich in aromatic hydrocarbons
Product remaining distillate after extracting aromatic hydrocarbons.Preferably, the solvent is the mixed solvent of hexamethylene and n-hexane, wherein
The weight ratio of hexamethylene and n-hexane is preferably (4-9): 1.The dosage of the solvent can be selected according to the amount of polymerized monomer
It selects.Generally, the dosage of the solvent makes in step (1) that monomer concentration is in the range of 5-30 weight %, preferably in 10-20
In the range of weight %.Preferably, in step (1), the structure regulator be used to making styrene monomer in step (1) and
Divinylic monomer realizes copolymerization, can be the common various compounds that can be realized above-mentioned function.Generally, the structure tune
Saving agent can be the compound containing oxygen atom, nitrogen-atoms, sulphur atom or phosphorus atoms in molecular structure.Specifically, the structure
Regulator can be selected from ether, butyl oxide, tetrahydrofuran (THF), glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofurfuryl alcohol second
Ether, tetrahydrofurfuryl alcohol butyl ether, dioxane, crown ether, triethylamine, tetramethylethylenediamine, hexamethylphosphoramide, potassium tert-butoxide, uncle
At least one of amylalcohol potassium, potassium lauryl, alkyl benzene sulphonate potassium and sodium alkyl benzene sulfonate, preferably tetrahydrofurfuryl alcohol ether.To institute
The dosage for stating structure regulator is not particularly limited, and those skilled in the art combine specific poly- according to the common sense of this field
Conjunction condition can make appropriate choice.Such as when select tetrahydrofurfuryl alcohol ether as structure regulator when, with all solvents with
On the basis of monomer gross mass, the additional amount of structure regulator can be 50-500ppm, preferably 200-400ppm.Preferably, exist
In step (1), the solution polymerization condition includes that temperature is 30-70 DEG C, and the time is 10-100 minutes.
Preferably, in terms of elemental lithium, the dosage molar ratio of the initiator and second coupling agent is the initiator
1:(1.5-10), more preferably 1:(3-5).Preferably, in step (2), the condition of the coupling reaction includes that temperature is
40-100 DEG C, the time is 10-60 minutes.
Preferably, in step (3), the condition blocked includes that temperature is 20-100 DEG C, and the time is 5-40 points
Clock.
In composition provided by the invention, the dience rubber can selected from polybutadiene rubber, oil-filled contain intermingle with fourth
At least one of benzene rubber and non-oil-filled solution polymerized butadiene styrene rubber.Preferably, at least containing oil-filled molten in the dience rubber
Poly- butadiene-styrene rubber.For example, the dience rubber is oil-filled solution polymerized butadiene styrene rubber or oil-filled solution polymerized butadiene styrene rubber and polybutadiene
The combination of alkene rubber perhaps combination or oil-filled solution polymerized butylbenzene of the oil-filled solution polymerized butadiene styrene rubber with non-oil-filled solution polymerized butadiene styrene rubber
The combination of rubber and polybutadiene rubber and non-oil-filled solution polymerized butadiene styrene rubber.
Preferably, the oil-filled solution polymerized butadiene styrene rubber of 0.1-100 weight % is contained in the dience rubber；It is more excellent
Selection of land, the oil-filled solution polymerized butadiene styrene rubber containing 50-100 weight % in the dience rubber；It is further preferred that described
Contain the oil-filled solution polymerized butadiene styrene rubber of 70-100 weight % in dience rubber.
Under preferable case, in the oil-filled solution polymerized butadiene styrene rubber content of styrol structural unit be 10-30 weight %, 1,
The content of 2 structures is 40-70 weight %, and Mooney viscosity 50-70, oil-filled number is 20-50 parts；In more preferred situation, institute
The content for stating styrol structural unit in oil-filled solution polymerized butadiene styrene rubber is 15-25 weight %, and the content of 1,2 structure is 50-65 weight
%, Mooney viscosity 55-65 are measured, oil-filled number is 30-40 parts.The rubber calculating that the oil-filled number refers to 100 parts by weight,
Fill the parts by weight of oil.
In the present invention, it should be strongly noted that unless stated otherwise, the metering in relation to oil-filled solution polymerized butadiene styrene rubber is equal
It is to be calculated on the basis of butt, that is to say, that do not include filling out in the metering of related oil-filled solution polymerized butadiene styrene rubber of the invention
Oil-filled number.
Preferably, the polybutadiene rubber is butadiene rubber.It is further preferred that the cis-structure in the butadiene rubber
Content is more than or equal to 95 weight %.
In composition provided by the invention, it is preferable that described on the basis of the dience rubber of 100 parts by weight
The content of liquid rubber is 5-35 parts by weight, and the content of the reinforcing agent is 50-95 parts by weight, and the content of the vulcanizing agent is
0.5-5 parts by weight, the content of the vulcanization accelerator are 1-6 parts by weight, and the content of the activator is 3-8 parts by weight, described
The content of first coupling agent is 3-10 parts by weight.
In more preferred situation, on the basis of the dience rubber of 100 parts by weight, the content of the liquid rubber is
8-30 parts by weight, the content of the reinforcing agent are 60-85 parts by weight, and the content of the vulcanizing agent is 1-3.5 parts by weight, the sulphur
The content for changing promotor is 2-4 parts by weight, and the content of the activator is 4-6 parts by weight, and the content of first coupling agent is
5-8 parts by weight.
Preferably, containing greater than 50 weight % white carbon blacks in the reinforcing agent；Contain 80- in the more preferred reinforcing agent
The white carbon black of 100 weight %.
Under preferable case, also contain carbon black in the reinforcing agent, it is preferable that in the reinforcing agent, the carbon black contains
Amount is 0.001-20 weight %, further preferably 5-15 weight %.
According to a kind of preferred embodiment, the reinforcing agent of the invention is made of white carbon black and carbon black.
Preferably, the vulcanizing agent is insoluble oil-filled sulphur, two thio morpholines and four vulcanize in two morpholines extremely
Few one kind.
Preferably, the vulcanization accelerator is sulfenamide vulcanization accelerator and/or guanidine vulcanization accelerator.It is more excellent
Selecting the sulfenamide vulcanization accelerator is N- tert-butyl -2-[4-morpholinodithio base sulfenamide (accelerator TBBS), N- hexamethylene
At least one of base -2-[4-morpholinodithio base sulfenamide and N- oxygen diethylidene -2-[4-morpholinodithio base sulfenamide.It is more excellent
Selecting the guanidine vulcanization accelerator is diphenylguanidine (diphenylguanidine) and/or di-o-tolylguanidine.It is particularly preferred that the vulcanization promotes
Agent 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 coupling agent of sulfur atom-containing and alkoxy.It is further preferred that described
First coupling agent is double-[γ-(triethoxysilicane) propyl] tetrasulfide (Si69) and/or double-(γ-triethoxy silicon substrate third
Base) disulphide (Si75).
Preferably, composition provided by the invention further contains anti-aging agent and/or microwax.
Preferably, the microwax is mainly by C20-60Cycloalkane and it is a small amount of just, isoparaffin composition, fusing point 60-
95 DEG C, molecular weight 580-700.
Preferably, described on the basis of the dience rubber of 100 parts by weight when containing anti-aging agent in the composition
The content of anti-aging agent is 1-5 parts by weight, preferably 2-4 parts by weight.
Preferably, described on the basis of the dience rubber of 100 parts by weight when containing microwax in the composition
The content of microwax is 0.1-2 parts by weight, preferably 0.5-1.5 parts by weight.
Preferably, the anti-aging agent is amines antioxidants and/or quinoline type antioxidant.The more preferred amines antioxidants
For N- isopropyl-N '-diphenyl-para-phenylene diamine, N- (1,3 dimethylbutyl)-N '-diphenyl-para-phenylene diamine and the bis- (1,4- bis- of N, N '-
At least one of methyl amyl) p-phenylenediamine.The more preferred quinoline type antioxidant is 2,2,4- trimethyl -1,2- dihydro
Change quinoline condensate, 6- ethyoxyl -2,2,4- trimethyl -1,2- dihyaroquinoline and 6- dodecyl -2,2, trimethyl -1 4-,
At least one of 2- dihyaroquinoline.
According to the second aspect of the invention, the present invention provides a kind of preparation method of vulcanized rubber, the method includes
Each component in above-mentioned composition is kneaded, rubber compound is obtained, then vulcanizes the rubber compound.
It is each in the rubber composition (also referred to as composition) in the preparation method of vulcanized rubber provided by the invention
The type and content of component can will not repeat herein according to being reasonably selected above.
In the preparation method of vulcanized rubber provided by the invention, the method and condition of the mixing can be this field
Conventional selection.For example, the mixing can carry out in open mill or mixer.
Preferably, it is 140-160 DEG C that the condition of the vulcanization, which includes the temperature of vulcanization, and the pressure of vulcanization is 5-15MPa, sulphur
The time of change is 10-50 minutes.
The method of a kind of preferred embodiment according to the present invention, the preparation vulcanized rubber can be according to as follows
Mode carries out:
(1) in mixer, dience rubber and liquid rubber is added, and be kneaded 30- at 50-80 DEG C of initial temperature
60s；
(2) reinforcing agent of the weight of the 1/2-3/4 of whole reinforcing agents and the activator of whole and whole are added
Silane coupling agent is kneaded 2-3min；
(3) remaining reinforcing agent, whole components other than vulcanizing agent and vulcanization accelerator is added, is reached to sizing material temperature
Reach 5-7min to mixing time after 150-160 DEG C or when sizing material temperature reaches 170 DEG C unloads sizing material；
(4) sizing material is passed through on the open mill that roll spacing is 3-7mm, roller temperature is 50 ± 5 DEG C three times, by the mixing glue of acquisition
Park 3-5h；
(5) mixing glue, vulcanizing agent and vulcanization accelerator that step (4) obtain are kneaded at 40 ± 5 DEG C of initial temperature, to
Sizing material temperature reaches 100-120 DEG C or when mixing time reaches 2-4min unloads sizing material；
(6) sizing material for obtaining step (5) passes through one on the open mill that roll spacing is 0.4-0.6mm, roller temperature is 50 ± 5 DEG C
It is secondary, roll spacing is then adjusted to 2-4mm, then by twice；The rubber compound of acquisition is parked into 18-30h；
(7) it will vulcanize 10-50 minutes under 140-160 DEG C, 5-15MPa pressure by the sizing material of step (6) processing, obtain
Vulcanized rubber.
According to the third aspect of the invention we, the present invention also provides vulcanized rubbers prepared by the above method.
According to the fourth aspect of the invention, the answering as tire tread material the present invention also provides above-mentioned vulcanized rubber
With.
It 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 commodity for being SSBR2535E purchased from the middle petrochemical industry Yanshan Petrochemical company trade mark, wherein benzene
The content of ethylene unit unit is 25 weight %, and the content of 1,2 structure is 62 weight %, Mooney viscosity 57, and oil-filled number is
37.5 parts.
Non- oil-filled solution polymerized butadiene styrene rubber is the commodity for being SSBR2506 purchased from the middle petrochemical industry Yanshan Petrochemical company trade mark, wherein
The content of styrol structural unit is 25 weight %, and the content of 1,2 structure is 60 weight %, Mooney viscosity 65.
Polybutadiene rubber is the commodity for being BR9000 purchased from the middle petrochemical industry Yanshan Petrochemical company trade mark, and cis-structure contains
Amount is 97 weight %.
White carbon black (reinforcing agent) is the commodity for being 165GR purchased from Rhodia (Qingdao) Co., Ltd trade mark.
Carbon black (reinforcing agent) is the commodity for being N330 purchased from the hundred million Bo Rui Chemical Co., Ltd. trade mark of Tianjin.
Si69, Si75 (the first coupling agent) are the commodity purchased from Shanghai Rui Shi Chemical Industry Science Co., Ltd.
SA (stearic acid) (activator) is the commodity purchased from Sinopharm Chemical Reagent Co., Ltd..
Antioxidant 4010 (anti-aging agent) is the commodity purchased from Gaoyi County benefit and Chemical Co., Ltd..
Microwax is the commodity for being W-445 purchased from the Tianjin source the perseverance Sheng Xin International Trading Company Ltd trade mark, carbon atom number
For 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 commodity purchased from Guangdong Du Ba new material Science and Technology Ltd..
Vulcanizing agent used below is two thio morpholines, is purchased from Hangzhou Hai Rui Chemical Co., Ltd..
Mixer is U.S. law Lai Er BR1600 type, mold cavity volume 1.5L.
Vulcanizing press is industrial (Anhui) the Co., Ltd production of huge rock oil pressure, model P-50-PCD-3L.
TDAE (Treated Distillate Aromatic Extract) (filling oil) is to moisten rubber purchased from Qingzhou City Ostwald-Folin
The commodity of glue Co., Ltd.
PEG4000 (polyethylene glycol) is the commodity purchased from Nanjing Run Bang Chemical Co., Ltd..
Preparation example 1-6 is for providing initiator.
Preparation example 1a-6a is for providing 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 total amount phase for the rubber composition being related to below
It together, is 1200g.
Preparation example 1
Under argon gas protection, in three neck round bottom flask, hexamethylene/n-hexane mixed solvent is added (by Sinopec Beijing
One factory of Yanshan Mountain branch company synthetic rubber provides, and the mass ratio of cyclohexane and n-hexane is 5:1, similarly hereinafter) and 1.05g lithium sand
(0.15mol containing lithium, the average grain diameter of lithium sand are 0.8mm).Then it is sucked with syringe molten by 40mL hexamethylene/n-hexane mixing
The mixture of agent and 0.059mol chloropropyl trimethyl silane composition, connects syringe with three-necked flask, the liquid in syringe
Body is added drop-wise in flask with the speed of 1.67mL/h, is reacted 40 hours under 0 DEG C and stirring condition.
Then stop stirring, stand 5 hours, the lithium chloride and lithia for generating reaction precipitate.It is protected again in argon gas
Under shield, supernatant is transferred in a new flask, is filtered out with the sand core filter bulb that average pore size is 3 μm remaining in supernatant
The inorganic matters such as lithium sand, lithium chloride and lithia obtain initiator Y1.
Preparation example 2
Under argon gas protection, in three neck round bottom flask, hexamethylene/n-hexane mixed solvent is added (by Sinopec Beijing
One factory of Yanshan Mountain branch company synthetic rubber provides, and the mass ratio of cyclohexane and n-hexane is 5:1, similarly hereinafter) and 1.05g lithium sand
(0.15mol containing lithium, the average grain diameter of lithium sand are 0.8mm).Then it is sucked with syringe molten by 50mL hexamethylene/n-hexane mixing
The mixture of agent and 0.03mol chloroethyl -1,2- dimethyl -3- ethylsilane composition, connects syringe with three-necked flask, infuses
Liquid in emitter is added drop-wise in flask with the speed of 2.0mL/h, is reacted 24 hours under 15 DEG C and stirring condition.
Then stop stirring, stand 2 hours, the lithium chloride and lithia for generating reaction precipitate.It is protected again in argon gas
Under shield, supernatant is transferred in a new flask, is filtered out with the sand core filter bulb that average pore size is 3 μm remaining in supernatant
The inorganic matters such as lithium sand, lithium chloride and lithia obtain initiator Y2.
Preparation example 3
Under argon gas protection, in three neck round bottom flask, hexamethylene/n-hexane mixed solvent is added (by Sinopec Beijing
One factory of Yanshan Mountain branch company synthetic rubber provides, and the mass ratio of cyclohexane and n-hexane is 5:1, similarly hereinafter) and 1.05g lithium sand
(0.15mol containing lithium, the average grain diameter of lithium sand are 0.8mm).Then it is sucked with syringe molten by 40mL hexamethylene/n-hexane mixing
The mixture of agent and 0.041mol bromoethyl -1- methyl -2,3- diethylsilane composition, connects syringe with three-necked flask,
Liquid in syringe 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 for generating reaction precipitate.It is protected again in argon gas
Under shield, supernatant is transferred in a new flask, is filtered out with the sand core filter bulb that average pore size is 3 μm remaining in supernatant
The inorganic matters such as lithium sand, lithium chloride and lithia obtain initiator Y3.
Preparation example 4
Initiator Y4 is prepared using method similar with preparation example 1, except that:
Halogenated silanes used in this preparation example is chloroethyl -1,2,3- triethylsilane, and chloroethyl -1,2, tri- second of 3-
The dosage molar ratio of base silane and lithium is 1:3.
Remaining is identical with preparation example 1.
Obtain initiator Y4.
Preparation example 5
Initiator Y5 is prepared using method similar with preparation example 2, except that:
Halogenated silanes used in this preparation example is chloropropyl -1- methyl -2- ethyl -3- propyl silane, and chloropropyl -1-
The dosage molar ratio of methyl -2- ethyl -3- propyl silane and lithium is 1:4.
Remaining is identical with preparation example 2.
Obtain initiator Y5.
Preparation example 6
Initiator Y6 is prepared using method similar with preparation example 3, except that:
Halogenated silanes used in this preparation example is chloropropyl -1,2- diethyl -3- propyl silane, and chloropropyl -1,2-
The dosage molar ratio of diethyl -3- propyl silane and lithium is 1:3.5.
Remaining is identical with preparation example 3.
Obtain initiator Y6.
Preparation example 1a
2350g hexamethylene/n-hexane mixed solvent is added into 5L stainless steel polymeric kettle, 1.08g tetrahydro chaff is then added
Alcohol ether, 52.5g styrene and 297.5g butadiene.When system temperature to be polymerized reaches 50 DEG C, 116.7mmol is added by above-mentioned
The initiator Y1 that preparation example 1 is prepared；System temperature after twenty minutes, is increased to 80 DEG C, adds 350mmol diethyl by reaction
Alkenyl benzene (is mixed by p-divinyl benzene and m-divinyl benzene according to the molar ratio of 1:1)；After coupling 30 minutes, it is added
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 obtained, the content of styrene is 15 weight %, 1,2 structure
Content is 50 weight %, number-average molecular weight 3000, molecular weight distribution 1.06.
Preparation example 2a
2350g hexamethylene/n-hexane mixed solvent is added into 5L stainless steel polymeric kettle, 1.21g tetrahydro chaff is then added
Alcohol butyl ether, 70g styrene and 280g butadiene.When system temperature to be polymerized reaches 70 DEG C, 116.7mmol is added by above-mentioned preparation
The initiator Y2 that example 2 is prepared；System temperature after twenty minutes, is increased to 85 DEG C, adds 460mmol to divinyl by reaction
Base benzene；After forty minutes, triethoxychlorosilane is added in coupling, reacts 30 minutes, obtains the star-like styrene-butadiene polymer of both-end Si modification
X2。
In the star-like styrene-butadiene polymer X2 of both-end Si modification obtained, the content of styrene is 18 weight %, 1,2 structure
Content is 59 weight %, number-average molecular weight 3700, molecular weight distribution 1.08.
Preparation example 3a
2350g hexamethylene/n-hexane mixed solvent is added into 5L stainless steel polymeric kettle, 1.08g tetrahydro chaff is then added
Alcohol ether, 105g styrene and 245g butadiene.When system temperature to be polymerized reaches 40 DEG C, 116.7mmol is added by above-mentioned system
The initiator Y3 that standby example 3 is prepared；System temperature after twenty minutes, is increased to 85 DEG C, adds diethyl between 525mmol by reaction
Alkenyl benzene；After coupling 30 minutes, trimethoxy chlorosilane is added, reacts 25 minutes, obtains the star-like butylbenzene polymerization of both-end Si modification
Object X3.
In the star-like styrene-butadiene polymer X3 of both-end Si modification obtained, the content of styrene is 22 weight %, 1,2 structure
Content is 55 weight %, number-average molecular weight 4500, molecular weight distribution 1.07.
Preparation example 4a
This preparation example is carried out using method similar with preparation example 1a, except that:
Initiator used in this preparation example is the initiator Y4 being prepared in preparation example 4, and the end-capping reagent used is γ-
Bromopropyl trimethoxy silane, and the dosage 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 %, and 1,2 structure contains
Amount is 55 weight %, number-average molecular weight 3300, molecular weight distribution 1.06.
Preparation example 5a
This preparation example is carried out using method similar with preparation example 2a, except that:
Initiator used in this preparation example is the initiator Y5 being prepared in preparation example 5, and the end-capping reagent used 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 %, and 1,2 structure contains
Amount is 61 weight %, number-average molecular weight 3700, molecular weight distribution 1.08.
Preparation example 6a
This preparation example is carried out using method similar with preparation example 3a, except that:
Initiator used in this preparation example is the initiator Y6 being prepared in preparation example 6, and the end-capping reagent used is two
One methoxyl group chlorosilane of ethyoxyl.
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 %, and 1,2 structure contains
Amount is 55 weight %, number-average molecular weight 4400, molecular weight distribution 1.07.
Embodiment 1
The preparation method of the vulcanized rubber SX1 of the present embodiment is carried out as follows:
(1) in mixer, under 90rpm revolving speed, dience rubber and liquid rubber are mixed at 80 DEG C of initial temperature
Refine 30s；
(2) 3/4 reinforcing agent, whole activators and the first whole couplings of the weight of the total reinforcing agent of Zhan is added
Agent Si69 is kneaded 2.5min；
(3) remaining reinforcing agent, the residue in the rubber composition Z1 other than vulcanizing agent and vulcanization accelerator is added
Component unloads sizing material after being kneaded 6min at this temperature after sizing material temperature reaches 150 DEG C；
(4) sizing material is passed through three times on the open mill that roll spacing is 5mm, roller temperature is 50 ± 5 DEG C, the mixing glue of acquisition is stopped
Put 4h；
(5) the mixing glue that step (4) obtain is kneaded at 40 ± 5 DEG C of initial temperature with vulcanizing agent and vulcanization accelerator,
Time to be mixed unloads sizing material when reaching 4min；
(6) sizing material for obtaining step (5) passes through primary on the open mill that roll spacing is 0.5mm, roller temperature is 50 ± 5 DEG C,
Then roll spacing is adjusted to 3mm, then by twice；The rubber compound of acquisition is parked for 24 hours；
(7) it will vulcanize 35 minutes under 160 DEG C, 15MPa pressure by the sizing material of step (6) processing, and obtain vulcanized rubber
SX1。
The relevant parameter of dience rubber T1 in the present embodiment is as shown in table 1；The rubber composition Z1's of the present embodiment
Composition and dosage (parts by weight) 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 mixer, under 90rpm revolving speed, dience rubber and liquid rubber are mixed at 60 DEG C of initial temperature
Refine 45s；
(2) 3/5 reinforcing agent, whole activators and the first whole couplings of the weight of the total reinforcing agent of Zhan is added
Agent Si69 is kneaded 2min；
(3) remaining reinforcing agent, the residue in the rubber composition Z2 other than vulcanizing agent and vulcanization accelerator is added
Component unloads sizing material when sizing material temperature reaches 170 DEG C；
(4) sizing material is passed through three times on the open mill that roll spacing is 5mm, roller temperature is 50 ± 5 DEG C, the mixing glue of acquisition is stopped
Put 5h；
(5) the mixing glue that step (4) obtain is kneaded at 40 ± 5 DEG C of initial temperature with vulcanizing agent and vulcanization accelerator,
Sizing material is unloaded when sizing material temperature reaches 110 DEG C；
(6) sizing material for obtaining step (5) passes through primary on the open mill that roll spacing is 0.5mm, roller temperature is 50 ± 5 DEG C,
Then roll spacing is adjusted to 3mm, then by twice；The rubber compound of acquisition is parked into 18h；
(7) it will vulcanize 40 minutes under 150 DEG C, 15MPa pressure by the sizing material of step (6) processing, and obtain vulcanized rubber
SX2。
The relevant parameter of dience rubber T2 in the present embodiment is as shown in table 1；The rubber composition Z2's of the present embodiment
Composition and dosage (parts by weight) 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 mixer, under 90rpm revolving speed, dience rubber and liquid rubber are mixed at 50 DEG C of initial temperature
Refine 45s；
(2) the silane coupled of 1/2 reinforcing agent of the weight of the total reinforcing agent of Zhan, the activator of whole and whole is added
Agent Si75 is kneaded 3min；
(3) remaining reinforcing agent, the residue in the rubber composition Z3 other than vulcanizing agent and vulcanization accelerator is added
Component unloads sizing material after being kneaded 5min at this temperature after sizing material temperature reaches 155 DEG C；
(4) sizing material is passed through three times on the open mill that roll spacing is 5mm, roller temperature is 50 ± 5 DEG C, the mixing glue of acquisition is stopped
Put 5h；
(5) the mixing glue that step (4) obtain is kneaded at 40 ± 5 DEG C of initial temperature with vulcanizing agent and vulcanization accelerator,
Sizing material is unloaded when sizing material temperature reaches 115 DEG C；
(6) sizing material for obtaining step (5) passes through primary on the open mill that roll spacing is 0.5mm, roller temperature is 50 ± 5 DEG C,
Then roll spacing is adjusted to 3mm, then by twice；The rubber compound of acquisition is parked into 30h；
(7) it will vulcanize 50 minutes under 140 DEG C, 14MPa pressure by the sizing material of step (6) processing, and obtain vulcanized rubber
SX3。
The relevant parameter of dience rubber T3 in the present embodiment is as shown in table 1；The rubber composition Z3's of the present embodiment
Composition and dosage (parts by weight) are as shown in table 2.
Embodiment 4
The present embodiment prepares vulcanized rubber SX4 using method similar to Example 1, the difference is that in the present embodiment
The rubber composition used is rubber composition Z4, and the composition of rubber composition Z4 and dosage (parts by weight) are 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, the difference is that in the present embodiment
The rubber composition used is rubber composition Z5, and the composition of rubber composition Z5 and dosage (parts by weight) are 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, the difference is that in the present embodiment
The rubber composition used is rubber composition Z6, and the composition of rubber composition Z6 and dosage (parts by weight) are 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, the difference is that in the present embodiment
The dience rubber used is T4, and the relevant parameter of T4 is as shown in table 1, and rubber composition used in the present embodiment is rubber
Composition Z7, and the composition of rubber composition Z7 and dosage (parts by weight) are 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, the difference is that in the present embodiment
The dience rubber used is T5, and the relevant parameter of T5 is as shown in table 1, and rubber composition used in the present embodiment is rubber
Composition Z8, and the composition of rubber composition Z8 and dosage (parts by weight) are 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, the difference is that in the present embodiment
The dience rubber used is T6, and the relevant parameter of T6 is as shown in table 1, and rubber composition used in the present embodiment is rubber
Composition Z9, and the composition of rubber composition Z9 and dosage (parts by weight) are 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, the difference is that in the present embodiment
The rubber composition used is rubber composition Z10, and the composition of rubber composition Z10 and dosage (parts by weight) such as institute in table 2
Show.
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, the difference is that in the present embodiment
The rubber composition used is rubber composition Z11, and the composition of rubber composition Z11 and dosage (parts by weight) such as institute in table 2
Show.
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, the difference is that in the present embodiment
The rubber composition used is rubber composition Z12, and the composition of rubber composition Z12 and dosage (parts by weight) such as institute in table 2
Show.
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, the difference is that in the present embodiment
The dience rubber used is T7, and the relevant parameter of T7 is as shown in table 1, and rubber composition used in the present embodiment is rubber
Composition Z13, and the composition of rubber composition Z13 and dosage (parts by weight) are 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, the difference is that in this comparative example
The rubber composition used is rubber composition DZ1, and the composition of rubber composition DZ1 and dosage (parts by weight) such as institute in table 2
Show.
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, the difference is that in this comparative example
The rubber composition used is rubber composition DZ2, and the composition of rubber composition DZ2 and dosage (parts by weight) such as institute in table 2
Show.
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 for the vulcanized rubber that test above-described embodiment and comparative example are prepared as follows.
(1) Mooney viscosity:
According to GB/T 1232.1-2000 standard testing.
It preheats 1 minute, tests 4 minutes at 100 ± 0.5 DEG C.
(2) tensile property is tested:
According in national standard " measurement of GB/T 528-1998 vulcanized rubber or thermoplastic elastomer tensile stress-strain performance "
Method test.
The AG-20KNG of puller system model Shimadzu Corporation production；Tear resistance is tested according to national standard " GB/T 529-1999
The measurement (trousers shape, square and crescent sample) of vulcanized rubber or thermoplastic elastomer tearing strength " in method test, pulling force
The AG-20KNG of machine model Shimadzu Corporation production.
Acquired results are as shown in table 3.
(" tensile strength/MPa ", " elongation/% ", " tearing strength/(kN/m) " in table 3, " 100% stretches/MPa surely "
" 300% stretches/MPa surely " data).
(3) dynamic mechanical:
Temperature scanning is on German GABO company EPLEXOR-500N dynamic thermomechanical analysis apparatus to the viscoelastic behavior of sample
It is tested.
Sample length is 35mm, width 8mm, with a thickness of 1.0mm.It tests and uses stretch mode, test frequency 11Hz,
Temperature range is -80~80 DEG C, and heating rate is 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 " data in table 3).
Table 3
From the results shown in Table 3, the property for the vulcanized rubber that rubber composition provided by the invention is prepared is bright
The property of the aobvious vulcanized rubber being prepared better than comparative example, and liquid rubber of the invention can substitute processing oil and help point
Powder, while being applied in combination with dience rubber interworking, it not only can be very good solution white carbon black and disperse to be stranded in rubber matrix
Difficulty and tire finished product processing oil during storage are readily migrate into tire finished surface, make tire finished product that color occur and become
Change and lead to the problem of quality fluctuation, moreover it is possible to the performance for significantly promoting vulcanizate, to obtain the wheel of excellent combination property
Tire tread glue material.Comparison between comparative example 1 and comparative example 2 can with it is further seen that, even if increasing polyethylene glycol
Dosage also still introduces silicon atoms not as good as passing through to the promotion effect of the performance of the vulcanized rubber of acquisition in rubber composition
Liquid rubber.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
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 also be regarded as the disclosure of the present invention.
Claims (28)
1. a kind of rubber composition, the composition contains dience rubber, liquid rubber, reinforcing agent, vulcanizing agent, vulcanization promotion
Agent, activator and the first coupling agent, which is characterized in that the liquid rubber is the star-like styrene-butadiene polymer of both-end Si modification, should
The star-like styrene-butadiene polymer of both-end Si modification is by the way that styrene monomer and divinylic monomer to be successively coupled with initiator, second
Agent, end-capping reagent are contacted and are made, wherein the initiator has the structure as shown in following formula (I):
Wherein, R1、R2And R3It is each independently selected from C1~C20Alkyl, C2~C20Monoene alkyl or C6~C20
Aralkyl, R4Selected from C1~C20Alkylidene, second coupling agent be p-divinyl benzene, m-divinyl benzene and
The dosage molar ratio of at least one of adjacent divinylbenzene, the initiator and second coupling agent is 1:(1.5-10)；
The number-average molecular weight of the star-like styrene-butadiene polymer of the both-end Si modification is 1000-30000, molecular weight distributing index 1.01-
1.20。
2. composition according to claim 1, wherein 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 %.
3. composition according to claim 2, wherein styrene knot in the star-like styrene-butadiene polymer of the both-end Si modification
The content of structure unit is 15-25 weight %, and 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.
4. composition according to claim 1, wherein the end-capping reagent is the alkoxy silane containing monochloro or single bromine.
5. composition according to claim 1, wherein R1、R2And R3It is each independently selected from the alkyl of C1~C12, R4Choosing
From the alkylidene of C2~C5.
6. composition according to claim 4, wherein the end-capping reagent is selected from trimethoxy chlorosilane, dimethoxy one
Ethyoxyl chlorosilane, one methoxyl group chlorosilane of diethoxy, triethoxychlorosilane, one ethyoxyl bromo-silicane of dimethoxy, two
One methoxyl group bromo-silicane of ethyoxyl, trimethoxy bromo-silicane, triethoxy bromo-silicane, r-chloropropyl trimethoxyl silane, chloropropyl
Triethoxysilane, one methoxy silane of chloropropyl diethoxy, bromopropyl trimethoxy silane, bromopropyl triethoxysilane
At least one of with one methoxy silane of bromopropyl diethoxy.
7. composition described in any one of -6 according to claim 1, wherein the dience rubber is selected from polybutadiene rubber
At least one of glue, oil-filled solution polymerized butadiene styrene rubber and non-oil-filled solution polymerized butadiene styrene rubber.
8. composition according to claim 7, wherein containing described in 0.1-100 weight % in the dience rubber
Oil-filled solution polymerized butadiene styrene rubber.
9. composition according to claim 8, wherein containing being filled described in 50-100 weight % in the dience rubber
Oily solution polymerized butadiene styrene rubber.
10. composition according to claim 8, wherein containing described in 70-100 weight % in the dience rubber
Oil-filled solution polymerized butadiene styrene rubber.
11. composition according to claim 7, wherein styrol structural unit in the oil-filled solution polymerized butadiene styrene rubber
Content is 10-30 weight %, and the content of 1,2 structure is 40-70 weight %, and Mooney viscosity 50-70, oil-filled number is 20-50
Part.
12. composition according to claim 11, wherein styrol structural unit in the oil-filled solution polymerized butadiene styrene rubber
Content is 15-25 weight %, and the content of 1,2 structure is 50-65 weight %, and Mooney viscosity 55-65, oil-filled number is 30-40
Part.
13. composition according to claim 7, wherein the polybutadiene rubber is butadiene rubber.
14. composition according to claim 13, wherein the cis-structure content in the butadiene rubber is more than or equal to 95
Weight %.
15. composition described in any one of -6 according to claim 1, wherein with the dience rubber of 100 parts by weight
On the basis of, the content of the liquid rubber is 5-35 parts by weight, and the content of the reinforcing agent is 50-95 parts by weight, the vulcanization
The content of agent is 0.5-5 parts by weight, and the content of the vulcanization accelerator is 1-6 parts by weight, and the content of the activator is 3-8 weight
Part is measured, the content of first coupling agent is 3-10 parts by weight.
16. composition according to claim 15, wherein described on the basis of the dience rubber of 100 parts by weight
The content of liquid rubber is 8-30 parts by weight, and the content of the reinforcing agent is 60-85 parts by weight, and the content of the vulcanizing agent is 1-
3.5 parts by weight, the content of the vulcanization accelerator are 2-4 parts by weight, and the content of the activator is 4-6 parts by weight, described the
The content of one coupling agent is 5-8 parts by weight.
17. composition described in any one of -6 according to claim 1, wherein containing greater than 50 weights in the reinforcing agent
Measure % white carbon black.
18. composition according to claim 17, wherein the white carbon black containing 80-100 weight % in the reinforcing agent.
19. composition according to claim 17, wherein also contain carbon black in the reinforcing agent.
20. composition described in any one of -6 according to claim 1, wherein
The vulcanizing agent is at least one of insoluble oil-filled sulphur, two thio morpholines and four two morpholines of vulcanization；
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 coupling agent of sulfur atom-containing and alkoxy.
21. composition described in any one of -6 according to claim 1, wherein further containing anti-old in the composition
Agent.
22. composition according to claim 21, wherein described anti-old on the basis of the dience rubber of 100 parts by weight
The content of agent is 1-5 parts by weight.
23. composition described in any one of -6 according to claim 1, wherein further contain crystallite in the composition
Wax.
24. composition according to claim 23, wherein on the basis of the dience rubber of 100 parts by weight, the crystallite
The content of wax is 0.1-2 parts by weight.
25. a kind of preparation method of vulcanized rubber, the method includes by group described in any one in claim 1-24
The each component closed in object is kneaded, and is obtained rubber compound, is then vulcanized the rubber compound.
26. according to the method for claim 25, wherein the condition of the vulcanization includes that the temperature of vulcanization is 140-160 DEG C,
The pressure of vulcanization is 5-15MPa, and the time of vulcanization is 10-50 minutes.
27. the vulcanized rubber that the method as described in claim 25 or 26 is prepared.
28. application of the vulcanized rubber described in claim 27 as tire tread material.
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| CN109575387B (en) * | 2017-09-29 | 2021-04-13 | 中国石油化工股份有限公司 | Tire tread rubber composition, vulcanized rubber, and preparation method and application thereof |
| CN107698831B (en) * | 2017-10-18 | 2020-07-28 | 正新橡胶（中国）有限公司 | Tire tread rubber composition |
| 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 |
| 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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| CN101142268A (en) * | 2005-03-14 | 2008-03-12 | 株式会社普利司通 | Rubber composition and pneumatic tire using the same |
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| CN102344529A (en) * | 2010-08-05 | 2012-02-08 | 中国石油天然气股份有限公司 | Preparation method of star-shaped solution polymerized butadiene styrene rubber with wide molecular weight distribution |
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| CN101142268A (en) * | 2005-03-14 | 2008-03-12 | 株式会社普利司通 | Rubber composition and pneumatic tire using the same |
| CN101456938A (en) * | 2008-12-31 | 2009-06-17 | 大连理工大学 | Star-shaped comb type butadiene/phenylethylene block copolymers and preparation method thereof |
| CN102344529A (en) * | 2010-08-05 | 2012-02-08 | 中国石油天然气股份有限公司 | Preparation method of star-shaped solution polymerized butadiene styrene rubber with wide molecular weight distribution |
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