CN106589425B - 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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- CN106589425B CN106589425B CN201510676942.6A CN201510676942A CN106589425B CN 106589425 B CN106589425 B CN 106589425B CN 201510676942 A CN201510676942 A CN 201510676942A CN 106589425 B CN106589425 B CN 106589425B
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Abstract
The present invention relates to rubber materials, provide a kind of branched polybutadiene rubber, a method of preparing the branched polybutadiene rubber, and the rubber compound as made from the branched polybutadiene rubber.The average branching index of the branched polybutadiene rubber is 0.5 × 10‑5‑11×10‑5mol/g；It is described preparation branched polybutadiene rubber method, including use ray to polybutadiene rubber carry out irradiation make its branched modification.The degree of branching of branched polybutadiene rubber of the invention is higher and is not easy to be crosslinked, obtained rubber compound and vulcanized rubber can have good processing performance and mechanical performance, the degree of branching of the easily controllable resulting branched polybutadiene rubber of the method for preparation branched polybutadiene rubber of the invention, it is and easy to operate to be conducive to industrialized production, it is possible to as a kind of simple and effective method for promoting traditional nickel polymerized BR quality.
Description
Technical field
The present invention relates to rubber materials, and in particular, to a kind of branched polybutadiene rubber, it is a kind of to prepare the poly- fourth of the branching
The method of diene rubber, and the rubber compound as made from the branched polybutadiene rubber.
Background technique
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 consumption on tire, and reduces the rolling resistance of tire, and it is green for improving the service life of tire
The important goal of colour wheel tire.
Existing tire tread glue basis glue be usually contain intermingle with or emulsion polymerized styrene butadiene rubber, cis-rich polybutadiene rubber (with
Down referred to as " butadiene rubber "), natural rubber and isoprene rubber etc. are used alone or are used in combination.But by these existing tires
Tread rubber rubber composition obtain it is rubber mixed in the prevalence of processing performance is not good enough, extrusion performance is poor, high speed
In extrusion process sizing material be also easy to produce flow instabilities so as to cause sizing material it is rough the problems such as, therefore it is traditional by these
The quality of tire product made from rubber composition is no longer satisfied 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 also used 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 trying pair
Traditional butadiene rubber is branched modification, to improve its processing performance and service 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.It is poly- to extract reduced branching degree from the solution that second step obtains for third step
Butadiene.
In the technology of existing preparation branching butadiene rubber, chemical treatment method is mainly used, such as polymerize in rubber
During structure regulator be added or be allowed to generate branched structure using the methods of catalyst, but chemical method often branching
Degree is lower, 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 are not able to satisfy 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 for being able to solve the above problem.
Summary of the invention
The purpose of the present invention is overcoming the drawbacks described above of the prior art, a kind of branched polybutadiene rubber, a kind of system are provided
The method of the standby branched polybutadiene rubber, and the rubber compound as made from the branched polybutadiene rubber.Branching of the invention
The degree of branching of polybutadiene rubber is higher and is not easy to be crosslinked, and obtained rubber compound and vulcanized rubber can have good machine
Tool performance and processing performance, the easily controllable resulting branched polybutadiene of method of preparation branched polybutadiene rubber of the invention
The degree of branching of rubber, and it is easy to operate conducive to industrialized production.
The present invention provides a kind of branched polybutadiene rubber, the average branching index of the branched polybutadiene rubber is
0.5×10-5-11×10-5mol/g。
The present invention also provides a kind of method for preparing branched polybutadiene rubber of the invention, this method includes that use is penetrated
Line, which carries out irradiation to polybutadiene rubber, makes its branched modification.
Invention additionally provides a kind of rubber compound, which contains branched polybutadiene rubber of the invention.
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 lower degree of branching, however, degree of branching obtained by chemical method used in the prior art is general
All over lower, 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 had been surprisingly found that during further investigation, use the method for x ray irradiation x preparation branched polybutadiene rubber can be with
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
Easily the phenomenon that crosslinking, so that the mechanical performance of sizing material and processing performance be made to be improved, and can be kneaded carrying out and
Energy is more saved when vulcanization.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, 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 the loss that i1~i2 obtained by I1~I5 obtained by embodiment and comparative example is measured through rubber machining analyzer RPA
The factor-frequency scanning curve；
Fig. 2 is the loss that i1~i2 obtained by I1~I5 obtained by embodiment and comparative example is measured through rubber machining analyzer RPA
The factor-strain sweep curve；
Fig. 3 is temperature-of the i1~i2 obtained by I1~I5 obtained by embodiment and comparative example in mixer when first segment mixing
Time graph；
Fig. 4 is power-of the i1~i2 obtained by I1~I5 obtained by embodiment and comparative example in mixer when first segment mixing
Time graph；
Fig. 5 is what ii1~ii2 obtained by II1~II5 obtained by embodiment and comparative example was measured through rubber machining analyzer RPA
Fissipation factor-strain sweep curve；
Fig. 6 is what ii1~ii2 obtained by II1~II5 obtained by embodiment and comparative example was measured through rubber machining analyzer RPA
Fissipation factor-frequency scanning curve.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of branched polybutadiene rubber, the average branching index of the branched polybutadiene rubber is
0.5×10-5-11×10-5mol/g。
In the present invention, average branching index is used to indicate the degree of branching of polybutadiene rubber, and the average branch refers 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 Industry of object, 1978,5:37-42) method is calculated.
In general, when the average branch of less or prior art when without crosslinking phenomena the branched polybutadiene rubber refers to
Number is generally lower than 0.5 × 10-5Mol/g, when the prior art branched polybutadiene rubber average branching index be 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,
It is more appropriate short-chain branched that reason may is that the branched polybutadiene rubber of average branching index within the above range has
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 are lower.In general, in a certain range (such as no more than 11 × 10-5When mol/g), average branch refers to
Number it is higher, 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 that (referred to as " branching is suitable for branching cis-rich polybutadiene rubber
Buna "), and on the basis of the total weight of the branched polybutadiene rubber, cis--Isosorbide-5-Nitrae-butadiene structure content is
The content of 95-99 weight %, anti-form-1,4- butadiene structure 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-
The content of butadiene structure is 95.5-97.5 weight %, anti-form-1, and the content of 4- butadiene structure is 1.5-2.5 weight %, 1,
The content of 2- butadiene structure is 1-2 weight %.Furthermore it is preferred that the branched polybutadiene rubber is branching nickel system along fourth
Rubber, wherein the nickel content in raw rubber is preferably micro- gram gram of 10-15, and the weight ratio of Al/Ni is preferably 1-2, the nickel in the raw rubber
It is actually that used catalyst remains in nickel and aluminium in raw rubber to butadiene rubber during the preparation process with aluminium.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 is somebody's turn to do the table of " raw rubber "
It states for being distinguished with " rubber compound " and " vulcanized rubber ".
In the present invention, the branched polybutadiene rubber does not have apparent crosslinking phenomena, generally, branching of the invention
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 company production measures.
In the present invention, the gel content of the branched polybutadiene rubber can be 1-10 weight %, preferably 5-8 weight
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 defined is tested, and wherein rotor selects greater trochanter shown in table 1 in the standard, temperature setting
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.
The present invention also provides a kind of method for preparing branched polybutadiene rubber, this method includes using ray to poly- fourth
Diene rubber, which carries out irradiation, makes its branched modification.
It was found by the inventors of the present invention that often there is branchings for the chemical method of traditional preparation branched polybutadiene rubber
Degree is lower, be easy to appear crosslinking phenomena, be complicated for operation, the degree of branching of gained branched modification product is more difficult to control, and should
The problems such as mechanical performance and still not good enough processing performance of gained branched modification product, and surprisingly sent out during further investigation
Now modification can be branched to polybutadiene rubber using the method for x ray irradiation x, this method is available be significantly higher than it is existing
The polybutadiene rubber of the degree of branching of technology, and the easily controllable degree of branching of this method, it is not easy to the phenomenon that crosslinking,
To make the mechanical performance of sizing material and processing performance be improved, and energy can be more saved when being kneaded and being vulcanized.
In the present invention, there is no particular limitation for ray used by irradiating, using conventional ray, such as can be with
For one of electron beam, gamma-rays and X-ray or a variety of, 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 decay generates.There is no particular limitation for the energy of ray,
It such as can be 0.8-2MeV, preferably 1-1.5MeV；When ray is60When the gamma-rays that Co decay generates, 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, generally, the dosage of x ray irradiation x of the invention (can irradiate branching relative to 1kg for 5-60kGy
The polybutadiene rubber before modification, the dosage of x ray irradiation x are 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
Weight %, preferably 0.3-1 weight %；Mooney viscosity can be 40-50, preferably 43-47；Weight average molecular weight can for 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 the preparation branched polybutadiene rubber can be conventional using this field
Environment, such as can be carried out in limit oxygen environment, when the limit oxygen environment refers to that the oxygen amount that limits in environment is that test specimen encapsulates
Oxygen amount in air.Oxygen amount in the air must be limited in certain range, under packaging environment, volume of air with it is to be processed
The ratio between the volume of (before irradiation branched modification) polybutadiene rubber range 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 performance, but dose of radiation is excessive, it will
Generate crosslinking and excessive degradation.Limit oxygen radiation can then improve such situation, adjoint because the oxygen and nitrogen content of radiation space is limited
The degradation that polar group introduces is not obvious, and radiation mainly causes the branching of strand.No a large amount of oxygen participates in crosslinking and drop
Solution reaction, to inhibit a large amount of introducings of oxygen-containing polar group in strand.The mode for providing limit oxygen environment is not special
It limits, such as can be sealed with plastic film.
Method of the invention can as adjust ray dosage easily control obtained by branched polybutadiene rubber branch
Change degree, and crosslinking phenomena is less likely to occur, so as to effectively improve the mechanical performance and processing performance of products obtained therefrom,
And energy can be more saved when being kneaded and being vulcanized.
Inventor has found during a large number of experiments, in general, can when the dosage of x ray irradiation x is 5-60kGy
Controlling the average branching index of gained branching butadiene rubber 0.5 × 10-5-11×10-5In the range of mol/g；When penetrating
When the dosage of line irradiation is 20-60kGy, the average branching index of gained branching butadiene rubber can be controlled 1 × 10-5-
11×10-5In the range of mol/g；It, can be by gained branching butadiene rubber when the dosage of x ray irradiation x is 30-60kGy
Average branching 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,
The average branching index of gained branching butadiene rubber can be controlled 6 × 10-5-9×10-5In the range of mol/g.Simultaneously
By using method of the invention, resulting branched polybutadiene rubber does not have apparent crosslinking phenomena, generally, of the invention
Total crosslink density XLD of branched polybutadiene rubber 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.
The branched polybutadiene rubber of the obtained average branching index of method of the invention within the above range have compared with
For suitable short-chain branched structure and strand spacing, strand is easy sliding when mixing, and compound viscosity is moderate, the torque of mixing
It reduces, reduces mixing energy, sizing material temperature rise is lower.And the process for branching of the prior art, branched structure are not easy to control, it may
It causes long chain branching more or is crosslinked, easily lead to macromolecule and tangle seriously, dyskinesia is unfavorable for reducing mixing energy instead；
It is less to be also possible to branched structure, for strand based on line style, strand spacing is small, and inter-chain action power is big, dyskinesia, also not
Conducive to reduction mixing energy.Therefore, there are better mechanical performance and processing performance using the obtained branched rubber of this method.
The present invention also provides a kind of rubber compound, which contains branched polybutadiene rubber of the invention.It is described mixed
There is no particular limitation for the component and preparation method of refining glue, adopts with the conventional methods in the field, such as can be according to " GBT
8660-2008 polymerisation in solution type butadiene rubber (BR) evaluation method " as defined in component and method be kneaded, specifically include:
Mixing method be two sections of mixer mixings, first segment mixing be added raw rubber (branched polybutadiene rubber i.e. of the invention), carbon black,
Oil, stearic acid, zinc oxide are operated, sizing material is discharged, sulphur, promotor is added in second segment mixing.Raw material used in it can be with
The conventional use of raw material of rubber compound is prepared for this field, details are not described herein.
It below will the present invention is further described in detail by specific embodiment.
Embodiment I1~I5 and comparative example i1~i2 is used to illustrate the preparation of branched polybutadiene rubber provided by the invention
Method and the branched polybutadiene rubber being prepared
Embodiment I1~I5
Embodiment I1~I5 respectively by unmodified basic glue limit oxygen environment (plastic film seals, volume of air with to
The ratio between volume of polybutadiene rubber is handled to carry out spoke according to irradiation dose shown in table 1 and radiographic source in 0.005:1)
According to, respectively obtain number be I1~I5 product.
Wherein, basic glue used in embodiment I1~I5 is the board of China Petrochemical Corp. Yanshan Mountain branch company production
Number butadiene rubber basis glue for being BR9000, nature parameters include: that 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 containing Al to be 15.4 micro- gram grams, is 11.4 micro- gram grams containing Ni, Al/Ni weight ratio is 1.35.
Table 1
| Number | 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 decay generates | 1.17 with 1.33 | BR9000 |
| Embodiment I4 | I4 | 40 | 60The gamma-rays that Co decay generates | 1.17 with 1.33 | BR9000 |
| Embodiment I5 | I5 | 60 | 60The gamma-rays that Co decay generates | 1.17 with 1.33 | BR9000 |
Comparative example i1
Using butadiene rubber basis glue BR9000 used in embodiment I1~I5, the difference is that according to US7030195B2
The method of embodiment 1 be branched modification, obtained product is denoted as i1.
Comparative example i2
The branching butadiene rubber of commercially available chemical method preparation, is denoted as i2: trade mark BR 1280, the production of LG chemical company, South Korea；Weight
Average molecular weight 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 structure content is 96.0 weight %, and anti-form-1,4- butadiene structure content is 1.8 weight %, 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, containing Ni is 16.8 micro- gram grams, Al/Ni
Weight ratio is 13.63, the Al/Ni weight ratio 1.35 much larger than BR9000, illustrates BR 1280 during synthesis using special
Catalyst, with the structure for being different from BR9000, LG chemical company official website is introduced, and BR 1280 has molecule chain branching knot
Structure.
Test case I1~I7
Test case I1~I7 respectively to branched polybutadiene rubber raw rubber product I 1~I5 and i1~i2 obtained above into
The following performance test of row:
(1) branched network structure
1~I5 of product I and aforementioned butadiene rubber basic collagen material BR9000 are taken, using IIC Dr.Kuhn GmbH&Co KG
The IIC XLDS-15HT type nuclear-magnetism crosslink density instrument of company's production tests their branched network structure, the results are shown in Table shown in 2.
Wherein, total crosslink density XLD includes the sum of physical entanglement point and chemical crosslinking dot density, and Mc refers to the average mark between crosslinking points
Son amount.Total crosslink density XLD reflects the quantity of physical entanglement point and chemical crosslinking point in branching butadiene rubber molecule.
Table 2
| Product number | 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 method of the invention before modified after XLD and Mc
It is not much different, this illustrates the embodiment product after branched modification via radiation, compared with the glue of unmodified butadiene rubber basis, not
Cross-linking reaction is generated, and branching appropriate is beneficial without processing performance raising of the crosslinking for butadiene rubber.
(2) average branching index
Average branching index λ (10-5Mol/g calculating λ=(M) is carried out according to the following formulabp -1-Mw -1)/2, acquired results are shown in Table 3
It is shown.
Wherein, MwRefer to the weight average molecular weight of branched polybutadiene rubber, test method are as follows: use 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 the main chain average molecular weight between adjacent two branch, calculation method are as follows: 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, 1978,5:37-42) method is calculated.
Table 3
| Product number | 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 |
It can be seen that branching obtained by the method using x ray irradiation x of the invention along fourth in conjunction with the data of table 1 and table 3
The average branching index of rubber is significantly larger than comparative example using branching butadiene rubber made from chemical method, and using the present invention
X ray irradiation x when, the average branching index of branching butadiene rubber increases with increasing for irradiation dose, easily controllable.
(3) gel content
I1~I5 and i1~i2 are put in stainless (steel) wire, certain time is impregnated in toluene, measurement is insoluble in toluene
Percentage shared by part, 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 1~I5 of branching butadiene rubber product I of embodiment I1~I5 is mostly significant
The gel content of branching butadiene rubber i1~i2 higher than comparative example i1 and i2.
(4) Mooney viscosity
Using GT-7080-S2 type Mooney viscosity machine (the high Inland Steel's production in Taiwan) according to standard GB/T/T1232.1-
2000 test I1~I5 and i1~i2 Mooney viscosity, rotor use greater trochanter, 100 DEG C of temperature, Mooney testing time 1+4min,
Being denoted as ML (1+4min, 100 DEG C) the results are shown in Table shown in 4.
From table 4, it can be seen that the Mooney viscosity of 1~I5 of branching butadiene rubber product I of embodiment I1~I5 is generally significant
The Mooney viscosity of branching butadiene rubber i1~i2 higher than comparative example i1 and i2.
(5) processing performance
I1~I5 and i1~i2 are tested using RPA2000 rubber machining analyzer (U.S.'s alpha Products),
Condition are as follows: frequency scanning: 100 DEG C of temperature, strain 7%；Strain sweep: 100 DEG C of temperature, frequency 1Hz.As a result see respectively Fig. 1 and
Fig. 2.
In fissipation factor-frequency curve (Fig. 1) of frequency scanning, the fissipation factor numerical value under low frequency is higher, under high frequency
Fissipation factor numerical value reduce, at higher frequencies, the fissipation factor numerical value of rubber of the same race is essentially identical, for a sample
Product scan from low to high, and fissipation factor reduction is smaller, and the degree of branching of strand is higher.Therefore, it will be seen from figure 1 that
The degree of branching of embodiment I1~I5 molecule is generally higher than the degree of branching of comparative example i1-i2.
In fissipation factor-strain curve (Fig. 2) of strain sweep, for a sample, fissipation factor is smaller, strand
Degree of branching it is higher.Therefore, from figure 2 it may also be seen that the degree of branching of embodiment molecule is higher than the degree of branching of comparative example.
Embodiment II1~II5 and comparative example ii1~ii2 is for illustrating rubber compound of the invention
It is kneaded, mixes according to formula as defined in " GBT 8660-2008 polymerisation in solution type butadiene rubber (BR) evaluation method "
Smelting method is two sections of mixer mixings, and branched polybutadiene rubber product I1 obtained by 100 parts by weight is added in first segment mixing
~I5 and i1~i2,60 parts by weight of carbon black per, 15 parts by weight operation oil, 2 parts by weight stearic acid, 3 part by weight of zinc oxide, are discharged glue
Material, second segment mixing are added 1.5 parts by weight sulphur and 0.9 parts by weight vulcanization accelerator, finally obtain compound manufacture and difference
It is denoted as II1~II5 and ii1~ii2 (respectively corresponding embodiment II1~II5 and comparative example ii1~ii2).
Mixing facilities are 1.6L mixer, and producer is Farrel Corp., the U.S., model BR1600
Raw materials used producer and the trade mark is as follows:
Carbon black: imported from America, the trade mark are ASTM IRB8 (Industry Reference Black)；
Sulphur: Science and Technology Ltd., trade mark S-80 are contained purchased from Guangzhou Jinchang；
Vulcanization accelerator: N tert butyl benzothiazole 2 sulfenamide is purchased from Huangyan, Zhejiang chemical plant, trade mark TBBS；
Activator: zinc oxide is purchased from Liuzhou Xin Pin Co., Ltd；
Activator: stearic acid is purchased from the polite Chemical Co., Ltd. in Hong Kong, trade mark SA1801；
Operation oil: imported from America, trade mark ASTM103#Oil.
In addition, the melting temperature and power recorded in sizing material first segment internal mixing pass becomes at any time during mixing
The curve of change, respectively as shown in figure 3 and figure 4.From Fig. 3 and Fig. 4 as can be seen that embodiment power curve-time have it is more
Fluctuation, it has also been found that sizing material not conglomeration in mixing process, is separated into more broken fritter, it may be possible to prop up in mixer mixing process
The molecule for changing structure is easy to produce flow instabilities under lower shear rate, caused by generating melt fracture.But it is kneaded
After, rubber compound can preferably clump together.And after the mixing later period, mixing time 240s, embodiment II1~II4
Melting temperature be lower than comparative example ii1 and ii2, and after mixing time 120s, the mixer power of embodiment II1~II5
Lower than comparative example ii1 and ii2, illustrate to save energy, processing performance than comparative example 1 and 2 when embodiment branching butadiene rubber is kneaded
Preferably.
Test case II1~II7
Test case II1~II7 respectively tests compound manufacture II1~II5 and ii1~ii2 obtained above, tool
Body mode is as follows:
(1) processing performance
It is tested, test condition using RPA2000 rubber machining analyzer (U.S.'s alpha Products) are as follows: strain
Scanning: temperature 60 C, frequency 1Hz；Frequency scanning: temperature 60 C, strain 7%.Acquired results are respectively as shown in Fig. 5 and Fig. 6.From
The strain sweep and frequency scanning curve of Fig. 5 and Fig. 6 rubber compound can be seen that under wider strain and frequency range, implement
The fissipation factor of example II1~II5 is lower than comparative example ii1~ii2, illustrates embodiment rubber compound machining energy loss ratio comparative example
It is small, there is preferable processing performance.
(2) curability
Using testing without curability of the rotor vulcameter to rubber compound purchased from the high Inland Steel in Taiwan, test condition
Are as follows: oscillation angle is 1 °, frequency 1.7Hz, and temperature is 145 DEG C.Acquired results are as shown in table 5, wherein MH (dNm) is indicated
Maximum torque, ML (dNm) indicate minimum torque, and ts1 (m:s) indicates time of scorch, reflects the vulcanization safety of rubber compound,
Tc10 (m:s), tc50 (m:s) and tc90 (m:s) indicate that vulcanization reaches the different degrees of time used, and wherein tc90 reflects mixed
The sulfurizing time of refining glue.
Table 5
* m:s indicates minute: second, as 11:44 is indicated 44 seconds 11 minutes.
For butadiene rubber, the sulfurizing time tc90 of embodiment II1-II2 is suitable with the tc90 of comparative example ii1 and ii2,
And the tc90 of embodiment II3-II5 is shorter than the tc90 of comparative example ii1 and ii2, illustrates the vulcanization time and comparative example phase of embodiment
When or than comparative example is short, when vulcanization, relatively saves energy.Ts1, tc10, tc50 of embodiment II1-II5 be shorter than comparative example ii1 and
Ii2 illustrates that embodiment time of scorch is short, and process safety is good, and curingprocess rate is fast.To a certain extent, curability also can
Reflect mechanical performance, it is considered that the maximum torque MH of curing curve is bigger, shows that rubber compound vulcanizes the vulcanizate to be formed and stretches surely
Stress is higher, and mechanical performance is better, to can also learn according to the obtained branched polybutadiene rubber of the present processes
Vulcanizate have higher mechanical performance.
In conclusion can be shown using the average branching index of the obtained branched polybutadiene rubber of method of the invention
It writes and is higher than the resulting branched polybutadiene rubber of chemical method, and method of the invention can be obtained by adjusting irradiation dose
The more appropriate degree of branching is without generating cross-linked structure.Moreover, adopting the branched polybutadiene rubber being obtained by the present invention
Energy is more saved when being kneaded and being vulcanized, and the processing performance of obtained mixing rubber and mechanical performance are also superior to comparison
Example.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.It is further to note that described in above-mentioned specific embodiment
Each particular technique feature can be combined in any appropriate way in the case of no contradiction, in order to avoid not
Necessary repetition, the invention will not be further described in various possible combinations.In addition, a variety of different implementations of the invention
Any 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 (10)
1. a kind of branched polybutadiene rubber, which is characterized in that the branched polybutadiene rubber is by using ray to poly- fourth
Diene rubber, which carries out irradiation, obtains its branched modification, wherein the average branching index of the branched polybutadiene rubber is
8.62×10-5-11×10-5mol/g；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.
2. branched polybutadiene rubber according to claim 1, wherein with the total weight of the branched polybutadiene rubber
On the basis of, cis--Isosorbide-5-Nitrae-butadiene structure content is 95-99 weight %, and anti-form-1, the content of 4- butadiene structure is 0.7-
2.5 weight %, the content of 1,2- butadiene structure are 0.3-2.5 weight %.
3. branched polybutadiene rubber according to claim 1, wherein the gel content of the branched polybutadiene rubber
For 1-10 weight %, Mooney viscosity 50-75.
4. branched polybutadiene rubber according to claim 3, wherein the Weight-average molecular of the branched polybutadiene rubber
Amount is 28 × 104-46×104G/mol, molecular weight distribution 2.9-5.1.
5. a kind of method for preparing branched polybutadiene rubber described in any one of claim 1-4, which is characterized in that should
Method includes carrying out irradiation to polybutadiene rubber using ray to make its branched modification；Wherein, the energy of the ray is 0.8-
2MeV, relative to polybutadiene rubber described in 1kg, the dosage of x ray irradiation x is 5-60kJ, the method in limit oxygen environment into
Row, the gel content of the polybutadiene rubber are 0.1-1.9 weight %, Mooney viscosity 40-50, the polybutadiene rubber
Molecular weight distribution be 2.9-5.1.
6. according to the method described in claim 5, wherein, the ray is one of electron beam, gamma-rays and X-ray or more
Kind.
7. according to the method described in claim 6, wherein, the ray is gamma-rays.
8. the method according to any one of claim 5-7, wherein relative to polybutadiene rubber described in 1kg, ray
The dosage of irradiation is 20-60kJ.
9. according to the method described in claim 5, wherein, the limit oxygen environment is to close polybutadiene rubber to be processed to pack
Environment, and in the closing pack environment, the ratio between volume of air and the volume of polybutadiene rubber to be processed range are
0.001-0.05:1.
10. a kind of rubber compound, which is characterized in that the rubber compound contains the poly- fourth of branching described in any one of claim 1-4
Diene rubber.
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