CN109575189A - Monovinylarene-conjugated diene polymer and its preparation method and application - Google Patents
Monovinylarene-conjugated diene polymer and its preparation method and application Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
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Abstract
The present invention relates to polymer arts, disclose a kind of monovinylarene-conjugated diene polymer and its preparation method and application, high polymer containing 1~10 weight % in the polymer and the oligomer by coupling acquisition, and the number-average molecular weight of the high polymer is 1,200,000 or more, the content of monovinylarene structural unit in the polymer is 10~50 weight %, and the content of conjugated diene structural unit is 50~90 weight %, molecular weight distribution index is 1.0~1.5.Containing the super high molecular weight high polymer that content is moderate in polymer provided by the invention, assign polymer excellent intensity and dynamic property.
Description
Technical field
The present invention relates to polymer arts, and in particular, to a kind of monovinylarene-conjugated diene polymer and
Prepare monovinylarene-conjugated diene polymer methods and applications.
Background technique
Solution polymerization styrene-butadiene rubber (SSBR, also referred to as solution polymerized butadiene styrene rubber) is by butadiene and styrene monomer with alkyl
Lithium is initiator, passes through copolymer rubber prepared by anionic solution polymerization in hydrocarbon solvent.
Since SSBR has excellent wearability, the cracking of resistance to rill, and to wet road surface gripping power, heat resistance and in high temperature
Flexible resistance after lower long-time exposure is good, has both mixer mixing heat is low, extrusion expansion rate is small, loading is high etc. in addition
Feature applies the ratio in terms of tire product increasing.
Using the wearability of SSBR, excellent dynamic property and low temperature tolerance characteristics etc., manufacture giant tire, snow may further be used to
Ground tire etc..
Angularly consider that SSBR is suitable for from wearability, tensile strength, vulcanization flatness, flexible resistance and heat resistance
Manufacture conveyer belt, especially heat resistance conveyor belt.
SSBR also has good electrical insulation capability, excellent color, low ash point and non-rubber component of low content etc.
Advantage.
From the perspective of processing performance and physical mechanical property balance, SSBR is the rubber articles for having both a variety of comprehensive performances
Kind.
In view of the excellent properties of solution polymerized butadiene styrene rubber, the research in this field is more, and CN1432586A discloses one kind and contains
The solution polymerized butadiene styrene rubber of high molecular weight, but its high molecular weight moieties content is 10-40 weight %, content is too high, after being unfavorable for
The product of phase is processed；Solution polymerized butadiene styrene rubber is prepared using the method that anionic initiator is repeatedly added dropwise in CN102344529A, so
And the complex process of the prior art, it is inconvenient.
Summary of the invention
The purpose of the present invention is to provide a kind of monovinylarene-conjugated dienes of high polymer containing super high molecular weight
Hydrocarbon polymer and preparation method thereof.
To achieve the goals above, the first aspect of the present invention provides a kind of monovinylarene-conjugate diene polymerization
Object, the high polymer containing 1~10 weight % and the oligomer obtained by coupling in the polymer, and the number of the high polymer is equal
Molecular weight is 1,200,000 or more, and the content of the monovinylarene structural unit in the polymer is 10~50 weight %, and
The content of conjugated diene structural unit is 50~90 weight %, and molecular weight distribution index is 1.0~1.5.
Second aspect, the present invention, which provides, a kind of prepares monovinylarene-conjugation described in aforementioned first aspect of the present invention
The method of diene polymer, this method comprises:
(1) in the presence of nonpolar solvent, mono vinyl arenes monomer, conjugated diene monomer, Third monomer, pole is added
Property regulator and anionic initiator to carry out the first polymerization reaction, the Third monomer is divinylbenzene；
(2) mono vinyl arenes monomer, conjugated diene monomer are added again after the monomer conversion completely in step (1)
With anionic initiator to carry out the second polymerization reaction；
(3) coupling agent, terminator is successively added into reaction system after the monomer conversion completely in step (2) and prevents old
Agent.
The third aspect, the present invention provides monovinylarene-conjugated diene polymers described in first aspect to take turns
Application in tire tread glue.
It is high containing the moderate super high molecular weight of content in monovinylarene-conjugated diene polymer provided by the invention
Polymers.
Monovinylarene-conjugated diene polymer provided by the invention is assigned due to the effect of its super high molecular weight
Polymer excellent intensity and dynamic property, and operating procedure is simple, it is easy to accomplish industrialization.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
As previously mentioned, the first aspect of the present invention provides a kind of monovinylarene-conjugated diene polymer, this is poly-
Close the high polymer containing 1~10 weight % and the oligomer obtained by coupling in object, and the number-average molecular weight of the high polymer
It is 1,200,000 or more, the content of the monovinylarene structural unit in the polymer is 10~50 weight %, and conjugation two
The content of olefin unit is 50~90 weight %, and molecular weight distribution index is 1.0~1.5.
Preferably, the content of the high polymer in the polymer is 3~8 weight % and the number of the high polymer is divided equally
Son amount is 1,200,000~2,000,000, and molecular weight distribution index is 1.05~1.25；It is highly preferred that the number-average molecular weight of the high polymer
It is 1,300,000~1,800,000.
Under preferable case, the content of the monovinylarene structural unit in the polymer is 20~30 weight %, with
And the content of conjugated diene structural unit is 70~80 weight %.
Under preferable case, the monovinylarene is selected from styrene, vinyltoluene, α-methylstyrene, the tertiary fourth of 4-
Base styrene, 4- methyl styrene, 3,5- diethyl, 3,5- di-n-butyl styrene, 4- n-propylbenzene ethylene and 4-
At least one of dodecylstyrene.It is highly preferred that the monovinylarene is styrene.
Under preferable case, the conjugated diene be selected from butadiene, isoprene, 1,3-pentadiene, 1,3- hexadiene and
At least one of 2,3 dimethyl butadiene；It is highly preferred that the conjugated diene is butadiene or isoprene；It is especially excellent
Selection of land, the conjugated diene are butadiene.
Under preferable case, the coupling efficiency of the oligomer obtained by coupling is 30~80 weight %；Basis before coupling
Peak number average molecular weight is 80,000~250,000.In particularly preferred situation, the coupling efficiency of the oligomer obtained by coupling is 45~
65 weight %.
As previously mentioned, the second aspect of the present invention provide it is a kind of prepare mono-vinyl described in first aspect present invention virtue
Hydrocarbon-conjugated diene polymer method, this method comprises:
(1) in the presence of nonpolar solvent, mono vinyl arenes monomer, conjugated diene monomer, Third monomer, pole is added
Property regulator and anionic initiator to carry out the first polymerization reaction, the Third monomer is divinylbenzene；
(2) mono vinyl arenes monomer, conjugated diene monomer are added again after the monomer conversion completely in step (1)
With anionic initiator to carry out the second polymerization reaction；
(3) coupling agent, terminator is successively added into reaction system after the monomer conversion completely in step (2) and prevents old
Agent.
Under preferable case, the Third monomer is p-divinyl benzene and/or m-divinyl benzene.
According to a kind of preferred embodiment, the Third monomer is p-divinyl benzene and m-divinyl benzene
Mixture.
It is described to divinyl in the mixture of the p-divinyl benzene and m-divinyl benzene under preferable case
The content molar ratio of benzene and m-divinyl benzene is 1:(0.5~2.5).It was found by the inventors of the present invention that using molar ratio for 1:
The p-divinyl benzene of (0.5~2.5) and the mixture of m-divinyl benzene are as the third list in preparation method of the invention
When body, thus obtained polymer can intensity and dynamic property it is more excellent.
Preferably, the mole dosage of the Third monomer is the mole dosage of the anionic initiator in step (1)
3~20 times, more preferably 4~10 times.
Under preferable case, the dosage of the nonpolar solvent makes rising for the polymerized monomer in the reaction system of step (1)
Beginning content is 0.1~1.5 weight %.
Preferably, the total amount of the mono vinyl arenes monomer and conjugated diene monomer that are added in step (1) and step (2)
The ratio between the mono vinyl arenes monomer of middle addition and the total amount (weight) of conjugated diene monomer are 1:(5~50)；More preferably
1:(10~35).
Preferably, the mole dosage of the anionic initiator in the mole dosage Yu step (2) of the coupling agent it
Than for 1:(1.2~10)；More preferably 1:(2.5~6).
Preferably, the dosage molar ratio of the anionic initiator in step (2) and the anionic initiator in step (1) is
(1~30): 1；Preferably (2~20): 1.
Preferably, the nonpolar solvent is selected from benzene, toluene, ethylbenzene, dimethylbenzene, pentane, hexane, heptane, octane, hexamethylene
Alkane, Mixed XYLENE, raffinate oil or aforementioned solvents in any combination of two or more, the preferably described nonpolar solvent is
The mixed solvent of hexamethylene or n-hexane and hexamethylene.
Preferably, the condition of first polymerization reaction and second polymerization reaction includes: that temperature is each independently
30~100 DEG C, more preferably 50~70 DEG C.
According to a kind of preferred embodiment, the time of first polymerization reaction is 0.2~2h, more preferably
0.5~1h.
According to another preferred embodiment, the time of second polymerization reaction is 0.2~2h, more preferably
0.8~1.5h.The timing end point of second polymerization reaction is at the time of being initially added into coupling agent.
According to there are also a kind of preferred embodiments, coupling agent is added in step (3) to carry out coupling reaction
Time is 0.3~2h, more preferably 0.5~1h.The time zero of the time of the coupling reaction is when being initially added into coupling agent.
Under preferable case, the anti-aging agent is in amines antioxidants, quinoline type antioxidant and benzimidazole anti-aging agent
It is at least one.For example, the anti-aging agent is antioxidant 4020.
Under preferable case, the anionic initiator is the compound with RLi structure, and wherein R is C1-C10Straight chain or
Branched alkyl；It is highly preferred that the R is selected from methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tertiary fourth
Base, n-pentyl, isopentyl, tertiary pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl and positive decyl.Particularly preferably it is described yin from
Sub- initiator is n-BuLi.
Under preferable case, the polar modifier (also referred to as structure regulator) be selected from ether, butyl oxide, tetrahydrofuran,
Glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofurfuryl alcohol ether, dioxane, crown ether, triethylamine, tetramethylethylenediamine, hexamethyl
Phosphoric triamide, potassium tert-butoxide, tert-pentyl alcohol potassium, potassium lauryl, alkyl benzene sulphonate potassium and sodium alkyl benzene sulfonate.Particularly preferably tetrahydro
Furfuryl alcohol ether (ETE).
Preferably, the dosage of the polar modifier makes the starting of the polar modifier in the reaction system of step (1)
Weight concentration is 100~1000ppm, more preferably 300~500ppm.
The coupling agent of the invention is preferably silicon tetrachloride, trichlorosilane, tin tetrachloride, tin trichloride, epoxy soybean
At least one of oil, divinylbenzene, methoxy base trichlorosilane and four bromo-silicanes, more preferably silicon tetrachloride and/or tetrachloro
Change tin.
As previously mentioned, the third aspect of the present invention provides monovinylarene-conjugated diene described in first aspect
Application of the polymer in tire tread glue.
It below will the present invention will be described in detail by example.In following instance, in case of no particular description,
The various raw materials used are all from commercially available.
In following instance, number-average molecular weight (Mn) using the ALLIANCE2690 type gel infiltration color of U.S. WATERS company
Spectrometer measurement, using the PLgel Mixed-C type gel chromatographic columns for being purchased from agilent company, using THF as mobile phase, with narrow ditribution
Polystyrene is standard specimen, and temperature is 25 DEG C.
In following instance, the content of the high polymer in polymer is measured by gel permeation chromatograph.
In following instance, tensile property is according to the method in national standard " GB/T 1040-92 plastic tensile method for testing performance "
Test, the AG-20KNG of puller system model Shimadzu Corporation production；Rate of extension is 500mm/min, and test temperature is 23 DEG C.Examination
The live part length of sample is 25mm, width 6mm.For every group of sample, 10 parallel laboratory tests are carried out, results are averaged.
In following instance, dynamic mechanical, on German GABO company EPLEXOR-500N dynamic thermomechanical analysis apparatus
The viscoelastic behavior of sample is tested.Sample length is 35mm, width 8mm, with a thickness of 1.0mm.Test uses stretching die
Formula, test frequency 11Hz, temperature range are -100~100 DEG C, and heating rate is 3 DEG C/min, and static strain 1% is dynamically answered
Become 0.25%.
Embodiment 1
In 5L stainless steel polymeric kettle, 2500g hexamethylene/hexane mixed solvent (volume ratio 15:85), 24g benzene second is added
(mix monomer is dissolved in 100g cyclohexane solvent, wherein the content weight of styrene and butadiene for alkene and butadiene mix monomer
Amount is than being 25:75), 4mmol aligns divinylbenzene, 0.84g tetrahydrofurfuryl alcohol ether, opens stirring, water bath with thermostatic control heating, polymerization
When temperature in the kettle reaches 50 DEG C, 0.5mmol n-BuLi is added into polymeric kettle, after reacting 0.5h, adds again into polymeric kettle
Enter the mixed liquor of 276g styrene as hereinbefore and butadiene, 1.1mmol n-BuLi is then added, under agitation
After reacting 1h, 0.2mmol silicon tetrachloride is added, reacts 0.5h, isopropanol is added and terminates reaction, antioxidant 4020, glue is added
It is handled using Wet agglomeration.
The content of high polymer in the resulting polymer of the present embodiment is measured as 5.1 weight %, and the equal molecule of number of high polymer
Amount is 1,550,000, molecular weight distribution index 1.20, and basic peak number average molecular weight of the oligomer before coupling is 250,000, coupling effect
Rate is 45%.
Comparative example 1
In 5L stainless steel polymeric kettle, 2500g hexamethylene/hexane mixed solvent (volume ratio is in the same manner as in Example 1) is added,
(mix monomer is dissolved in 100g cyclohexane solvent, wherein styrene and butadiene for 300g styrene and butadiene mix monomer
Content weight ratio be 25:75), 4mmol align divinylbenzene, 0.84g tetrahydrofurfuryl alcohol ether, open stirring, water bath with thermostatic control
1.6mmol n-BuLi is added into polymeric kettle when polymerization temperature in the kettle reaches 50 DEG C for heating, after reacting 1.5h, is added
0.2mmol silicon tetrachloride reacts 0.5h, and isopropanol is added and terminates reaction, antioxidant 4020 is added, glue is using at Wet agglomeration
Reason.
Measure the high polymer without super high molecular weight in the resulting polymer of this comparative example, basic peak of the oligomer before coupling
Number-average molecular weight is 18.5 ten thousand, coupling efficiency 58%.
Embodiment 2
In 5L stainless steel polymeric kettle, 2500g hexamethylene/hexane mixed solvent (volume ratio is in the same manner as in Example 1) is added,
(mix monomer is dissolved in 100g cyclohexane solvent, wherein styrene and butadiene for 9g styrene and butadiene mix monomer
Content weight ratio is 30:70), 2.0mmol meta position divinylbenzene, 1.4g tetrahydrofurfuryl alcohol ether open stirring, and water bath with thermostatic control adds
0.2mmol n-BuLi is added into polymeric kettle when polymerization temperature in the kettle reaches 60 DEG C for heat, after reacting 1h, again to polymeric kettle
The middle mixed liquor that 291g styrene as hereinbefore and butadiene is added, is then added 3.7mmol n-BuLi, in stirring bar
After reacting 1.5h under part, 1.1mmol tin tetrachloride is added, reacts 0.8h, isopropanol is added and terminates reaction, anti-aging agent is added
4020, glue is handled using Wet agglomeration.
The content of high polymer in the resulting polymer of the present embodiment is measured as 4.8 weight %, and the equal molecule of number of high polymer
Amount is 1,700,000, molecular weight distribution index 1.25, and basic peak number average molecular weight of the oligomer before coupling is 80,000, coupling efficiency
It is 65%.
Embodiment 3
In 5L stainless steel polymeric kettle, 2500g hexamethylene/hexane mixed solvent (volume ratio is in the same manner as in Example 1) is added,
(mix monomer is dissolved in 100g cyclohexane solvent, wherein styrene and butadiene for 15g styrene and butadiene mix monomer
Content weight ratio is 20:80), 1.0mmol aligns divinylbenzene, 1.0mmol meta position divinylbenzene, 1.0g tetrahydrofurfuryl alcohol second
Ether, opens stirring, and 0.25mmol normal-butyl is added into polymeric kettle when polymerization temperature in the kettle reaches 55 DEG C for water bath with thermostatic control heating
After reacting 0.5h, the mixed liquor of 285g styrene as hereinbefore and butadiene is added in lithium into polymeric kettle again, then plus
Enter 1.9mmol n-BuLi, after reacting 1h under agitation, 0.5mmol silicon tetrachloride is added, reacts 1h, isopropanol is added
Reaction is terminated, antioxidant 4020 is added, glue is handled using Wet agglomeration.
The content of high polymer in the resulting polymer of the present embodiment is measured as 6.5 weight %, and the equal molecule of number of high polymer
Amount is 1,600,000, molecular weight distribution index 1.21, and basic peak number average molecular weight of the oligomer before coupling is 150,000, coupling effect
Rate is 55%.
Embodiment 4
The present embodiment is carried out using method similar to Example 1, except that:
The weight of styrene and butadiene mix monomer (in the same manner as in Example 1) that first time in the present embodiment is added
For 20g, ETE dosage is 0.95g, and the dosage for aligning divinylbenzene is 2.5mmol, and the n-BuLi being added for the first time is
0.25mmol；The weight of the cyclohexane solution of second of the styrene being added and butadiene is 280g, second of positive fourth being added
Base lithium is 1.6mmol；The additional amount of coupling agent silicon tetrachloride is 0.5mmol.
Remaining is same as Example 1.
The content of high polymer in the resulting polymer of the present embodiment is measured as 7.7 weight %, and the equal molecule of number of high polymer
Amount is 1,300,000, molecular weight distribution index 1.09, and basic peak number average molecular weight of the oligomer before coupling is 180,000, coupling effect
Rate is 50%.
Embodiment 5
The present embodiment is carried out using method similar to Example 2, except that:
The weight of styrene and butadiene mix monomer (in the same manner as in Example 2) that first time in the present embodiment is added
For 11g, ETE dosage is 1.1g, and the dosage of meta position divinylbenzene is 1.8mmol, and the n-BuLi being added for the first time is
0.2mmol；The weight of the cyclohexane solution of second of the styrene being added and butadiene is 289g, second of normal-butyl being added
Lithium is 1.5mmol；The additional amount of coupling agent tin tetrachloride is 0.4mmol.
Remaining is same as Example 2.
The content of high polymer in the resulting polymer of the present embodiment is measured as 5.0 weight %, and the equal molecule of number of high polymer
Amount is 1,800,000, molecular weight distribution index 1.24, and basic peak number average molecular weight of the oligomer before coupling is 200,000, coupling effect
Rate is 60%.
Test case
White carbon black system is respectively adopted in the polymer (100 parts by weight) that above-described embodiment and comparative example are prepared to mend
By force, white carbon black selects the 165GR of Rhodia, and white carbon black additive amount is 60 parts by weight, 10 parts by weight of 8# reference black, operation
Oily TDAE (Qingzhou City Ostwald-Folin moistens limited rubber company) 15 parts by weight, zinc oxide (Sinopharm Chemical Reagent Co., Ltd.) 3.0
Parts by weight, 2.0 parts by weight of stearic acid (Sinopharm Chemical Reagent Co., Ltd.), sulphur (the limited public affairs of Chinese medicines group chemical reagent
Department) 1.5 parts by weight, (Gaoyi County benefit and Chemical Co., Ltd. are 2.0 parts by weight, diphenylguanidine (Shijiazhuang City morning to antioxidant 4020
Sunlight Chemical Co., Ltd.) 1.5 parts by weight, accelerator TBBS (Guangdong Du Ba new material Science and Technology Ltd.) 1.5 parts by weight, and it is each
It is only polymer source difference in the test of a embodiment and comparative example, remaining is all the same.Mixer is U.S. law Lai Er
BR1600 type, mold cavity volume 1.5L；Vulcanizing press is industrial (Anhui) the Co., Ltd production of huge rock oil pressure, model P-
50-PCD-3L (curing temperature be 150 DEG C, sulfide stress 20MPa, vulcanization time 50min).Obtain vulcanized rubber.
The property of gained vulcanized rubber is as shown in table 1.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative example 1 | |
| Tensile strength/MPa | 25.1 | 24.7 | 25.5 | 22.3 | 24.3 | 20.0 |
| 100% stretches/MPa surely | 5.3 | 5.1 | 5.5 | 5.0 | 4.9 | 4.7 |
| 300% stretches/MPa surely | 21.3 | 20.9 | 22.3 | 18.9 | 21.6 | 17.2 |
| Elongation/% | 400 | 398 | 411 | 351 | 403 | 323 |
| Tearing strength/KN/m | 27.6 | 26.9 | 28.1 | 25.6 | 27.5 | 23.4 |
| tanδ(0℃) | 0.952 | 0.945 | 0.968 | 0.853 | 0.922 | 0.782 |
| tanδ(60℃) | 0.083 | 0.087 | 0.082 | 0.093 | 0.088 | 0.101 |
Gather in polymer provided by the invention containing the moderate super high molecular weight height of content it can be seen from the above results
Object assigns polymer excellent intensity and dynamic property.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (17)
1. a kind of monovinylarene-conjugated diene polymer, in the polymer high polymer containing 1~10 weight % and
The oligomer obtained by coupling, and the number-average molecular weight of the high polymer is 1,200,000 or more, the mono-vinyl in the polymer
The content of aromatic hydrocarbons structural unit is 10~50 weight % and the content of conjugated diene structural unit is 50~90 weight %,
Molecular weight distribution index is 1.0~1.5.
2. polymer according to claim 1, wherein the content of the high polymer in the polymer is 3~8 weight %,
And the number-average molecular weight of the high polymer is 1,200,000~2,000,000, molecular weight distribution index is 1.05~1.25；Preferably,
The number-average molecular weight of the high polymer is 1,300,000~1,800,000.
3. polymer according to claim 1 or 2, wherein monovinylarene structural unit in the polymer
Content is 20~30 weight % and the content of conjugated diene structural unit is 70~80 weight %.
4. polymer described in any one of -3 according to claim 1, wherein the monovinylarene be selected from styrene,
Vinyltoluene, α-methylstyrene, 4- t-butyl styrene, 4- methyl styrene, 3,5- diethyl, 3,5- bis- are just
At least one of butylstyrene, 4- n-propylbenzene ethylene and 4- dodecylstyrene；Preferably,
The monovinylarene is styrene.
5. polymer described in any one of -3 according to claim 1, wherein the conjugated diene is selected from butadiene, different
At least one of pentadiene, 1,3- pentadiene, 1,3- hexadiene and 2,3 dimethyl butadiene；Preferably,
The conjugated diene is butadiene or isoprene.
6. polymer according to claim 1, wherein the coupling efficiency of the oligomer obtained by coupling is 30~80
Weight %, preferably 45~65 weight %；Basic peak number average molecular weight is 80,000~250,000 before coupling.
7. a kind of prepare monovinylarene-conjugated diene polymer method described in any one of claim 1-6,
This method comprises:
(1) in the presence of nonpolar solvent, mono vinyl arenes monomer, conjugated diene monomer, Third monomer, polarity tune is added
To carry out the first polymerization reaction, the Third monomer is divinylbenzene for section agent and anionic initiator；
(2) mono vinyl arenes monomer, conjugated diene monomer and yin are added again after the monomer conversion completely in step (1)
Ionic initiator is to carry out the second polymerization reaction；
(3) coupling agent, terminator and anti-aging agent are successively added into reaction system after the monomer conversion completely in step (2).
8. according to the method described in claim 7, wherein, the Third monomer is p-divinyl benzene and/or divinyl
Benzene；Preferably,
The Third monomer is the mixture of p-divinyl benzene and m-divinyl benzene；Preferably,
In the mixture of the p-divinyl benzene and m-divinyl benzene, the p-divinyl benzene and m-divinyl benzene
Content molar ratio be 1:(0.5~2.5)；Preferably,
The mole dosage of the Third monomer is 3~20 times of the mole dosage of the anionic initiator in step (1), excellent
It is selected as 4~10 times.
9. method according to claim 7 or 8, wherein the dosage of the nonpolar solvent makes the reactant of step (1)
The initial content of polymerized monomer in system is 0.1~1.5 weight %.
10. according to the method described in claim 7, wherein, the condition of first polymerization reaction and second polymerization reaction
Include: each independently temperature be 30~100 DEG C, preferably 50~70 DEG C.
11. the method according to claim 7 or 10, wherein the time of first polymerization reaction is 0.2~2h, preferably
For 0.5~1h；Preferably,
The time of second polymerization reaction is 0.2~2h, preferably 0.8~1.5h；Preferably,
Coupling agent is added in step (3) to carry out the time of coupling reaction as 0.3~2h, preferably 0.5~1h.
12. the anionic initiator is the compound with RLi structure according to the method described in claim 7, wherein,
Middle R is C1-C10Linear or branched alkyl group；Preferably,
The R is selected from methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tert-butyl, n-pentyl, isoamyl
Base, tertiary pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl and positive decyl.
13. according to the method described in claim 7, wherein, the polar modifier is selected from ether, butyl oxide, tetrahydrofuran, second
Glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofurfuryl alcohol ether, dioxane, crown ether, triethylamine, tetramethylethylenediamine, hempa
Acyl triamine, potassium tert-butoxide, tert-pentyl alcohol potassium, potassium lauryl, alkyl benzene sulphonate potassium and sodium alkyl benzene sulfonate；Preferably,
The dosage of the polar modifier makes the starting weight concentration of the polar modifier in the reaction system of step (1) to be
100~1000ppm, preferably 300~500ppm.
14. according to the method described in claim 7, wherein, the mono vinyl arenes monomer and conjugated diene that are added in step (1)
The ratio between total weight of the mono vinyl arenes monomer and conjugated diene monomer that are added in the total amount of hydrocarbon monomer and step (2) is 1:
(5~50)；Preferably 1:(10~35).
15. according to the method described in claim 7, wherein, the mole dosage of the coupling agent and the yin in step (2) from
The ratio between mole dosage of sub- initiator is 1:(1.2~10)；Preferably 1:(2.5~6).
16. according to the method described in claim 7, wherein, the yin in anionic initiator and step (1) in step (2) from
The dosage molar ratio of sub- initiator is (1~30): 1；Preferably (2~20): 1.
17. monovinylarene-conjugated diene polymer described in any one of claim 1-6 is in tire tread glue
In application.
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