CN106589488B - A kind of rubber composition and vulcanized rubber and its preparation method and application - Google Patents
A kind of rubber composition and vulcanized rubber and its preparation method and application Download PDFInfo
- Publication number
- CN106589488B CN106589488B CN201510676929.0A CN201510676929A CN106589488B CN 106589488 B CN106589488 B CN 106589488B CN 201510676929 A CN201510676929 A CN 201510676929A CN 106589488 B CN106589488 B CN 106589488B
- Authority
- CN
- China
- Prior art keywords
- rubber
- rubber composition
- weight
- composition according
- branched
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/246—Intercrosslinking of at least two polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
Abstract
It the present invention relates to rubber materials, provides and is related to a kind of rubber composition, by the application of the rubber composition prepares the method for vulcanized rubber and is prepared vulcanized rubber and the vulcanized rubber.The rubber composition contains polybutadiene rubber, carbon black and operation oil, and the polybutadiene rubber is branched polybutadiene rubber and its average branching index is 0.5 × 10‑5‑11×10‑5mol/g.The rubber composition of the present invention has preferable processing performance and mechanical performance, the vulcanized rubber of the present invention has preferable mechanical performance, specifically include higher hardness, 100% stress at definite elongation, preferable resilience performance, compression deflect performance, dynamic mechanical and ageing-resistant performance, it is thus particularly suitable for applications in and prepares in tire or tyre element, such as tyre surface glue material to be made.
Description
Technical field
The present invention relates to a kind of rubber materials, and in particular, to a kind of rubber composition prepares sulphur by the rubber composition
Change the application of the method and the vulcanized rubber and the vulcanized rubber being prepared of rubber.
Background technology
With the increasingly reduction of fossil fuel and raw material resources, automobile industry requirement energy-efficient to tire is also increasingly compeled
It cuts, automobile energy consumption is greatly to consume on tire, and reduce the rolling resistance of tire, and the service life for improving tire is green
The important goal of colour wheel tire.
Existing tire tread glue basis glue is typically to contain intermingle with or emulsion polymerized styrene butadiene rubber, cis-polybutadiene rubber are (following
Referred to as " butadiene rubber "), natural rubber and isoprene rubber etc. be used alone or be used in combination.But by these existing tires
Face glue rubber composition obtains rubber mixed in the prevalence of processing performance is not good enough, extrusion performance is poor, is squeezed in high speed
During going out sizing material be also easy to produce flow instabilities so as to cause sizing material it is rough the problems such as, therefore by these traditional rubbers
The quality of tire product made from glue composition cannot meet the requirement of people.
In above-mentioned several glue kinds, butadiene rubber, especially nickel polymerized BR, due to its preferable wearability and resistance to song
One of the main glue kind that fatigue behaviour becomes manufacture tire is scratched, generally with natural rubber and/or butadiene-styrene rubber and with being used for
Tread rubber, is additionally operable to tire shoulder glue, but that there is also processing performances is general, is also easy to produce shakiness when squeezing out processing for traditional butadiene rubber
The defects of constant current is dynamic, wet-sliding resistant performance is poor, rolling resistance is larger.In order to overcome drawbacks described above, the prior art is begun attempt to pair
Traditional butadiene rubber is branched modification, to improve its processing performance and performance.
US7030195B2 discloses a kind of preparation method of reduced branching degree butadiene rubber.The first step, butadiene is organic molten
Reaction in agent and catalyst (neodymium compound, alkyl aluminum and the aluminium compound containing halogens such as chlorine), conversion ratio ＞ 98% are generated suitable
Formula-Isosorbide-5-Nitrae-content ＞ 93%, line style cis polybutadiene of the molecular weight distribution mw/mn between 2.2-2.9.Second step, it is used
The polymer solution that the oxide process first step obtains.Third walks, and it is poly- that reduced branching degree is extracted in the solution obtained from second step
Butadiene.
In the existing technology for preparing branched butadiene rubber, chemical treatment method is mainly used, such as polymerize in rubber
During be added and structure regulator or be allowed to generate branched structure using the methods of catalyst, but chemical method is often branched
Degree is relatively low, or it is easy to appear crosslinking phenomenas when attempting to obtain higher branch degree, so as to cause gained branched modification
The mechanical performance and processing performance of product cannot meet higher requirement, be in addition also usually present complicated for operation, degree of branching compared with
The problems such as difficult to control.It is, therefore, desirable to provide a kind of new method for the branched modification that can be solved the above problems.
Invention content
The purpose of the present invention is overcoming the drawbacks described above of the prior art, a kind of rubber composition is provided, by the building rubber compound
Object prepares the application of the method and the vulcanized rubber and the vulcanized rubber being prepared of vulcanized rubber.The building rubber compound of the present invention
There is object preferable processing performance and mechanical performance, vulcanized rubber of the invention to have preferable mechanical performance, specifically include
Higher hardness, 100% stress at definite elongation, preferable resilience performance, compression deflect performance, dynamic mechanical and resistance to ag(e)ing
Can, thus be particularly suitable for applications in and prepare in tire or tyre element, such as tyre surface glue material to be made.
The present invention provides a kind of rubber composition, which contains polybutadiene rubber, carbon black and operation oil；
Wherein, the polybutadiene rubber is branched polybutadiene rubber and its average branching index is 0.5 × 10-5-11×10- 5mol/g。
The present invention also provides a kind of preparation method of vulcanized rubber, the method includes by the rubber composition of the present invention
It is kneaded to obtain rubber compound, then the rubber compound is vulcanized.
Invention further provides the vulcanized rubbers being prepared according to the preparation method of above-mentioned vulcanized rubber.
Invention additionally provides application of the above-mentioned vulcanized rubber in preparing tire or tyre element.
It was found by the inventors of the present invention that in a certain range, the processing performance of the polybutadiene rubber of higher branch degree
It can be better than the polybutadiene rubber of relatively low degree of branching, however, degree of branching obtained by chemical method used in the prior art is general
All over relatively low, and the phenomenon that when the chemical method of the prior art attempts to improve degree of branching, it is easy to appear crosslinkings.The present invention
Inventor have been surprisingly found that using x ray irradiation x to prepare the method for branched polybutadiene rubber can be with during further investigation
The polybutadiene rubber for the degree of branching for being significantly higher than the prior art, and the easily controllable degree of branching of this method are obtained, is not allowed
The phenomenon that easily crosslinking, the rubber composition thus further obtained have better mechanical performance and processing performance, and
Energy can be more saved when being kneaded and being vulcanized.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Attached drawing is to be used to provide further understanding of the present invention, an and part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is that raw rubber H1-H5 and the raw rubber DH1-DH2 of comparative example obtained by preparation example are measured through rubber machining analyzer RPA
Fissipation factor-frequency scanning curve；
Fig. 2 is vulcanizate DS1-DS2 obtained by vulcanizate S1-S5 and comparative example obtained by embodiment through dynamic visco-elasticity analyser
(DMA) fissipation factor-temperature curve measured.
Specific implementation mode
The specific implementation mode of the present invention is described in detail 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.
The present invention provides a kind of rubber composition, which contains polybutadiene rubber, carbon black and operation oil,
The polybutadiene rubber is branched polybutadiene rubber and its average branching index is 0.5 × 10-5-11×10-5mol/g。
In the present invention, average branching index is used to indicate that the degree of branching of polybutadiene rubber, the average branch to refer to
Number=(Mbp -1-Mw -1)/2, wherein MbpFor the main chain average molecular weight between adjacent two branch, MwFor polymer average molecular weight.
Wherein, MwDual detector gel permeation chromatograph (GPC, the allianee GPC V2000 of Waters, US) can be passed through
It measures, dual detector is differential refraction (DRI) and capillary automatic viscometer (Vis), and 40 DEG C of measuring temperature, mobile phase solvent is
Tetrahydrofuran (THF)；MbpIt can be according to MwWith the viscosity results of Vis, (is calculated and polymerize with electronic computer according to Wang Dehua et al.
The degree of branching and molecular weight distribution [J] China Synthetic Rubber Industries of object, 1978,5：Method 37-42) is calculated.
In general, when less or no crosslinking phenomena, the average branch of the branched polybutadiene rubber of the prior art refers to
Number is generally less than 0.5 × 10-5Mol/g, when the prior art branched polybutadiene rubber average branching index higher than 0.5 ×
10-5It usually will appear crosslinking phenomena when mol/g, and when average branching index is also not up to 5 × 10-5Crosslinking phenomena when mol/g
It is very serious.It was found by the inventors of the present invention that when the branched polybutadiene rubber average branching index be 0.5 ×
10-5-11×10-5Mol/g and when not having crosslinking phenomena, the comprehensive performance of mechanical performance and processing performance is more excellent,
Reason may is that：The branched polybutadiene rubber of average branching index within the above range has more suitable short-chain branched
Structure and strand spacing, strand is easy sliding when mixing, and compound viscosity is moderate, and the torque of mixing reduces, and reduces mixing
Energy, sizing material temperature rise relatively low.In general, in a certain range (such as no more than 11 × 10-5When mol/g), average branch refers to
Number is higher, and branched polybutadiene rubber and its obtained rubber compound processing performance are better, the mechanical performance of vulcanized rubber also compared with
Good, therefore, in the present invention, the average branching index of the branched polybutadiene rubber can be 0.5 × 10-5-11×10- 5Mol/g, preferably 1 × 10-5-11×10-5Mol/g, further preferably 2 × 10-5-11×10-5Mol/g, further preferably
It is 5 × 10-5-11×10-5Mol/g, further preferably 5 × 10-5-10×10-5Mol/g, further preferably 6 × 10-5-9
×10-5mol/g。
In the present invention, the branched polybutadiene rubber is branched cis-rich polybutadiene rubber (referred to as " along fourth rubber
Glue "), and on the basis of the total weight of the branched polybutadiene rubber, the content of cis--Isosorbide-5-Nitrae-butadiene structure is 95-
The content of 99 weight %, anti-form-1,4- butadiene structures are 0.7-2.5 weight %, and the content of 1,2- butadiene structure is 0.3-
2.5 weight %；It is further preferred that on the basis of the total weight of the branched polybutadiene rubber, wherein cis--Isosorbide-5-Nitrae-fourth two
The content of alkene structure is 95.5-97.5 weight %, and the content of anti-form-1,4- butadiene structures is 1.5-2.5 weight %, 1,2- fourth
The content of diene structure is 1-2 weight %.Furthermore it is preferred that the branched polybutadiene rubber is branched nickel polymerized BR,
Nickel content wherein in raw rubber is preferably the micro- gram grams of 10-15, and the weight ratio of Al/Ni is preferably 1-2, the nickel in the raw rubber and aluminium
Actually butadiene rubber catalyst used in preparation process remains in nickel and aluminium in raw rubber.In the present invention, term
" raw rubber " continues to use the meaning of this field routine, refers to and the rubber product that auxiliary agent is kneaded is not added, and the statement for being somebody's turn to do " raw rubber " is used
It is distinguished in " rubber compound " and " vulcanized rubber ".
In the present invention, the branched polybutadiene rubber does not have apparent crosslinking phenomena, and usually, of the invention is branched
Total crosslink density (referred to as XLD) of polybutadiene rubber is 2 × 10-5-6×10-5mol/cm3, preferably 3.5 × 10-5-4.5
×10-5mol/cm3, the average molecular weight (referred to as Mc) between crosslinking points is 18-30kg/mol, preferably 21-26kg/mol.Its
Described in XLD include physical entanglement point and chemical crosslinking the sum of dot density, XLD and Mc pass through IIC Dr.Kuhn GmbH＆
The IIC XLDS-15HT type nuclear-magnetism crosslink density instrument of Co KG companies production measures.
In the present invention, the gel content of the branched polybutadiene rubber can be 1-10 weight %, preferably 5-8 weights
Measure %；Mooney viscosity can be 50-75, preferably 55-72.In the present invention, Mooney viscosity GB/ according to national standards
The method of T1232.1-2000 defineds is tested, and wherein rotor selects greater trochanter shown in table 1 in the standard, temperature setting
It it is 100 DEG C, the Mooney testing time is 1+4min, which is denoted as ML (1+4min, 100 DEG C), in the art
The Parameter units are Mooney point M, and traditionally the result of Mooney viscosity omits M, i.e. numerical value 1 represents a Mooney point.
In the present invention, usually, the weight average molecular weight of the branched polybutadiene rubber can be 28 × 104-46
×104G/mol, preferably 30 × 104-45×104G/mol, molecular weight distribution can be 2.9-5.1, preferably 3-4.5.
In the present invention, it is preferred to which the branched polybutadiene rubber is to carry out spoke to polybutadiene rubber using ray
It is obtained according to its branched modification is made.It was found by the inventors of the present invention that the chemical method of traditional preparation branched polybutadiene rubber
That often there is degrees of branching is relatively low, be susceptible to crosslinking phenomena, be complicated for operation, the degree of branching of gained branched modification product compared with
The problems such as difficult to control and the gained branched modification product mechanical performance and still not good enough processing performance, and furtheing investigate
During have been surprisingly found that the method that x ray irradiation x may be used is branched modification to polybutadiene rubber, this method can obtain
To the polybutadiene rubber for the degree of branching for being significantly higher than the prior art, and the easily controllable degree of branching of this method, it is not easy to
The phenomenon that crosslinking, mechanical performance and processing performance to make sizing material are improved, and can carry out mixing and sulphur
Energy is more saved when change.
In the present invention, there is no particular limitation for ray used by irradiating, using conventional ray, such as can be with
To be one or more in electron beam, gamma-rays and X-ray, preferably gamma-rays；It is by which kind of radioactivity member for gamma-rays
What element decay generated is not particularly limited, preferably60The gamma-rays that Co decays generate.There is no particular limitation for the energy of ray,
Such as can be 0.8-2MeV, preferably 1-1.5MeV；When ray is60When the gamma-rays that Co decays generate, the energy of ray is excellent
It is selected as 1.17MeV and/or 1.33MeV.
In the present invention, there is no particular limitation for the dosage of x ray irradiation x, can be according to the type and degree of branching of ray
Demand selected, usually, the dosage of x ray irradiation x of the invention can be 5-60kGy (i.e. branched relative to 1kg irradiation
The dosage of polybutadiene rubber before modification, x ray irradiation x is 5-60kJ), preferably 20-60kGy (i.e. 20-60kJ/kg),
Further preferably 30-60kGy (i.e. 30-60kJ/kg) is still more preferably 35-50kGy (i.e. 35-50kJ/kg).
In the present invention, the gel content for irradiating the polybutadiene rubber before branched modification can be 0.1-1.9 weights
Measure %, preferably 0.3-1 weight %；Mooney viscosity can be 40-50, preferably 43-47；Weight average molecular weight can be 28 ×
104-46×104G/mol, preferably 30 × 104-40×104g/mol；Molecular weight distribution can be 2.9-5.1, preferably 3-4.
In the present invention, this field routine may be used in the implementation environment of the method for preparing branched polybutadiene rubber
Environment, such as can be carried out in limiting oxygen environment, the limit oxygen environment refer to the oxygen amount that is limited in environment as test specimen encapsulate when
Oxygen amount in air.Oxygen amount in the air must be limited in certain range, and under packaging environment, volume of air and irradiation are branched
The ratio between volume of polybutadiene rubber before modification ranging from 0.001-0.05：1, preferably 0.004-0.03：1, for example,
0.004-0.006：1.The radiation of air small can introduce oxygen-containing polar group (mainly carbonyl group) in strand, can
To improve the binding ability of rubber and polar filler, improve processing performance, but dose of radiation is excessive, just will produce crosslinking and excessively
Degradation.Limit oxygen radiation can then improve such situation, because the oxygen and nitrogen content of radiation space is limited, be introduced with polar group
Degradation is not obvious, and radiation mainly causes the branched of strand.No a large amount of oxygen participates in crosslinking and degradation reaction, to inhibit
The a large amount of introducings of oxygen-containing polar group in strand.There is no particular limitation for the mode of offer limit oxygen environment, such as can use
Plastic film seals.
By the method for above-mentioned irradiation, the branched polybutadiene rubber as obtained by adjusting the dosage of ray and easily control
The degree of branching of glue, and crosslinking phenomena is less likely to occur, so as to effectively improve the mechanical performance of products obtained therefrom and add
Work performance, and energy can be more saved when being kneaded and being vulcanized.Inventor has found during a large number of experiments, generally
For, when the dosage of x ray irradiation x is 5-60kGy, the average branching index of gained branched polybutadiene rubber can be controlled
0.5 × 10-5-11×10-5In the range of mol/g；It, can be branched by gained when the dosage of x ray irradiation x is 20-60kGy
The average branching index of polybutadiene rubber is controlled 1 × 10-5-11×10-5In the range of mol/g；When the dosage of x ray irradiation x
For 30-60kGy when, can by the average branching index of gained branched polybutadiene rubber control 5 × 10-5-11×10- 5In the range of mol/g；It, being averaged gained branched polybutadiene rubber when the dosage of x ray irradiation x is 35-50kGy
Branch index is controlled 6 × 10-5-9×10-5In the range of mol/g.Simultaneously by the method for above-mentioned irradiation, the branched of gained gathers
Butadiene rubber does not have apparent crosslinking phenomena, and usually, total crosslink density XLD of branched polybutadiene rubber of the invention is
2×10-5-6×10-5mol/cm3, preferably 3.5 × 10-5-4.5×10-5mol/cm3, the average molecular weight Mc between crosslinking points is
18-30kg/mol, preferably 21-26kg/mol.
It was found by the inventors of the present invention that passing through the obtained average branching index of irradiance method within the above range branched
Polybutadiene rubber has more suitable short-chain branched structure and a strand spacing, and strand is easy sliding, sizing material when mixing
The torque of modest viscosity, mixing reduces, and reduces mixing energy, and sizing material temperature rises relatively low.And the process for branching of the prior art, it is branched
Structure is not easy to control, is likely to result in that long chain branching is more or crosslinking, easily leads to macromolecule and tangles serious, dyskinesia, instead
It is unfavorable for reducing mixing energy；It is less to be also possible to branched structure, for strand based on line style, strand spacing is small, and interchain is made
Firmly big, dyskinesia is also unfavorable for reducing mixing energy.Therefore, the obtained branched rubber of irradiance method using the present invention
Glue has better mechanical performance and processing performance.
In the present invention, the rubber composition also contains carbon black and operation oil.The carbon black rises in rubber composition
To the effect of filler, there is no particular limitation for content, is selected according to the content row of the carbon black of this field routine, for example,
By the content of polybutadiene rubber in the rubber composition in terms of 100 parts by weight, the content of the carbon black can be 30-70 weights
Measure part, preferably 40-60 parts by weight；Also there is no particular limitation for the type of the carbon black, such as can be existing various energy
The carbon black of rubber composition described in enough reinforcement, and can be commercially available, such as the carbon black can be selected from industrial reference
It is one or more in carbon black and industrial production carbon black.Wherein, the industrial reference black includes No. 7 charcoals of ASTM industry reference
Black, industrial No. 8 carbon blacks of reference of ASTM etc. it is one or more, the industrial production carbon black include high wear-resistant carbon black, in it is super resistance to
Grind the one or more of carbon black etc..There is no particular limitation for the content and type of the operation oil, according to the behaviour of this field routine
The content and type for making oil are selected, for example, with the content of polybutadiene rubber in the rubber composition for 100 weights
Part meter is measured, the content of the operation oil can be 5-20 parts by weight, preferably 10-15 parts by weight；The type of the operation oil is excellent
It is one or more in petroleum plasticizer, fat oil system plasticizer and synthesis plasticizer.Wherein, the petroleum increases
Moulding agent can be selected from one or more in naphthenic oil, aromatic naphtha；Fat oil system plasticizer can be selected from glycerine, soybean
It is one or more in oil, oleic acid and zinc stearate；The synthesis plasticizer can be selected from repefral, adjacent benzene two
It is one or more in formic acid diethylester and epoxidized soybean oil.
In the case of in the present invention, it is preferred to, the rubber composition also contains activator.The activator is to refer to increase
Add the activity of vulcanization accelerator, and then reduces the dosage of the vulcanization accelerator or shorten the substance of vulcanization time.Activity is added
Agent can significantly improve the sulphidity and heat resistance of the rubber.In the present invention, the activator can be existing each
Kind activator, such as can be inorganic activator and/or organic activator；Wherein, the inorganic activator can be zinc oxide,
It is for example, one or more in indirect process zinc oxide, American process zinc oxide and activated zinc oxide；The organic activator can be with
It is one or more in stearic acid, lauric acid and octanoic acid.There is no particular limitation for the dosage of the activator, for example, with
The content of polybutadiene rubber is 100 parts by weight meters in the rubber composition, and the content of the activator is 2-6.5 weight
Part；Preferably, the activator is mixed by inorganic activator and organic activator, wherein the content of the inorganic activator
The content of preferably 1-4 parts by weight, the organic activator is preferably 1-2.5 parts by weight.
In the case of in the present invention, it is preferred to, the rubber composition also contains vulcanizing agent.The vulcanizing agent ensures rubber group
Conjunction object full cure be vulcanized rubber, by the content of polybutadiene rubber in the rubber composition be 100 parts by weight in terms of,
The content of the vulcanizing agent can be 0.5-2 parts by weight.The vulcanizing agent can be various conventional vulcanizing agents, such as can be
Elemental sulfur and/or sulfur-containing compound；Wherein, the elemental sulfur can be sulphur, for example, Cosan, insoluble sulfur, colloid
One or more in sulphur, precipitation sulphur, Sublimated Sulphur and acidless sulfur, it is thio that the sulfur-containing compound can be selected from two
Coffee quinoline and/or four two morpholines of vulcanization.Preferably, the vulcanizing agent is insoluble sulfur；The insoluble sulfur is sulphur
Allotrope does not dissolve in sulfur dioxide and other solvents, is also insoluble in rubber, exists with dispersity in rubber；When
After reaching curing temperature, these are dispersed in there are one the tools of the insoluble sulfur in rubber " activation stage ", i.e. chain type depolymerisation,
So that curingprocess rate is accelerated, reduce sulfur consumption, is conducive to the ageing properties for improving rubber.
In the case of in the present invention, it is preferred to, the rubber composition also contains vulcanization accelerator.With the rubber composition
The content of middle polybutadiene rubber is 100 parts by weight meters, and the content of the vulcanization accelerator is 0.2-1.5 parts by weight.According to this
Invention, the vulcanization accelerator can be that existing various vulcanization time, reduction curing temperature, the reduction vulcanizing agents of capable of shortening is used
Measure and improve the substance of the physical mechanical property of rubber, for example, can be selected from sulfenamide accelerator, thiazole accelerator and
It is one or more in guanidines.Wherein, the sulfenamide accelerator can be selected from N- tertiary butyls -2-[4-morpholinodithio
Base sulfenamide (trade name accelerator TBBS or NS), N- tertiary butyls-bis- (2-[4-morpholinodithio) sulfenamide (trade name
For：Accelerator TBSI) and N- cyclohexyl -2-[4-morpholinodithio base sulfenamide (trade name：Accelerant C BBS) in one kind or
A variety of, the thiazole accelerator can be selected from N- cyclohexyl -2-[4-morpholinodithio base sulfenamide (trade name：Accelerant CZ)
With 2, one or more in 2 '-dibenzothiazyl disulfides, the guanidines can be selected from diphenylguanidine (trade name：
Diphenylguanidine), it is one or more in triphenyl guanidine and di-o-tolylguanidine.Preferably, the combination of the vulcanizing agent and vulcanization accelerator
For sulphur and N- tertiary butyls -2-[4-morpholinodithio base sulfenamide.
The present invention also provides a kind of preparation method of vulcanized rubber, the method includes by the rubber composition of the present invention
It is kneaded to obtain rubber compound, then the rubber compound is vulcanized.
The method and condition of the mixing be can be various conventional mixing method and condition, it is usually, described mixed
Refining can carry out in open mill or mixer.Wherein, the mixing between each substance can be carried out at the same time, can also substep into
Row, preferably substep carry out, such as the process of the mixing carried out step by step may include：First by rubber composition in addition to vulcanizing agent
First segment mixing is carried out with the ingredient other than vulcanization accelerator, vulcanizing agent is then added and vulcanization accelerator progress second segment is close
Refining.In addition, in order to enable each substance to mix to be more uniformly distributed, to obtain the more excellent rubber of performance, under preferable case, institute
The temperature for stating mixing is 30-150 DEG C, and the pressure of mixing is 0-0.8MPa, and the time of mixing is 10-40 minutes.
According to the present invention, usually, the method and condition that the rubber compound obtained through above-mentioned mixing is vulcanized is this
Well known to field technology personnel.For example, the vulcanization can carry out in vulcanization bed or vulcanizing press；The conditions of vulcanization is logical
It include often temperature, pressure and the time of vulcanization, wherein as long as the temperature of the vulcanization, pressure and time can ensure described gather
Butadiene rubber is crosslinked with vulcanizing agent to react, for example, the temperature of the vulcanization can be 140-160 DEG C, vulcanization
Pressure can be 3.5-7.0MPa, and the time of vulcanization can be 0.15-1.0 hours.
In addition, the answering in preparing tire or tyre element the present invention also provides vulcanized rubber provided by the present invention
With.Wherein, the tyre element can be the tread rubber of tire.
The present invention will be further described in detail by specific embodiment below.
Preparation example I1~I5 is used to illustrate the preparation of branched polybutadiene rubber and obtained branched polybutadiene rubber
Preparation example I1-I5
Preparation example I1-I5 respectively by unmodified basic glue limit oxygen environment (plastic film seals, volume of air with wait locating
It is 0.005 to manage the ratio between volume of polybutadiene rubber：1) it is irradiated according to irradiation dose and radiographic source shown in table 1 in,
Respectively obtain the branched polybutadiene raw rubber product that number is H1~H5.
Wherein, the basic glue used in preparation example I1-I5 is the board of Yanshan Mountain branch company of China Petrochemical Corp. production
Number butadiene rubber basis glue for being BR9000, nature parameters include：Weight average molecular weight is 38.2 ten thousand, and molecular weight distribution is
3.91, Mooney viscosity ML (1+4min, 100 DEG C) are 45 ± 4；Wherein cis- Isosorbide-5-Nitrae-butadiene structure content is 96.5 weight %, instead
Formula-Isosorbide-5-Nitrae-butadiene structure content is 2.0 weight %, and 1,2- butadiene structure content is 1.5 weight %；Raw rubber elemental analysis knot
Fruit shows that containing Al be 15.4 micro- gram grams, is 11.4 micro- gram grams containing Ni, and Al/Ni weight ratios are 1.35.
Table 1
| Number | Irradiation dose (kGy) | Radiographic source | Ray energy (MeV) | Basic glue | |
| Embodiment I1 | H1 | 5 | Electron beam | 1.0 | BR9000 |
| Embodiment I2 | H2 | 20 | X-ray | 1.5 | BR9000 |
| Embodiment I3 | H3 | 30 | 60The gamma-rays that Co decays generate | 1.17 with 1.33 | BR9000 |
| Embodiment I4 | H4 | 40 | 60The gamma-rays that Co decays generate | 1.17 with 1.33 | BR9000 |
| Embodiment I5 | H5 | 60 | 60The gamma-rays that Co decays generate | 1.17 with 1.33 | BR9000 |
Embodiment 1-5
Embodiment 1-5 is used to illustrate the rubber composition of the present invention and is kneaded and is vulcanized to prepare vulcanization rubber
The method of glue.
(1) it is kneaded
By butadiene rubber raw rubber H1~H5 modified obtained by preparation example according to the formula of embodiment 1-5 shown in table 2
(in parts by weight) it is kneaded, according to《GBT 8660-2008 polymerisation in solution type butadiene rubber (BR) evaluation method》Method A
Mixer mixing operating procedure carries out, and raw rubber, carbon black, operation oil, stearic acid, zinc oxide is added in first segment mixing, and sizing material is discharged,
Vulcanizing agent, vulcanization accelerator is added in second segment mixing, finally obtains compound manufacture and is denoted as H ' 1~H ' 5 respectively and (corresponds to respectively
Embodiment 1-5).
Mixing facilities are 1.6L mixers, and producer is Farrel Corp. of the U.S., model BR1600。
Raw materials used producer and the trade mark is as follows：
Operation oil：Code name " oil 1 " is that the trade mark of China Petroleum Karamay, Xinjiang petro-chemical corporation production is Naphthenic
The naphthenic oil of oil 100, code name " oil 2 " are that the trade mark of Sinopec asphalt in Shenli Refinery production is Aromatic oil 90
High aromatic oil, code name " oil 3 " are that the trade mark of imported from America is ASTM103#Rubber processing oil；
Carbon black：Code name " charcoal 1 " is the high wear-resistant carbon black that the trade mark of Tianjin Carbon Black Factory's production is N330, and code name " charcoal 2 " is day
The intermediate super abrasion furnace black that the trade mark of Tianjin carbon black plant production is N220, code name " charcoal 3 " is that the trade mark of imported from America is ASTM IRB8
The industrial reference black of (Industry Reference Black)；
Vulcanizing agent：Code name " sulphur 1 " is that the trade mark of the Shanghai Nanhui county chemical plant Wa Xie production is the two thio of vulcanizing agent DTDM
Morpholine, code name " sulphur 2 " are four two morpholines of vulcanization of the Shanghai Nanhui county chemical plant Wa Xie production, and code name " sulphur 3 " is purchased from wide
The trade mark that Science and Technology Ltd. is contained in state Jinchang is S-80 sulphur；
Vulcanization accelerator：Code name " promoting 1 " is that the trade mark of Huangyan, Zhejiang chemical plant production is 2,2 '-curing of altax
Bisbenzothiazole, code name " promoting 2 " are bis- (the 2- mercaptos of N- cyclohexyl-that the trade mark of Huangyan, Zhejiang chemical plant production is accelerant C BBS
Base benzothiazole) sulfenamide, code name " promoting 3 " is the tertiary fourths of N- that the trade mark purchased from Huangyan, Zhejiang chemical plant is accelerator TBBS
Base -2-[4-morpholinodithio base sulfenamide；
Zinc oxide, activator：Purchased from Liuzhou Xin Pin Co., Ltds；
Stearic acid, activator：Purchased from the polite Chemical Co., Ltd. in Hong Kong, trade mark SA1801.
Table 2
(2) vulcanize
At 145 DEG C, 5MPa, gained rubber compound H ' 1~H ' 5 (are purchased from the first rubber manufacturing machinery of Shanghai in vulcanizing press
Factory) vulcanizing treatment 35min is carried out, obtain vulcanized rubber S1-S5.
Comparative example 1
The procedure of Example 1 was followed except that butadiene rubber of the raw rubber using not irradiated branched modification
BR9000 is denoted as DH1, and obtains rubber compound DH ' 1 and vulcanized rubber according to progress is formulated shown in table 2 in mixing process
DS1。
Comparative example 2
The procedure of Example 1 was followed except that raw rubber uses branched butadiene rubber made from ordinary chemical method
BR1280 is denoted as DH2, and obtains rubber compound DH ' 2 and vulcanized rubber according to progress is formulated shown in table 2 in mixing process
DS2。
Wherein, the product information of the branched butadiene rubber BR1280 is as follows：LG chemical companies of South Korea produce；Weight-average molecular
Amount is 39.26 ten thousand, molecular weight distribution 5.10, and Mooney viscosity ML (1+4min, 100 DEG C) is 42.6；Wherein cis- 1,4- butadiene
Structural content is 96.0 weight %, and anti-form-1,4- butadiene structure contents are 1.8 weight %, and 1,2- butadiene structure content is
2.2 weight %；Raw rubber elemental analysis is the result shows that be 229 micro- gram grams containing Al, it is 16.8 micro- gram grams, Al/Ni weight ratios to contain Ni
It is 13.63, is much larger than the Al/Ni weight ratios 1.35 of BR9000, illustrates that BR 1280 uses special catalysis during synthesis
Agent, with the structure different from BR9000, LG chemical companies official website is introduced, and BR1280 has strand branched structure.
Test case H1~H5 and DH1~DH2
Test case H1~H5 and DH1~DH2 are respectively to branched polybutadiene raw rubber H1~H5 obtained by preparation example and commercially available poly-
Butadiene raw rubber DH1~DH2 carries out following performance tests：
(1) branched network structure
H1~H5 and aforementioned butadiene rubber basic collagen material (i.e. DH1) are taken, it is public using IIC Dr.Kuhn GmbH＆Co KG
The IIC XLDS-15HT type nuclear-magnetism crosslink density instrument of department's production tests their branched network structure, the results are shown in Table shown in 3.Its
In, total crosslink density XLD includes the sum of physical entanglement point and chemical crosslinking dot density, and Mc refers to the mean molecule between crosslinking points
Amount.Total crosslink density XLD reflects the quantity of physical entanglement point and chemical crosslinking point in branched butadiene rubber molecule.
Table 3
| Product identification | Total crosslink density XLD (10-5mol/cm3) | Mc(kg/mol) |
| H1 | 4.34 | 21.91 |
| H2 | 4.25 | 23.30 |
| H3 | 3.96 | 23.97 |
| H4 | 4.34 | 21.87 |
| H5 | 3.79 | 25.04 |
| Basic glue (DH1) | 4.67 | 30.24 |
As can be seen from Table 3, after butadiene rubber basis glue method using the present invention before modified after XLD and Mc
It is not much different, this illustrates the preparation example product after branched modification via radiation, compared with the glue of unmodified butadiene rubber basis, not
Cross-linking reaction is generated, and branched improved for the processing performance of butadiene rubber without crosslinking appropriate is beneficial.
(2) average branching index
Average branching index λ (10-5Mol/g) according to formula λ=(Mbp -1-Mw -1)/2 are calculated, and acquired results are shown in Table 4
It is shown.
Wherein, MwRefer to that the weight average molecular weight of branched polybutadiene rubber, test method are：Using dual detector gel
Permeation chromatograph (GPC, the allianee GPC V2000 of Waters, US) measures, and wherein detector is differential refraction
(DRI) and capillary automatic viscometer (Vis), measuring temperature are 40 DEG C, and mobile phase solvent is tetrahydrofuran (THF)；
MbpRefer to that the main chain average molecular weight between adjacent two branch, computational methods are：According to above-mentioned MwAnd Vis as a result
Viscosity results, and according to Wang Dehua et al. (with electronic computer calculate polymer the degree of branching and molecular weight distribution [J] close
Synthetic rubber industry, 1978,5：Method 37-42) is calculated.
Table 4
The branch index λ of H1~H5 is significantly higher than the λ of DH1~DH2 it can be seen from 4 data of table, and with irradiation dose
Increase, the λ of H1 to H5 is also sequentially increased.Though wherein DH1 is without branched modification, its own contains certain branched structure,
Therefore λ is not zero.
(2) gel content
Raw rubber H1~H5 and DH1~DH2 are put in stainless (steel) wire, impregnated in toluene certain time, measurement does not dissolve in
Percentage shared by the part of toluene, as gel content, the results are shown in Table shown in 4.
As can be seen from Table 4, the gel content of raw rubber H1~H5 is significantly higher than the gel content of raw rubber DH1~DH2 mostly.
(3) Mooney viscosity
Using GT-7080-S2 type Mooney viscosities machine (the high Inland Steel's production in Taiwan) test raw rubber H1~H5 and DH1~DH2
Mooney viscosity, rotor use greater trochanter, 100 DEG C of temperature, Mooney testing time 1+4min.It the results are shown in Table shown in 4.
From table 4, it can be seen that the Mooney viscosity of raw rubber H1~H5 is generally significantly higher than the Mooney viscosity of DH1~DH2.
(4) processing performance
It is tested using RPA2000 rubber machining analyzers (U.S.'s alpha Products), condition is：Frequency scanning：Temperature
100 DEG C, strain 7%.The result is shown in Figure 1 of gained fissipation factor-frequency curve.
In fissipation factor-frequency curve of raw rubber frequency scanning, the fissipation factor numerical value under low frequency is higher, under high frequency
Fissipation factor numerical value reduces, and at higher frequencies, the fissipation factor numerical value of rubber of the same race is essentially identical, for a sample,
It scans from low to high, fissipation factor reduction is smaller, and the degree of branching of strand is higher.Therefore, it will be seen from figure 1 that H1
The degree of branching of the degree of branching ratio DH1 of~H5 molecules is high；And the branched journey of degree of branching ratio DH1~DH2 of H2~H5 molecules
Degree is high.The fissipation factor numerical value of the raw rubber of the higher present invention of degree of branching at low frequency is relatively low, and loss is smaller, has preferable
Processing performance.
Test case H ' 1~H ' 5 and DH ' 1~DH ' 2
Test case H ' 1~H ' 5 and DH ' 1~DH ' 2 are respectively to obtained by rubber compound H ' 1~H ' 5 obtained by embodiment and comparative example
Rubber compound DH ' 1~DH ' 2 are according to national standard《The assessment of carbon black and carbon black/silica dispersion is fast in GB/T 6030-2006 rubber
Fast comparison method》Regulation carry out carbon black dispersion performance test, characterization carbon black dispersion performance grade index be X values and Y value, X, Y
Value is closer to 10, and carbon black dispersion performance is better, and acquired results are as shown in table 5.
Table 5
It can be seen from the data of table 5 the X values of 5 rubber compound carbon black dispersion performances of H ' 1~H ' and DH ' 1~DH ' 2 quite or
The Y value for being better than DH ' 1~DH ' 2, H ' 1, H ' 2 and 4 rubber compound carbon black dispersion performances of H ' is better than DH ' 1~DH ' 2, rubber of the present invention point
The branched structure that son radiation generates provides preferable mixed refining process performance for sizing material, in mixing process easily and carbon black dispersion,
To make rubber compound maintain preferably carbon black dispersion performance.
Test case S1~S5 and DS1~DS2
Test case S1~S5 and DS1~DS2 are respectively to vulcanization obtained by vulcanized rubber S1~S5 obtained by embodiment and comparative example
Rubber DS1~DS2 carries out following performance tests：
(1) static mechanical property
By vulcanized rubber S1~S5 and DS1~DS2 according to national standard《GB/T 528-1998 vulcanized rubbers or thermoplastic elastomer
The measurement of tensile stress-strain performance》Its tensile property of regulation test, the AG-20KNG of puller system model Shimadzu Corporation production,
Obtain 100% stress at definite elongation (MPa)；According to《The pocket hardometer penetration hardness test method of GB/T531-1999 rubber》Test it
Shao's A hardness (units：Shore A)；According to《GB/T 528-1998 vulcanized rubbers or thermoplastic elastomer tensile stress-strain performance
Measurement Appendix B setafter breaks measurement and calculating》Method used tests it and is permanently deformed (%).Test result is shown in
Shown in table 6.
Table 6
| Product designation | Shao's A hardness | 100% stress at definite elongation/MPa | Permanent deformation/% |
| S1 | 54 | 2.3 | 6 |
| S2 | 48 | 1.9 | 7 |
| S3 | 66 | 4.2 | 4 |
| S4 | 64 | 3.7 | 5 |
| S5 | 64 | 3.9 | 4 |
| DS1 | 52 | 2.0 | 4 |
| DS2 | 52 | 2.0 | 6 |
As can be seen from Table 6,100% stress at definite elongation of S1~S5 and hardness are universal quite or is higher than DS1~DS2,
Permanent deformation is suitable with DS1~DS2.
(2) resilience performance of vulcanizate
According to national standard《GB/T 1681-1991 vulcanized rubber resiliences measure》Regulation test, resiliometer model
GT-7042-RE, Taiwan high ferro Products, acquired results are shown in Table 7.
Table 7
| Product designation | Resilience performance/% |
| S1 | 57 |
| S2 | 52 |
| S3 | 57 |
| S4 | 54 |
| S5 | 55 |
| DS1 | 54 |
| DS2 | 55 |
The resilience performance that can be seen that S1, S3 from 7 vulcanizate resilience performance data of table is better than DS1~DS2, remaining implementation
The resilience performance and DS1~DS2 of example are roughly the same, therefore the vulcanizate of the present invention maintains preferable resilience performance.
(3) compression deflects performance test
According to national standard《GB/T 1687-93 vulcanized rubbers are in the measurement the 2nd for deflecting experiment medium temperature liter and fatigue performance
Point：Compression deflects experiment》Regulation test, Tensile ＆ Elongation Tester model Y3000E, Beijing You Shen Electron equipment Co., Ltd product.
Acquired results are shown in Table 8.
Table 8
| Code name | S1 | S2 | S3 | S4 | S5 | DS1 | DS2 |
| Deformation percentage of static compression/% | -17.6 | -23.5 | -13.4 | -14.8 | -14.9 | -18.1 | -19.8 |
| First motion compression deformation rate/% | -10.6 | -17.2 | -6.4 | -8.6 | -8.4 | -10.9 | -12.8 |
Flexion data, which are compressed, from 8 vulcanizate of table can be seen that S1~S5 deformation percentage of static compression and first motion compression deformation rate
Absolute value is generally less than DS1~DS2, shows that irradiation branching modification improves the ability that vulcanizate resists compressive deformation.
(4) dynamic mechanical of vulcanizate
By rubber vulcanization at the piece of 1mm, it is measured using German GAOBO companies EPLEXOR500N type viscoelastic spectrometers,
In, frequency 11Hz, heating rate is 3 DEG C/min, and sample size is 40mm × 5mm × 1mm.With (0 DEG C) characterization vulcanization of tan δ
The wet-sliding resistant performance of rubber, tan δ (0 DEG C) are bigger, indicate that vulcanized rubber wet-sliding resistant performance is better；With (60 DEG C) characterization sulphur of tan δ
Change the rolling resistance of rubber, tan δ (60 DEG C) are smaller, indicate that vulcanized rubber rolling resistance is smaller；With glass transition temperature Tg table
The wear-resisting property of vulcanized rubber is levied, Tg is smaller, indicates that vulcanized rubber wear-resisting property is better.Acquired results are shown in Table 9, and are passed through
Fissipation factor-temperature curve that dynamic visco-elasticity analyser (DMA) measures is as shown in Figure 2.
Table 9
| Code name | S1 | S2 | S3 | S4 | S5 | DS1 | DS2 |
| Tanδ(0℃) | 0.1591 | 0.1795 | 0.1402 | 0.1448 | 0.1384 | 0.1573 | 0.1647 |
| Tanδ(60℃) | 0.1409 | 0.1722 | 0.1257 | 0.1394 | 0.1337 | 0.1393 | 0.1383 |
| Tg(℃) | -88.0 | -86.10 | -85.30 | -86.30 | -86.90 | -85.40 | -89.70 |
From table 9 and Fig. 2 vulcanizate dynamic mechanical data can be seen that the wet-sliding resistant performance of vulcanizate S1 and DS1~
DS2 is suitable, and the wet-sliding resistant performance of vulcanizate S2 is better than DS1~DS2, and the rolling resistance of vulcanizate S3 is less than DS1~DS2, S1,
The rolling resistance of S4 and S5 is suitable with DS1~DS2.Data above shows the wet-sliding resistant performance of embodiment vulcanizate S1~S5, rolling
Dynamic resistance is suitable with DS1~DS2 or is better than DS1~DS2.
(5) ageing-resistant performance of vulcanizate
According to national standard《GB3512-2001 vulcanized rubbers or the accelerated ageing of thermoplastic elastomer hot-air and heat resistant test》Regulation
Test, ageing oven model 401A, Nantong Hongda Experiment Instruments Co., Ltd.'s production, 100 DEG C of aging temperature, 48 hours time.Knot
Fruit is shown in Table 10.
Table 10
Note：
* performance change rate computational methods：
P=(Xa-X0)/X0* 100%
Wherein：P --- performance change rate, %
Xa--- the performance measure after sample aging
X0--- the performance measure before sample aging
* firmness change computational methods：
H=Xa-X0
Wherein：H --- performance change
Xa--- the hardness measurements after sample aging
X0--- the hardness measurements before sample aging
As can be seen from Table 10, the change rate before and after the aging of vulcanized rubber S1~S5 obtained by method of the invention with
DS1~DS2 is quite or better than DS1~DS2.
In conclusion the rubber composition of the present invention and the mechanical performance of the processing performance of rubber compound and vulcanized rubber with it is existing
There is technology to compare to be kept or improved.
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 can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, this
A little simple variants all belong to the scope of protection of the present invention.It is further to note that described in above-mentioned specific implementation mode
Each particular technique feature can be combined by any suitable means, in order to avoid not in the case of no contradiction
Necessary repetition, the present invention no longer separately illustrate various combinations of possible ways.In addition, a variety of different implementations of the present invention
Arbitrary combination can also be carried out between mode, as long as it does not violate the idea of the present invention, it is public equally to should be considered as institute of the invention
The content opened.
Claims (25)
1. a kind of rubber composition, which contains polybutadiene rubber, carbon black and operation oil, the polybutadiene rubber
Glue is branched polybutadiene rubber and its average branching index is 0.5 × 10-5-11×10-5mol/g；
Wherein, the branched polybutadiene rubber is to carry out irradiation to polybutadiene rubber using ray its branched modification is made to obtain
's；
Wherein, relative to polybutadiene rubber described in 1kg, the dosage of x ray irradiation x is 5-60kJ.
2. rubber composition according to claim 1, wherein the average branching index of the branched polybutadiene rubber is
1×10-5-11×10-5mol/g。
3. rubber composition according to claim 2, wherein the average branching index of the branched polybutadiene rubber is
5×10-5-11×10-5mol/g。
4. rubber composition according to claim 1, wherein using the total weight of the branched polybutadiene rubber as base
The content of standard, cis--Isosorbide-5-Nitrae-butadiene structure is 95-99 weight %, and the content of anti-form-1,4- butadiene structures is 0.7-2.5
The content of weight %, 1,2- butadiene structure are 0.3-2.5 weight %.
5. rubber composition according to claim 4, wherein total crosslink density of the branched polybutadiene rubber is 2
×10-5-6×10-5mol/cm3, the average molecular weight between crosslinking points is 18-30kg/mol.
6. rubber composition according to claim 1, wherein the gel content of the branched polybutadiene rubber is 1-10
Weight %, Mooney viscosity 50-75.
7. rubber composition according to claim 6, wherein the weight average molecular weight of the branched polybutadiene rubber is 28
×104-46×104G/mol, molecular weight distribution 2.9-5.1.
8. rubber composition according to claim 1, wherein the ray is one in electron beam, gamma-rays and X-ray
Kind is a variety of.
9. rubber composition according to claim 8, wherein the ray is gamma-rays.
10. rubber composition according to claim 9, wherein the energy of ray is 0.8-2MeV.
11. rubber composition according to claim 1, wherein relative to polybutadiene rubber described in 1kg, x ray irradiation x
Dosage be 20-60kJ.
12. rubber composition according to claim 1, wherein contained with polybutadiene rubber in the rubber composition
Amount is 100 parts by weight meters, and the content of the carbon black is 30-70 parts by weight.
13. rubber composition according to claim 12, wherein the carbon black is selected from industrial reference black and industrial production
With one or more in carbon black.
14. rubber composition according to claim 1, wherein contained with polybutadiene rubber in the rubber composition
Amount is 100 parts by weight meters, and the content of the operation oil is 5-20 parts by weight.
15. rubber composition according to claim 14, wherein the operation oil is selected from petroleum plasticizer, fat oil
It is one or more in plasticizer and synthesis plasticizer.
16. rubber composition according to claim 1, wherein the rubber composition also contains activator, the activator
It is mixed by inorganic activator and organic activator.
17. rubber composition according to claim 16, wherein contained with polybutadiene rubber in the rubber composition
Amount is 100 parts by weight meters, and the content of the activator is 2-6.5 parts by weight.
18. rubber composition according to claim 17, wherein contained with polybutadiene rubber in the rubber composition
Amount is 100 parts by weight meters, and the content of the inorganic activator is 1-4 parts by weight, and the content of the organic activator is 1-2.5 weights
Measure part.
19. rubber composition according to claim 1, wherein the rubber composition also contains vulcanizing agent and/or vulcanization
Accelerating agent.
20. rubber composition according to claim 19, wherein contained with polybutadiene rubber in the rubber composition
Amount is 100 parts by weight meters, and the content of the vulcanizing agent is 0.5-2 parts by weight, and the vulcanizing agent is elemental sulfur and/or sulfur-bearing chemical combination
Object.
21. rubber composition according to claim 20, wherein contained with polybutadiene rubber in the rubber composition
Amount is 100 parts by weight meters, and the content of the vulcanization accelerator is 0.2-1.5 parts by weight, and the vulcanization accelerator is selected from time yellow acyl
It is one or more in amine type accelerator, thiazole accelerator and guanidines.
22. a kind of preparation method of vulcanized rubber, which is characterized in that the method includes by any one of claim 1-21
The rubber composition is kneaded to obtain rubber compound, is then vulcanized to the rubber compound.
23. preparation method according to claim 22, wherein the process of the mixing includes：It first will be in rubber composition
Ingredient other than vulcanizing agent and vulcanization accelerator carries out first segment mixing, and vulcanizing agent is then added and vulcanization accelerator carries out
Second segment mixing.
24. the vulcanized rubber that the method according to claim 22 or 23 is prepared.
25. application of the vulcanized rubber described in claim 24 in preparing tire or tyre element.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510676929.0A CN106589488B (en) | 2015-10-19 | 2015-10-19 | A kind of rubber composition and vulcanized rubber and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510676929.0A CN106589488B (en) | 2015-10-19 | 2015-10-19 | A kind of rubber composition and vulcanized rubber and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106589488A CN106589488A (en) | 2017-04-26 |
| CN106589488B true CN106589488B (en) | 2018-07-20 |
Family
ID=58554187
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510676929.0A Active CN106589488B (en) | 2015-10-19 | 2015-10-19 | A kind of rubber composition and vulcanized rubber and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106589488B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109442119A (en) * | 2018-12-28 | 2019-03-08 | 深圳市鑫明兴科技有限公司 | A kind of anchor ear quickly couples crimping air hose |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6812277B2 (en) * | 2001-10-31 | 2004-11-02 | The Goodyear Tire & Rubber Company | Tire with component comprised of a blend of polybutadiene-rich rubber composition which contains a minor portion of styrene-rich styrene/isoprene elastomer |
| JP2010163590A (en) * | 2008-12-19 | 2010-07-29 | Ube Ind Ltd | Method for producing conjugated diene polymer, polybutadiene, and rubber composition using the same |
-
2015
- 2015-10-19 CN CN201510676929.0A patent/CN106589488B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN106589488A (en) | 2017-04-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103435858B (en) | Tyre inner liner rubber and preparation method thereof | |
| CN103865122A (en) | Tire side rubber for tire and preparation method of rubber | |
| CN107955232B (en) | Application of maleic acid monomer, rubber composition, vulcanized rubber and preparation method thereof | |
| CN104629126B (en) | The application of rubber composition and vulcanized rubber and vulcanized rubber | |
| CN102675701B (en) | Rubber composition with low compression heat and small rolling resistance | |
| CN107641228B (en) | Use of organosilanes and rubber compositions and vulcanizates and process for their preparation | |
| CN106674655B (en) | Rubber composition and vulcanized rubber and its preparation method and application | |
| Xu et al. | Influence of nanocrystalline cellulose on structure and properties of natural rubber/silica composites | |
| CN109929160B (en) | Application of organosilane coupling agent, rubber composition, vulcanized rubber and preparation method and application thereof | |
| CN109929159B (en) | Rubber composition and vulcanized rubber for tire tread as well as preparation method and application of rubber composition and vulcanized rubber | |
| CN104629125B (en) | The application of rubber composition and vulcanized rubber and preparation method thereof and vulcanized rubber | |
| CN103788432B (en) | The application of rubber combination and vulcanized rubber and preparation method thereof and vulcanized rubber | |
| CN110483996A (en) | A kind of silicone rubber O-ring sizing material and preparation method for wall-breaking machine main shaft seal | |
| CN106589488B (en) | A kind of rubber composition and vulcanized rubber and its preparation method and application | |
| Zhu et al. | Neodymium‐Based Catalyst for the Coordination Polymerization of Butadiene: From Fundamental Research to Industrial Application | |
| CN103254473B (en) | Rubber composition, vulcanized rubber, and preparation method thereof | |
| Pires et al. | Performance evaluation of high‐cis 1, 4‐polybutadienes | |
| CN106589425B (en) | Branched polybutadiene rubber and preparation method thereof and rubber compound | |
| CN110396265A (en) | Rubber composition and vulcanized rubber with self-healing function and its preparation method and application | |
| CN111363209A (en) | Formula and application of tire rubber containing multifunctional vulcanizing agent | |
| CN104497378A (en) | Anti-cracking high-performance rubber composite material and preparation method thereof | |
| JP6540750B2 (en) | Rubber composition and tire | |
| CN106032417B (en) | Rubber composition and vulcanized rubber and its application | |
| Cheng et al. | Experimental and application of continuous regeneration of waste rubber | |
| CN108178853A (en) | Modified host rubber and preparation method thereof and rubber composition and vulcanization rubber and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |