CN106589425A - Branched polybutadiene rubber and preparation method thereof and rubber compound - Google Patents
Branched polybutadiene rubber and preparation method thereof and rubber compound Download PDFInfo
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Abstract
The invention relates to the field of rubber and provides branched polybutadiene rubber, a method for preparing the polybutadiene rubber and a rubber compound prepared from the branched polybutadiene rubber. The average branching index of the branched polybutadiene rubber is 0.5*10<5>-11*10<5>mol/g; and the method for preparing the branched polybutadiene rubber comprises a step of irradiating the polybutadiene rubber with rays for branching modification. In the invention, the branching degree of the branched polybutadiene rubber is relatively high while crosslinking does not happen frequently; the obtained rubber compound and vulcanized rubber can obtain perfect processing property and mechanical property; in the method for preparing the branched polybutadiene rubber, the branching degree of the obtained branched polybutadiene rubber is easily controlled, and the operation is simple and industrial production is facilitated; and the method is likely to become a simple and effective method for improving the quality of traditional nickel butadiene rubber.
Description
Technical field
The present invention relates to rubber materials, in particular it relates to a kind of branched polybutadiene rubber, one kind system
The method of the standby branched polybutadiene rubber, and knead by obtained in the branched polybutadiene rubber
Glue.
Background technology
With the increasingly reduction of fossil fuel and raw material resources, requirement of the automobile industry to tire energy-conservation
Also more and more urgent, automobile energy consumption is consumed on tire, and reduces the rolling of tire
Dynamic resistance, the life-span for improving tire is the important goal of green tire.
Existing tire tread glue basis glue is typically contained intermingle with or emulsion polymerized styrene butadiene rubber, high-cis polybutadiene
Alkene rubber (hereinafter referred to as " butadiene rubber "), natural rubber and isoprene rubber etc. be used alone or and
With.But, rubber mixed generally deposited by what these existing tire tread glue rubber compositions were obtained
Processing characteristics not enough good, extrusion performance it is poor, sizing material is also easy to produce shakiness during high speed extrusion
Constant current it is dynamic so as to caused sizing material it is rough the problems such as, therefore by these traditional rubber compositions
The quality of obtained tire product can not meet the requirement of people.
In above-mentioned several glue kinds, butadiene rubber, especially nickel polymerized BR are preferable due to its
Wearability and warping strength fatigue behaviour become one of main glue kind of manufacture tire, typically with it is natural
Rubber and/or butadiene-styrene rubber and with for tread rubber, being additionally operable to tire shoulder glue, but traditional butadiene rubber
There is also processing characteristics general, extrusion plus man-hour is also easy to produce that flow instabilities, wet-sliding resistant performance be poor, rolling
The defect such as dynamic resistance is larger.In order to overcome drawbacks described above, prior art to begin attempt to traditional suitable fourth
Rubber be branched it is modified, to improve its processing characteristics and performance.
US7030195B2 discloses a kind of preparation method of reduced branching degree butadiene rubber.The first step, fourth
Diene is in organic solvent and catalyst (aluminium compound of neodymium compound, alkyl aluminum and the halogen such as chloride)
Reaction, conversion ratio ＞ 98% generates cis-Isosorbide-5-Nitrae-content ＞ 93%, and molecular weight distribution mw/mn exists
Line style cis polybutadiene between 2.2-2.9.Second step, is obtained with the peroxide treatment first step
Polymer solution.3rd step, extracts reduced branching degree polybutadiene in the solution obtained from second step.
In the existing technology for preparing branched butadiene rubber, mainly using chemical treatment method, for example
Structure regulator is added during rubber is polymerized or be allowed to produce branched knot using methods such as catalyst
Structure, but often degree of branching is relatively low for chemical method, or hold very much when attempting to obtain higher branch degree
Easily there is crosslinking phenomena, so as to the mechanical performance and processing characteristics that cause gained branched modification product can not expire
The higher requirement of foot, the problems such as the more difficult control of complex operation, degree of branching is also usually present in addition.Therefore,
Need to propose a kind of new method of the branched modification that can solve the problem that the problems referred to above.
The content of the invention
The purpose of the present invention is the drawbacks described above for overcoming prior art, there is provided a kind of branched polybutadiene rubber
Glue, a kind of method for preparing the branched polybutadiene rubber, and by the branched polybutadiene rubber system
The elastomeric compound for obtaining.The present invention branched polybutadiene rubber degree of branching it is higher and be difficult crosslinking, it is made
The elastomeric compound for obtaining and vulcanized rubber can have good mechanical performance and processing characteristics, the preparation of the present invention
The degree of branching of the branched polybutadiene rubber of the easily controllable gained of method of branched polybutadiene rubber, and
And it is simple to operate beneficial to industrialized production.
The invention provides a kind of branched polybutadiene rubber, average of the branched polybutadiene rubber
It is 0.5 × 10 to change index-5-11×10-5mol/g。
Present invention also offers a kind of method of the branched polybutadiene rubber for preparing the present invention, the method
Its branched modification is made including irradiation is carried out to polybutadiene rubber using ray.
Invention additionally provides a kind of elastomeric compound, the elastomeric compound contains the branched polybutadiene of the present invention
Rubber.
It was found by the inventors of the present invention that within the specific limits, the polybutadiene rubber of higher branch degree
Processing characteristics can be better than the polybutadiene rubber of relatively low degree of branching, however, the change that prior art is used
Method gained degree of branching is generally relatively low, and when the chemical method of prior art is attempted improving branched journey
The phenomenon for crosslinking occur is easy to when spending.The present inventor surprisingly sends out during further investigation
Existing, the method for preparing branched polybutadiene rubber using x ray irradiation x can obtain being significantly higher than existing skill
The polybutadiene rubber of the degree of branching of art, and the easily controllable degree of branching of the method, it is not easy to occur
The phenomenon of crosslinking, so that the mechanical performance and processing characteristics of sizing material are improved, and can carried out
Energy is more saved when mixing and sulfuration.
Other features and advantages of the present invention will give specifically in subsequent specific embodiment part
It is bright.
Description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute the part of specification,
It is used to explain the present invention together with detailed description below, but does not constitute the limit to the present invention
System.In the accompanying drawings：
Fig. 1 is embodiment gained I1～I5 and comparative example gained i1～i2 Jing rubber machining analyzers RPA is surveyed
Fixed fissipation factor-frequency scanning curve；
Fig. 2 is embodiment gained I1～I5 and comparative example gained i1～i2 Jing rubber machining analyzers RPA is surveyed
Fixed fissipation factor-strain sweep curve；
Fig. 3 is embodiment gained I1～I5 and comparative example gained i1～i2 is in banbury during first paragraph banburying
Temperature-time curve；
Fig. 4 is embodiment gained I1～I5 and comparative example gained i1～i2 is in banbury during first paragraph banburying
Power against time curve；
Fig. 5 is embodiment gained II1～II5 and comparative example gained ii1～ii2 Jing rubber machining analyzer RPA
The fissipation factor of measure-strain sweep curve；
Fig. 6 is embodiment gained II1～II5 and comparative example gained ii1～ii2 Jing rubber machining analyzer RPA
The fissipation factor of measure-frequency scanning curve.
Specific embodiment
The specific embodiment of the present invention is described in detail below.It should be appreciated that this place
The specific embodiment of description is merely to illustrate and explains the present invention, is not limited to the present invention.
The invention provides a kind of branched polybutadiene rubber, average of the branched polybutadiene rubber
It is 0.5 × 10 to change index-5-11×10-5mol/g。
In the present invention, average branching index is used to represent the degree of branching of polybutadiene rubber, described
Average branching index=(Mbp -1-Mw -1)/2, wherein MbpFor the main chain mean molecule between adjacent two side chain
Amount, MwFor polymer average molecular weight.Wherein, MwDual detector gel permeation chromatograph can be passed through
(GPC, the allianee GPC V2000 of Waters, US) is measured, and dual detector is to show poor folding
Light (DRI) and capillary automatic viscometer (Vis), 40 DEG C of temperature of the measurement, mobile phase solvent is tetrahydrochysene
Furans (THF)；MbpCan be according to MwWith the viscosity results of Vis, according to Wang Dehua et al. (electricity consumptions
Sub- computer calculates the degree of branching and molecular weight distribution [J] of polymer. China Synthetic Rubber Industry, 1978,5：
Method 37-42) is calculated.
In general, it is flat when less or prior art during without crosslinking phenomena branched polybutadiene rubber
Branch index is generally less than 0.5 × 10-5Mol/g, when prior art branched polybutadiene rubber it is flat
Branch index is higher than 0.5 × 10-5Crosslinking phenomena generally occurs during mol/g, and when average branch refers to
Number also not up to 5 × 10-5Crosslinking phenomena is very serious during mol/g.It was found by the inventors of the present invention that
When the average branching index of the branched polybutadiene rubber is 0.5 × 10-5-11×10-5Mol/g and do not have
During crosslinking phenomenon, the combination property of its mechanical performance and processing characteristics is more excellent, and its reason may
It is：Average branching index branched polybutadiene rubber within the above range has more suitable short
Chain branching structure and strand spacing, strand easy sliding during mixing, compound viscosity is moderate, mixing
Moment of torsion reduce, reduce mixing energy, sizing material temperature rise is relatively low.In general, within the specific limits
(for example it is not more than 11 × 10-5During mol/g), average branching index is higher, branched polybutadiene rubber and
Elastomeric compound processing characteristics obtained by it is better, and the mechanical performance of vulcanized rubber is also preferable, therefore, at this
In 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, more preferably 2 × 10-5-11×
10-5Mol/g, more preferably 5 × 10-5-11×10-5Mol/g, more preferably 5 × 10-5-10×
10-5Mol/g, more preferably 6 × 10-5-9×10-5mol/g。
In the present invention, the branched polybutadiene rubber is branched cis-rich polybutadiene rubber (abbreviation
For " branched butadiene rubber "), and on the basis of the gross weight of the branched polybutadiene rubber, it is suitable
The content of formula-Isosorbide-5-Nitrae-butadiene structure is 95-99 weight %, anti-form-1, and the content of 4- butadiene structures is
0.7-2.5 weight %, the content of 1,2- butadiene structure is 0.3-2.5 weight %；It is further preferred that with
On the basis of the gross weight of the branched polybutadiene rubber, wherein the content of cis-Isosorbide-5-Nitrae-butadiene structure
For 95.5-97.5 weight %, anti-form-1, the content of 4- butadiene structures is 1.5-2.5 weight %, 1,2- fourth two
The content of alkene structure is 1-2 weight %.Furthermore it is preferred that the branched polybutadiene rubber is branched
Nickel content in nickel polymerized BR, wherein rubber is preferably the micro- gram grams of 10-15, the weight ratio of Al/Ni
Preferably 1-2, the nickel and aluminium in the rubber is actually butadiene rubber catalysis used in preparation process
Agent remains in nickel and aluminium in rubber.In the present invention, term " rubber " continues to use containing for this area routine
Justice, refers to the rubber product for not adding auxiliary agent to be kneaded, and being somebody's turn to do the statement of " rubber " is used for and " mixing
Glue " and " vulcanized rubber " make a distinction.
In the present invention, the branched polybutadiene rubber does not have obvious crosslinking phenomena, usually, this
Total crosslink density (referred to as XLD) of the branched polybutadiene rubber of invention is 2 × 10-5-6×
10-5mol/cm3, preferably 3.5 × 10-5-4.5×10-5mol/cm3, the mean molecule quantity (letter between crosslinking points
Referred to as Mc) it is 18-30kg/mol, preferably 21-26kg/mol.Wherein described XLD is twined including physics
Node and chemical crosslinking dot density sum, XLD and Mc passes through IIC Dr.Kuhn GmbH＆Co
The IIC XLDS-15HT type nuclear-magnetism crosslink density instrument of KG companies production is measured.
In the present invention, the gel content of the branched polybutadiene rubber can be 1-10 weight %,
Preferably 5-8 weight %；Mooney viscosity can be 50-75, preferably 55-72.In the present invention, door
Buddhist nun's viscosity is tested according to the method for standard GB/T/T1232.1-2000 defineds, wherein rotor choosing
With the greater trochanter in the standard shown in table 1, temperature is set as 100 DEG C, and the Mooney testing time is
1+4min, is denoted as ML (1+4min, 100 DEG C), in the art the parameter list by the Mooney viscosity parameter
Position is Mooney point M, and traditionally the result of Mooney viscosity omits M, i.e. numerical value 1 and represents a Mooney point.
In the present invention, as a rule, 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.
Present invention also offers a kind of method for preparing branched polybutadiene rubber, the method includes using
Ray carries out irradiation and makes its branched modification to polybutadiene rubber.
It was found by the inventors of the present invention that the chemical method of traditional preparation branched polybutadiene rubber is often
Exist that degree of branching is relatively low, crosslinking phenomena easily occur, complex operation, gained branched modification product
The more difficult control of degree of branching, and the mechanical performance and processing characteristics of the gained branched modification product be still inadequate
Good the problems such as, and have been surprisingly found that the method that can adopt x ray irradiation x to poly- during further investigation
Butadiene rubber is branched modified, and the method can obtain being significantly higher than the degree of branching of prior art
Polybutadiene rubber, and the easily controllable degree of branching of the method, it is not easy to the phenomenon for crosslinking,
So that the mechanical performance and processing characteristics of sizing material are improved, and being kneaded and can be vulcanized
When more save energy.
In the present invention, there is no particular limitation for the ray that irradiation is adopted, and is using conventional ray
Can, for example can be one or more in electron beam, gamma-rays and X-ray, preferably gamma-rays；
For gamma-rays is being not particularly limited by which kind of radioactive element decay generation, preferably60Co decays
The gamma-rays of generation.There is no particular limitation for the energy of ray, for example, can be 0.8-2MeV, preferably
For 1-1.5MeV；When ray is60During the gamma-rays that Co decays are produced, the energy of ray is preferably
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 species of ray
Selected with the demand of degree of branching, usually, the dosage of the x ray irradiation x of the present invention can be
5-60kGy is (i.e. relative to the polybutadiene rubber before 1kg irradiation branched modifications, x ray irradiation x
Dosage be 5-60kJ), preferably 20-60kGy (i.e. 20-60kJ/kg), more 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 of the polybutadiene rubber before irradiation branched modification can be with
For 0.1-1.9 weight %, 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, the implementation environment of the method for preparing branched polybutadiene rubber can be adopted
The conventional environment in this area, for example, can be carried out in limit oxygen environment, and the limit oxygen environment refers to environment
The middle oxygen amount for limiting as test specimen encapsulate when air in oxygen amount.Oxygen amount in the air must be limited in necessarily
Scope, under packaging environment, volume of air and pending (before irradiation branched modification) polybutadiene
The ratio scope of the volume of rubber is 0.001-0.05：1, preferably 0.004-0.03：1, for example,
0.004-0.006：1.It is (main that the radiation of air small can introduce oxygen-containing polar group in strand
It is carbonyl group), the binding ability of rubber and polar filler can be improved, improve processing characteristics, but spoke
Penetrate dosage excessive, crosslinking and excessive degradation will be produced.Limit oxygen radiation can then improve this kind of situation, because
Oxygen and nitrogen content for radiation space is limited, and the degraded introduced with polar group is not obvious, and radiation is main
Cause the branched of strand.Crosslinking and degradation reaction are participated in without substantial amounts of oxygen, so as to inhibit strand
In oxygen-containing polar group a large amount of introducings.There is no particular limitation for the mode of offer limit oxygen environment, for example may be used
To be sealed with plastic sheeting.
The method of the present invention can as adjust ray dosage easily control obtained by branched polybutadiene
The degree of branching of rubber, and crosslinking phenomena is less likely to occur such that it is able to effectively improve products obtained therefrom
Mechanical performance and processing characteristics, and energy can be more saved when being kneaded and being vulcanized.
Inventor has found during lot of experiments, in general, when the dosage of x ray irradiation x is
During 5-60kGy, can by the control of the average branching index of gained branched butadiene rubber 0.5 ×
10-5-11×10-5In the range of mol/g；When the dosage of x ray irradiation x is 20-60kGy, can be by institute
The average branching index for obtaining branched butadiene rubber is controlled 1 × 10-5-11×10-5In the range of mol/g；
When the dosage of x ray irradiation x is 30-60kGy, can be by the average branch of the branched butadiene rubber of gained
Index is controlled 5 × 10-5-11×10-5In the range of mol/g；When the dosage of x ray irradiation x is 35-50kGy
When, the average branching index of the branched butadiene rubber of gained can be controlled 6 × 10-5-9×
10-5In the range of mol/g.Simultaneously by using the method for the present invention, the branched polybutadiene rubber of gained
Without obvious crosslinking phenomena, usually, total crosslink density of the branched polybutadiene rubber of the present invention
XLD is 2 × 10-5-6×10-5mol/cm3, preferably 3.5 × 10-5-4.5×10-5mol/cm3, crosslinking points
Between mean molecule quantity Mc be 18-30kg/mol, preferably 21-26kg/mol.
Average branching index obtained by method of the present invention branched polybutadiene rubber within the above range
Glue has more suitable short-chain branched structure and a strand spacing, strand easy sliding during mixing,
Compound viscosity is moderate, and the moment of torsion of mixing is reduced, and reduces mixing energy, and sizing material temperature rise is relatively low.And show
Have the process for branching of technology, branched structure is wayward, be likely to result in long chain branching it is more or crosslinking,
It is easily caused macromolecule to tangle seriously, dyskinesia is unfavorable for reducing mixing energy on the contrary；It is also possible to prop up
Change structure is less, and strand is based on line style, and strand spacing is little, and inter-chain action power is big, dyskinesia,
Also it is unfavorable for reducing mixing energy.Therefore, there is more preferable machinery using the branched rubber obtained by this method
Performance and processing characteristics.
Present invention also offers a kind of elastomeric compound, the elastomeric compound contains the branched polybutadiene rubber of the present invention
Glue.There is no particular limitation for the component and preparation method of the elastomeric compound, using the conventional side in this area
Method, for example can be according to《GBT 8660-2008 polymerisation in solutions type butadiene rubber (BR) evaluation side
Method》The component and method of regulation is kneaded, and is specifically included：Compounding process is two sections of mixer mixings,
First paragraph banburying adds rubber (branched polybutadiene rubber i.e. of the invention), carbon black, operation oily, hard
Resin acid, zinc oxide, discharge sizing material, and second segment banburying adds sulphur, accelerator.Original wherein used
Material can prepare the conventional use of raw material of elastomeric compound for this area, will not be described here.
The present invention will be further described in detail by specific embodiment below.
Embodiment I1～I5 and comparative example i1～i2 is used to illustrate the branched polybutadiene rubber of present invention offer
Preparation method and the branched polybutadiene rubber for preparing
Embodiment I1～I5
Respectively by unmodified basic glue, in limit oxygen environment, (plastic sheeting is sealed embodiment I1～I5, air
Volume is 0.005 with the ratio of the volume of pending polybutadiene rubber：1) according to the spoke shown in table 1 in
Irradiation is carried out according to dosage and radiographic source, the product that numbering is I1～I5 is respectively obtained.
Wherein, the basic glue used by embodiment I1～I5 is Yanshan Mountain branch company of China Petrochemical Corp.
The trade mark of production is the butadiene rubber basis glue of BR9000, and its nature parameters includes：Weight average molecular weight is
38.2 ten thousand, molecular weight distribution is 3.91, and Mooney viscosity ML (1+4min, 100 DEG C) is 45 ± 4；Wherein
Cis- Isosorbide-5-Nitrae-butadiene structure content is 96.5 weight %, and anti-form-1,4- butadiene structures content is 2.0 weights
Amount %, 1,2- butadiene structure content is 1.5 weight %；Rubber elementary analysis result shows
15.4 micro- gram grams, are 11.4 micro- gram grams containing Ni, and Al/Ni weight ratio is 1.35.
Table 1
| Numbering | Irradiation dose (kGy) | Radiographic source | Ray energy (MeV) | Basic glue | |
| Embodiment I1 | I1 | 5 | Electron beam | 1.0 | BR9000 |
| Embodiment I2 | I2 | 20 | X-ray | 1.5 | BR9000 |
| Embodiment I3 | I3 | 30 | 60The gamma-rays that Co decays are produced | 1.17 with 1.33 | BR9000 |
| Embodiment I4 | I4 | 40 | 60The gamma-rays that Co decays are produced | 1.17 with 1.33 | BR9000 |
| Embodiment I5 | I5 | 60 | 60The gamma-rays that Co decays are produced | 1.17 with 1.33 | BR9000 |
Comparative example i1
Using the butadiene rubber basis glue BR9000 used by embodiment I1～I5, except that, according to
The method of the embodiment 1 of US7030195B2 is branched modified, and the product for obtaining is designated as i1.
Comparative example i2
Branched butadiene rubber prepared by commercially available chemical method, is designated as i2：Trade mark BR 1280, Korea's LGization
Company produces；Weight average molecular weight is 39.26 ten thousand, and molecular weight distribution is 5.10, Mooney viscosity
ML (1+4min, 100 DEG C) is 42.6；Wherein cis- Isosorbide-5-Nitrae-butadiene structure content is 96.0 weight %, instead
Formula-Isosorbide-5-Nitrae-butadiene structure content is 1.8 weight %, and 1,2- butadiene structure content is 2.2 weight %；It is raw
Glue elementary analysis result shows that containing Al be 229 micro- gram grams, is 16.8 micro- gram grams containing Ni, and Al/Ni is heavy
Than being 13.63, the Al/Ni weight much larger than BR9000 compares 1.35 to amount, illustrates BR 1280 in synthesis
During adopt special catalyst, be allowed to have different from BR9000 structure, LG chemical companies official
Net is introduced, and BR 1280 has strand branched structure.
Test case I1～I7
Test case I1～I7 respectively to 1～I5 of branched polybutadiene rubber raw rubber product I obtained above and
I1～i2 carries out following performance test：
(1) branched network structure
1～I5 of product I and aforementioned butadiene rubber basic collagen material BR9000 is taken, using IIC Dr.Kuhn
The IIC XLDS-15HT type nuclear-magnetism crosslink density instrument of GmbH＆Co KG companies production tests theirs
Branched network structure, the results are shown in Table shown in 2.Wherein, total crosslink density XLD includes physical entanglement point
And dot density sum is chemically crosslinked, Mc refers to the mean molecule quantity between crosslinking points.Total crosslink density XLD
Reflect the quantity of physical entanglement point and chemical crosslinking point in branched butadiene rubber molecule.
Table 2
| Production code member | Total crosslink density XLD (10-5mol/cm3) | Mc(kg/mol) |
| I1 | 4.34 | 21.91 |
| I2 | 4.25 | 23.30 |
| I3 | 3.96 | 23.97 |
| I4 | 4.34 | 21.87 |
| I5 | 3.79 | 25.04 |
| Basic glue | 4.67 | 30.24 |
As can be seen from Table 2, butadiene rubber basis glue using after the method for the present invention before modified after
XLD and Mc be more or less the same, this explanation embodiment product via radiation after branched modification and does not change
Property butadiene rubber basis glue compare, do not produce cross-linking reaction, and it is appropriate branched and be not crosslinked for
It is beneficial that the processing characteristics of butadiene rubber is improved.
(2) average branching index
Average branching index λ (10-5Mol/g) calculating λ=(M is carried out according to following formulabp -1-Mw -1)/2, gained knot
Fruit is shown in Table 3.
Wherein, MwThe weight average molecular weight of branched polybutadiene rubber is referred to, method of testing is：Using
Dual detector gel permeation chromatograph (GPC, the allianee GPC V2000 of Waters, US)
Measure, wherein detector is differential refraction (DRI) and capillary automatic viscometer (Vis), determines temperature
Spend for 40 DEG C, mobile phase solvent is tetrahydrofuran (THF)；
MbpThe main chain mean molecule quantity between adjacent two side chain is referred to, computational methods are：According to above-mentioned
MwAs a result with the viscosity results of Vis, and polymer (is calculated with electronic computer according to Wang Dehua et al.
The degree of branching and molecular weight distribution [J]. China Synthetic Rubber Industry, 1978,5：Method 37-42) is calculated
Arrive.
Table 3
| Production code member | Average branching index λ (10-5mol/g) | |
| Test case I1 | I1 | 0.51 |
| Test case I2 | I2 | 1.50 |
| Test case I3 | I3 | 8.62 |
| Test case I4 | I4 | 8.80 |
| Test case I5 | I5 | 10.10 |
| Test case I6 | i1 | 0.45 |
| Test case I7 | i2 | 0.23 |
With reference to obtained by the data of table 1 and table 3 can be seen that the method using the x ray irradiation x of the present invention
The average branching index of branched butadiene rubber be significantly larger than comparative example using branched obtained in chemical method
Butadiene rubber, and using the present invention x ray irradiation x when, the average branching index of branched butadiene rubber with
Increasing for irradiation dose and increase, it is easy to control.
(3) gel content
I1～I5 and i1～i2 are put in stainless (steel) wire, certain hour is soaked in toluene, measured insoluble
In the percentage shared by the part of toluene, as gel content the results are shown in Table shown in 4.
Table 4
| Product designation | Gel content (%) | Mooney viscosity | |
| Test case I1 | I1 | 1.920 | 57 |
| Test case I2 | I2 | 5.954 | 61 |
| Test case I3 | I3 | 7.449 | 66 |
| Test case I4 | I4 | 5.646 | 72 |
| Test case I5 | I5 | 7.480 | 71 |
| Test case I6 | i1 | 1.057 | 51 |
| Test case I7 | i2 | 1.9170 | 43 |
As can be seen from Table 4, the gel content of the 1～I5 of branched butadiene rubber product I of embodiment I1～I5
The gel content of the branched butadiene rubber i1～i2 of comparative example i1 and i2 is significantly higher than mostly.
(4) Mooney viscosity
Using GT-7080-S2 type Mooney viscosity machines (the high Inland Steel's production in Taiwan) according to national standard
GB/T1232.1-2000 tests the Mooney viscosity of I1～I5 and i1～i2, and rotor adopts greater trochanter, temperature
100 DEG C, Mooney testing time 1+4min is denoted as ML (1+4min, 100 DEG C) and the results are shown in Table shown in 4.
From table 4, it can be seen that the Mooney viscosity of the 1～I5 of branched butadiene rubber product I of embodiment I1～I5
Generally it is significantly higher than the Mooney viscosity of the branched butadiene rubber i1～i2 of comparative example i1 and i2.
(5) processing characteristics
Using RPA2000 rubber machining analyzers (U.S.'s alpha Products) to I1～I5 and i1～i2
Tested, condition is：Frequency scanning：100 DEG C of temperature, strain 7%；Strain sweep：Temperature
100 DEG C, frequency 1Hz.As a result Fig. 1 and Fig. 2 is seen respectively.
Frequency scanning fissipation factor-frequency curve (Fig. 1) in, the fissipation factor numerical value under low frequency compared with
Fissipation factor numerical value under height, high frequency is reduced, at higher frequencies, the fissipation factor number of rubber of the same race
Value is essentially identical, for a sample, scans from low to high, and fissipation factor reduces less, molecule
The degree of branching of chain is higher.Therefore, it will be seen from figure 1 that the degree of branching of embodiment I1～I5 molecules
Degree of branching generally than comparative example i1-i2 is high.
In the fissipation factor-strain curve (Fig. 2) of strain sweep, for a sample, fissipation factor
Less, the degree of branching of strand is higher.Therefore, from figure 2 it may also be seen that embodiment molecule
Change degree is higher than the degree of branching of comparative example.
Embodiment II1～II5 and comparative example ii1～ii2 is used to illustrate the elastomeric compound of the present invention
According to《GBT 8660-2008 polymerisation in solution type butadiene rubber (BR) evaluation methods》What is specified matches somebody with somebody
Side's mixing, compounding process is two sections of mixer mixings, and first paragraph banburying is added obtained by 100 weight portions
Branched polybutadiene rubber product I1～I5 and i1～i2,60 parts by weight of carbon black per, 15 weight portions operation oil, 2
Weight portion stearic acid, 3 part by weight of zinc oxide, discharge sizing material, and second segment banburying adds 1.5 weight portion sulphur
Sulphur and 0.9 weight portion vulcanization accelerator, finally give compound manufacture and be designated as respectively II1～II5 and
Ii1～ii2 (corresponds to respectively embodiment II1～II5 and comparative example ii1～ii2).
Mixing facilities be 1.6L banburies, producer be Farrel Corp. of the U.S., model BR1600Raw materials used producer and the trade mark is as follows：
Carbon black：Imported from America, the trade mark is ASTM IRB8 (Industry Reference Black)；
Sulphur：Science and Technology Ltd. is contained purchased from Guangzhou Jinchang, the trade mark is S-80；
Vulcanization accelerator：N tert butyl benzothiazole 2 sulfenamide, purchased from Huangyan, Zhejiang chemical plant, board
Number be TBBS；
Zinc oxide, activator：Purchased from Liuzhou Xin Pin Co., Ltds；
Stearic acid, activator：Purchased from the polite Chemical Co., Ltd. in Hong Kong, the trade mark is SA1801；
Operation oil：Imported from America, the trade mark is ASTM103#Oil.
In addition, during mixing, recording the melting temperature and power in sizing material first paragraph internal mixing pass
Time dependent curve, respectively as shown in Fig. 3 and Fig. 4.As can be seen that real from Fig. 3 and Fig. 4
Applying the power curve-time of example has more fluctuation, it has also been found that mixing process in mixer mixing process
The not conglomeration of middle sizing material, is separated into more broken fritter, it may be possible to which the molecule of branched structure is in relatively low shearing
Flow instabilities are easily produced under speed, produces what melt fracture caused.But, after mixing terminates,
Elastomeric compound can preferably clump together.And in mixing later stage, after mixing time 240s, embodiment
After the melting temperature of II1～II4 is less than comparative example ii1 and ii2, and mixing time 120s, embodiment
The mixer power of II1～II5 also below comparative example ii1 and ii2, when illustrating that the branched butadiene rubber of embodiment is kneaded
Energy is saved than comparative example 1 and 2, processing characteristics is preferable.
Test case II1～II7
Test case II1～II7 is tested compound manufacture II1～II5 and ii1～ii2 obtained above respectively,
Concrete mode is as follows：
(1) processing characteristics
Tested using RPA2000 rubber machining analyzers (U.S.'s alpha Products), tested
Condition is：Strain sweep：Temperature 60 C, frequency 1Hz；Frequency scanning：Temperature 60 C, strain 7%.
Acquired results are respectively as shown in Fig. 5 and Fig. 6.Sweep from the strain sweep and frequency of Fig. 5 and Fig. 6 elastomeric compounds
Retouch curve to can be seen that under wider strain and frequency range, the fissipation factor of embodiment II1～II5
Less than comparative example ii1～ii2, illustrate that embodiment elastomeric compound machining energy loss ratio comparative example is little, with preferable
Processing characteristics.
(2) curability
Using surveying to the curability of elastomeric compound without rotor vulcameter purchased from the high Inland Steel in Taiwan
Try, test condition is：Oscillation angle is 1 °, and frequency is 1.7Hz, and temperature is 145 DEG C.Acquired results
As shown in table 5, wherein, MH (dNm) represents maximum torque, and ML (dNm) represents minimum turn
Square, ts1 (m:S) time of scorch is represented, reflects the sulfuration security of elastomeric compound, tc10 (m:s)、
tc50(m:S) with tc90 (m:S) represent that sulfuration reaches the time used in various degree, wherein tc90 is anti-
The sulfurizing time of elastomeric compound is reflected.
Table 5
*m：S represents minute：Second, such as 11:44 represent 44 seconds 11 minutes.
For butadiene rubber, the sulfurizing time tc90 of embodiment II1-II2 and comparative example ii1 and ii2's
Tc90 is suitable, and the tc90 of embodiment II3-II5 is shorter than the tc90 of comparative example ii1 and ii2, illustrates to implement
The cure time of example is suitable with comparative example or shorter than comparative example, and energy is relatively saved during sulfuration.Embodiment II1-II5
Ts1, tc10, tc50 be shorter than comparative example ii1 and ii2, illustrate that embodiment time of scorch is short, processing peace
Good perfection, curingprocess rate is fast.To a certain extent, curability can also reflect mechanical performance, typically
Think that the maximum torque MH of curing curve is bigger, show that elastomeric compound vulcanizes the vulcanizate stress at definite elongation to be formed
Higher, mechanical performance is better, so as to the branched poly- fourth obtained by can also learning according to the present processes
The vulcanizate of diene rubber has higher mechanical performance.
In sum, using the average branch of the branched polybutadiene rubber obtained by the method for the present invention
Index can be significantly higher than the branched polybutadiene rubber obtained by chemical method, and the method for the present invention can
Cross-linked structure is not produced to obtain the more suitable degree of branching by regulation irradiation dose.And, adopt
The branched polybutadiene rubber being obtained by the present invention more saves energy when being kneaded and being vulcanized
Amount, and the processing characteristics and mechanical performance of resulting mixing of rubber is also superior to comparative example.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned
Detail in embodiment, in the range of the technology design of the present invention, can be to the skill of the present invention
Art scheme carries out various simple variants, and these simple variants belong to protection scope of the present invention.In addition
It should be noted that each particular technique feature described in above-mentioned specific embodiment, not
In the case of contradiction, can be combined by any suitable means, in order to avoid unnecessary weight
Multiple, the present invention is no longer separately illustrated to various possible combinations.Additionally, the present invention it is various not
Can also be combined between same embodiment, as long as its thought without prejudice to the present invention, its
Content disclosed in this invention should be equally considered as.
Claims (10)
1. a kind of branched polybutadiene rubber, it is characterised in that the branched polybutadiene rubber it is average
Branch index is 0.5 × 10-5-11×10-5mol/g。
2. branched polybutadiene rubber according to claim 1, wherein, the branched polybutadiene
The average branching index of alkene rubber is 1 × 10-5-11×10-5Mol/g, more preferably 5 × 10-5-11×
10-5mol/g。
3. branched polybutadiene rubber according to claim 1 and 2, wherein, with described branched
On the basis of the gross weight of polybutadiene rubber, the content of cis-Isosorbide-5-Nitrae-butadiene structure is 95-99 weights
Amount %, anti-form-1, the content of 4- butadiene structures is 0.7-2.5 weight %, the content of 1,2- butadiene structure
For 0.3-2.5 weight %.
4. branched polybutadiene rubber according to claim 1 and 2, wherein, it is described branched poly-
Total crosslink density of butadiene rubber is 2 × 10-5-6×10-5mol/cm3, the mean molecule quantity between crosslinking points
For 18-30kg/mol.
5. branched polybutadiene rubber according to claim 1 and 2, wherein, it is described branched poly-
The gel content of butadiene rubber is 1-10 weight %, and Mooney viscosity is 50-75；
Preferably, the weight average molecular weight of the branched polybutadiene rubber is 28 × 104-46×104G/mol,
Molecular weight distribution is 2.9-5.1.
6. a kind of side for preparing the branched polybutadiene rubber in claim 1-5 described in any one
Method, it is characterised in that the method includes that carrying out irradiation to polybutadiene rubber using ray makes its branched
It is modified.
7. method according to claim 6, wherein, the ray be electron beam, gamma-rays and
One or more in X-ray, preferably gamma-rays；
Preferably, the energy of ray is 0.8-2MeV.
8. the method according to claim 6 or 7, wherein, relative to polybutadiene described in 1kg
Rubber, the dosage of x ray irradiation x is 5-60kJ, preferably 20-60kJ.
9. method according to claim 6, wherein, methods described is carried out in limit oxygen environment；
Preferably, the limit oxygen environment is that pending polybutadiene rubber is closed the environment of packaging, and
In the closing pack environment, volume of air is with the ratio scope of the volume of pending polybutadiene rubber
0.001-0.05：1.
10. a kind of elastomeric compound, it is characterised in that the elastomeric compound contains any one in claim 1-5
Described branched polybutadiene rubber.
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