CN109575189B - Monovinylarene-conjugated diene polymer and preparation method and application thereof - Google Patents
Monovinylarene-conjugated diene polymer and preparation method and application thereof 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
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Abstract
The invention relates to the field of polymers, and discloses a monovinylarene-conjugated diene polymer, and a preparation method and application thereof, wherein the polymer contains 1-10 wt% of high polymer and oligomer obtained by coupling, the number average molecular weight of the high polymer is more than 120 ten thousand, the content of a monovinylarene structural unit in the polymer is 10-50 wt%, the content of a conjugated diene structural unit in the polymer is 50-90 wt%, and the molecular weight distribution coefficient is 1.0-1.5. The polymer provided by the invention contains ultrahigh molecular weight high polymer with moderate content, and endows the polymer with excellent strength and dynamic performance.
Description
Technical Field
The invention relates to the field of polymers, in particular to a monovinylarene-conjugated diene polymer, and a method and application for preparing the monovinylarene-conjugated diene polymer.
Background
Solution polymerized styrene butadiene rubber (SSBR, also known as solution polymerized styrene butadiene rubber) is a copolymer rubber prepared by anionic solution polymerization of butadiene and styrene monomers in a hydrocarbon solvent with alkyllithium as an initiator.
Since SSBR has excellent wear resistance, resistance to crack formation, grip on wet road, heat resistance, and flexing resistance after long-term exposure at high temperature, and also has the characteristics of low heat generation during mixing in an internal mixer, small extrusion expansion rate, high filling amount, and the like, the proportion of SSBR applied to tire products is increasing.
The SSBR has excellent wear resistance, dynamic performance and low temperature resistance, and can be used for manufacturing large tires, snow tires, and the like.
From the viewpoint of abrasion resistance, tensile strength, flatness by vulcanization, flex resistance, heat resistance and the like, SSBR is suitable for use in the production of conveyor belts, particularly heat-resistant conveyor belts.
SSBR also has the advantages of good electrical insulation properties, excellent color, low ash, and low non-rubber content.
From the viewpoint of balance between processability and physical and mechanical properties, SSBR is a rubber product having a variety of comprehensive properties.
In view of the excellent properties of the solution-polymerized styrene-butadiene rubber, much research in this field has been conducted, and CN1432586A discloses a solution-polymerized styrene-butadiene rubber containing high molecular weight, but the content of the high molecular weight part is 10-40 wt%, which is too high to be beneficial to the later-stage product processing; CN102344529A adopts a method of dripping an anionic initiator for a plurality of times to prepare solution-polymerized styrene-butadiene rubber, however, the prior art has complex process and inconvenient operation.
Disclosure of Invention
The invention aims to provide a monovinylarene-conjugated diene polymer containing an ultrahigh molecular weight polymer and a preparation method thereof.
In order to achieve the above object, a first aspect of the present invention provides a monovinylarene-conjugated diene polymer, which contains 1 to 10 wt% of a high polymer and an oligomer obtained by coupling, wherein the number average molecular weight of the high polymer is 120 ten thousand or more, the content of a monovinylarene structural unit in the polymer is 10 to 50 wt%, the content of a conjugated diene structural unit in the polymer is 50 to 90 wt%, and the molecular weight distribution coefficient is 1.0 to 1.5.
In a second aspect, the present invention provides a process for preparing the monovinylarene-conjugated diene polymer of the first aspect of the present invention, comprising:
(1) in the presence of a non-polar solvent, adding a monovinylarene monomer, a conjugated diene monomer, a third monomer, a polarity regulator and an anionic initiator to perform a first polymerization reaction, wherein the third monomer is divinylbenzene;
(2) after the monomer in the step (1) is completely converted, adding the monovinylarene monomer, the conjugated diene monomer and the anionic initiator again to carry out a second polymerization reaction;
(3) and (3) after the monomer in the step (2) is completely converted, sequentially adding a coupling agent, a terminating agent and an anti-aging agent into the reaction system.
In a third aspect, the present invention provides the use of a monovinylarene-conjugated diene polymer according to the first aspect in a rubber for a tire tread.
The monovinylarene-conjugated diene polymer provided by the invention contains ultrahigh molecular weight high polymer with moderate content.
The monovinylarene-conjugated diene polymer provided by the invention has the advantages of excellent strength and dynamic performance due to the action of ultrahigh molecular weight, simple operation process and easy realization of industrialization.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
As described above, the first aspect of the present invention provides a monovinylarene-conjugated diene polymer, which contains 1 to 10 wt% of a high polymer and an oligomer obtained by coupling, wherein the number average molecular weight of the high polymer is 120 ten thousand or more, the content of a monovinylarene structural unit in the polymer is 10 to 50 wt%, the content of a conjugated diene structural unit in the polymer is 50 to 90 wt%, and the molecular weight distribution coefficient is 1.0 to 1.5.
Preferably, the content of the high polymer in the polymer is 3-8 wt%, the number average molecular weight of the high polymer is 120-200 ten thousand, and the molecular weight distribution coefficient is 1.05-1.25; more preferably, the number average molecular weight of the polymer is 130 to 180 ten thousand.
Preferably, the content of the monovinylarene structural unit in the polymer is 20-30 wt%, and the content of the conjugated diene structural unit in the polymer is 70-80 wt%.
Preferably, the monovinyl aromatic hydrocarbon is at least one selected from the group consisting of styrene, vinyltoluene, α -methylstyrene, 4-tert-butylstyrene, 4-methylstyrene, 3, 5-diethylstyrene, 3, 5-di-n-butylstyrene, 4-n-propylstyrene and 4-dodecylstyrene. More preferably, the monovinylarene is styrene.
Preferably, the conjugated diene is at least one selected from the group consisting of butadiene, isoprene, 1, 3-pentadiene, 1, 3-hexadiene and 2, 3-dimethylbutadiene; more preferably, the conjugated diene is butadiene or isoprene; particularly preferably, the conjugated diene is butadiene.
Preferably, the coupling efficiency of the oligomer obtained by coupling is 30 to 80 wt%; the number average molecular weight of the basic peak before coupling is 8-25 ten thousand. Particularly preferably, the oligomer obtained by the coupling has a coupling efficiency of 45 to 65% by weight.
As previously stated, a second aspect of the present invention provides a process for preparing the monovinylarene-conjugated diene polymer of the first aspect of the present invention, the process comprising:
(1) in the presence of a non-polar solvent, adding a monovinylarene monomer, a conjugated diene monomer, a third monomer, a polarity regulator and an anionic initiator to perform a first polymerization reaction, wherein the third monomer is divinylbenzene;
(2) after the monomer in the step (1) is completely converted, adding the monovinylarene monomer, the conjugated diene monomer and the anionic initiator again to carry out a second polymerization reaction;
(3) and (3) after the monomer in the step (2) is completely converted, sequentially adding a coupling agent, a terminating agent and an anti-aging agent into the reaction system.
Preferably, the third monomer is p-divinylbenzene and/or m-divinylbenzene.
According to a preferred embodiment, the third monomer is a mixture of p-divinylbenzene and m-divinylbenzene.
Preferably, in the mixture of p-divinylbenzene and m-divinylbenzene, the content molar ratio of p-divinylbenzene to m-divinylbenzene is 1: (0.5-2.5). The inventors of the present invention found that the molar ratio of 1: (0.5 to 2.5) of a mixture of p-divinylbenzene and m-divinylbenzene as the third monomer in the preparation method of the present invention, the polymer thus obtained can be more excellent in strength and dynamic properties.
Preferably, the molar amount of the third monomer is 3 to 20 times, and more preferably 4 to 10 times that of the anionic initiator in the step (1).
Preferably, the nonpolar solvent is used in an amount such that the initial content of the polymerized monomer in the reaction system of step (1) is 0.1 to 1.5 wt%.
Preferably, the ratio of the total amount of monovinylarene monomer and conjugated diene monomer added in step (1) to the total amount of monovinylarene monomer and conjugated diene monomer added in step (2) (by weight) is 1: (5-50); more preferably 1: (10-35).
Preferably, the ratio of the molar amount of coupling agent to the molar amount of anionic initiator in step (2) is 1: (1.2-10); more preferably 1: (2.5-6).
Preferably, the molar ratio of the used amount of the anionic initiator in the step (2) to the used amount of the anionic initiator in the step (1) is (1-30): 1; preferably (2-20): 1.
preferably, the non-polar solvent is selected from benzene, toluene, ethylbenzene, xylene, pentane, hexane, heptane, octane, cyclohexane, mixed xylenes, raffinate oil, or any combination of two or more of the foregoing solvents, preferably the non-polar solvent is cyclohexane or a mixed solvent of n-hexane and cyclohexane.
Preferably, the conditions of the first polymerization reaction and the second polymerization reaction each independently comprise: the temperature is 30 to 100 ℃, and more preferably 50 to 70 ℃.
According to a preferred embodiment, the time of the first polymerization reaction is 0.2 to 2 hours, more preferably 0.5 to 1 hour.
According to another preferred embodiment, the time of the second polymerization reaction is 0.2 to 2 hours, and more preferably 0.8 to 1.5 hours. The timing end point of the second polymerization reaction is the time point of starting to add the coupling agent.
According to still another preferred embodiment, the time for adding the coupling agent to carry out the coupling reaction in step (3) is 0.3 to 2 hours, and more preferably 0.5 to 1 hour. The starting point of the coupling reaction time is when the coupling agent is started to be added.
Preferably, the antioxidant is at least one of an amine antioxidant, a quinoline antioxidant and a benzimidazole antioxidant. For example, the antioxidant is antioxidant 4020.
Preferably, the anionic initiator is a compound having the structure RLi, wherein R is C1-C10Linear or branched alkyl of (a); more preferably, said R is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl and n-decyl. It is particularly preferred that the anionic initiator is n-butyllithium.
Preferably, the polarity modifier (also referred to as a structure modifier) is selected from the group consisting of diethyl ether, dibutyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofurfuryl alcohol ether, dioxane, crown ether, triethylamine, tetramethylethylenediamine, hexamethylphosphoric triamide, potassium tert-butoxide, potassium lauryl alkoxide, potassium alkyl benzene sulfonate and sodium alkyl benzene sulfonate. Tetrahydrofurfuryl alcohol ether (ETE) is particularly preferred.
Preferably, the amount of the polarity modifier is such that the initial weight concentration of the polarity modifier in the reaction system of step (1) is 100-1000 ppm, more preferably 300-500 ppm.
The coupling agent of the present invention is preferably at least one of silicon tetrachloride, trichlorosilane, tin tetrachloride, tin trichloride, epoxidized soybean oil, divinylbenzene, methoxytrichlorosilane, and tetrabromosilane, and more preferably silicon tetrachloride and/or tin tetrachloride.
As previously mentioned, a third aspect of the present invention provides the use of the monovinylarene-conjugated diene polymer of the first aspect in a rubber for a tire tread.
The present invention will be described in detail below by way of examples. In the following examples, various raw materials used are commercially available without specific description.
In the following examples, number average molecular weight (M)n) The measurement was carried out by means of an ALLIANCE model 2690 gel permeation chromatograph from WATERS, USA, using a PLgel Mixed-C gel column from Agilent, THF as the mobile phase, narrow-distribution polystyrene as the standard and a temperature of 25 ℃.
In the following examples, the content of the high polymer in the polymer was measured by gel permeation chromatography.
In the following examples, tensile properties were measured according to the method of the national Standard "test method for tensile Properties of plastics GB/T1040-92", model AG-20KNG manufactured by Shimadzu corporation; the tensile rate was 500mm/min and the test temperature was 23 ℃. The effective portion of the sample had a length of 25mm and a width of 6 mm. For each set of samples, 10 replicates were run and the results averaged.
In the following examples, the viscoelastic behaviour of the samples was tested on a dynamic thermomechanical analyzer eplex-500N, GABO, germany. The sample had a length of 35mm, a width of 8mm and a thickness of 1.0 mm. The test adopts a stretching mode, the test frequency is 11Hz, the temperature range is-100 ℃, the heating rate is 3 ℃/min, the static strain is 1 percent, and the dynamic strain is 0.25 percent.
Example 1
Adding 2500g of cyclohexane/hexane mixed solvent (the volume ratio is 15: 85) and 24g of mixed monomer of styrene and butadiene (the mixed monomer is dissolved in 100g of cyclohexane solvent, wherein the weight ratio of the styrene to the butadiene is 25: 75), 4mmol of p-divinylbenzene and 0.84g of tetrahydrofurfuryl alcohol ether into a 5L stainless steel polymerization kettle, opening and stirring, heating in a constant-temperature water bath, adding 0.5mmol of n-butyl lithium into the polymerization kettle when the temperature in the polymerization kettle reaches 50 ℃, reacting for 0.5h, adding 276g of the same mixed solution of styrene and butadiene into the polymerization kettle, adding 1.1mmol of n-butyl lithium, reacting for 1h under stirring, adding 0.2mmol of silicon tetrachloride, reacting for 0.5h, adding isopropanol to terminate the reaction, adding an anti-aging agent 4020, and performing wet coagulation treatment on a glue solution.
It was found that the content of the polymer in the polymer obtained in this example was 5.1% by weight, the number average molecular weight of the polymer was 155 ten thousand, the molecular weight distribution coefficient was 1.20, the number average molecular weight of the base peak of the oligomer before coupling was 25 ten thousand, and the coupling efficiency was 45%.
Comparative example 1
2500g of cyclohexane/hexane mixed solvent (volume ratio is the same as that in example 1) is added into a 5L stainless steel polymerization kettle, 300g of mixed monomer of styrene and butadiene (the mixed monomer is dissolved in 100g of cyclohexane solvent, wherein the weight ratio of the contents of styrene and butadiene is 25: 75), 4mmol of p-divinylbenzene and 0.84g of tetrahydrofurfuryl alcohol ether are added, stirring is started, constant-temperature water bath heating is carried out, when the temperature in the polymerization kettle reaches 50 ℃, 1.6mmol of n-butyl lithium is added into the polymerization kettle, after 1.5h of reaction, 0.2mmol of silicon tetrachloride is added, the reaction is carried out for 0.5h, isopropanol is added to terminate the reaction, an anti-aging agent 4020 is added, and wet coagulation treatment is carried out on glue solution.
It was found that the polymer obtained in this comparative example did not contain a polymer having an ultrahigh molecular weight, the number average molecular weight of the base peak of the oligomer before coupling was 18.5 ten thousand, and the coupling efficiency was 58%.
Example 2
2500g of cyclohexane/hexane mixed solvent (volume ratio is the same as that in example 1), 9g of mixed monomer of styrene and butadiene (the mixed monomer is dissolved in 100g of cyclohexane solvent, wherein the weight ratio of the styrene to the butadiene is 30: 70), 2.0mmol of m-divinylbenzene and 1.4g of tetrahydrofurfuryl alcohol ether are added into a 5L stainless steel polymerization kettle, stirring is started, heating is carried out in a constant-temperature water bath, when the temperature in the polymerization kettle reaches 60 ℃, 0.2mmol of n-butyl lithium is added into the polymerization kettle, after 1 hour of reaction, 291g of the same mixed solution of styrene and butadiene is added into the polymerization kettle again, then 3.7mmol of n-butyl lithium is added, after 1.5 hours of reaction under stirring, 1.1mmol of tin tetrachloride is added, after 0.8 hour of reaction, isopropanol is added to stop the reaction, an anti-aging agent 4020 is added, and the glue solution is subjected to wet coagulation treatment.
It was found that the content of the polymer in the polymer obtained in this example was 4.8% by weight, the number average molecular weight of the polymer was 170 ten thousand, the molecular weight distribution coefficient was 1.25, the number average molecular weight of the base peak of the oligomer before coupling was 8 ten thousand, and the coupling efficiency was 65%.
Example 3
2500g of cyclohexane/hexane mixed solvent (volume ratio same as in example 1), 15g of mixed monomer of styrene and butadiene (mixed monomer dissolved in 100g of cyclohexane solvent, wherein the weight ratio of styrene to butadiene is 20: 80), 1.0mmol of p-divinylbenzene, 1.0mmol of m-divinylbenzene, and 1.0g of tetrahydrofurfuryl alcohol ether were charged into a 5L stainless steel polymerizer, and heated in a constant temperature water bath until the temperature in the polymerizer reached 55 ℃, 0.25mmol of n-butyllithium was charged into the polymerization reactor, and after 0.5 hour of reaction, 285g of the same mixture of styrene and butadiene as described above was charged into the polymerization reactor again, followed by 1.9mmol of n-butyllithium, reacting for 1h under stirring, adding 0.5mmol of silicon tetrachloride, reacting for 1h, adding isopropanol to terminate the reaction, adding anti-aging agent 4020, and performing wet coagulation treatment on the glue solution.
It was found that the content of the polymer in the polymer obtained in this example was 6.5% by weight, the number average molecular weight of the polymer was 160 ten thousand, the molecular weight distribution coefficient was 1.21, the number average molecular weight of the base peak of the oligomer before coupling was 15 ten thousand, and the coupling efficiency was 55%.
Example 4
This example was carried out in a similar manner to example 1, except that:
the weight of the first-charged mixed monomer of styrene and butadiene (the same as in example 1) in this example was 20g, the amount of ETE was 0.95g, the amount of p-divinylbenzene was 2.5mmol, and the amount of n-butyllithium charged for the first time was 0.25 mmol; the weight of the cyclohexane solution of styrene and butadiene charged for the second time was 280g, and the n-butyllithium charged for the second time was 1.6 mmol; the addition amount of the coupling agent silicon tetrachloride is 0.5 mmol.
The rest is the same as in example 1.
It was found that the content of the polymer in the polymer obtained in this example was 7.7% by weight, the number average molecular weight of the polymer was 130 ten thousand, the molecular weight distribution coefficient was 1.09, the number average molecular weight of the base peak of the oligomer before coupling was 18 ten thousand, and the coupling efficiency was 50%.
Example 5
This example was carried out in a similar manner to example 2, except that:
the weight of the first-charged mixed monomer of styrene and butadiene (the same as in example 2) in this example was 11g, the amount of ETE was 1.1g, the amount of meta-divinylbenzene was 1.8mmol, and the amount of n-butyllithium charged for the first time was 0.2 mmol; the weight of the cyclohexane solution of styrene and butadiene charged for the second time was 289g, and the n-butyllithium charged for the second time was 1.5 mmol; the amount of tin tetrachloride added as a coupling agent was 0.4 mmol.
The rest is the same as in example 2.
It was found that the content of the polymer in the polymer obtained in this example was 5.0% by weight, the number average molecular weight of the polymer was 180 ten thousand, the molecular weight distribution coefficient was 1.24, the number average molecular weight of the base peak of the oligomer before coupling was 20 ten thousand, and the coupling efficiency was 60%.
Test example
The polymers (100 weight portions) prepared in the above examples and comparative examples are reinforced by white carbon black system, the white carbon black is 165GR from Rodiya corporation, the white carbon black is added in 60 weight portions, 8# reference carbon black is 10 weight portions, operation oil TDAE (Oufun rubber Co., Ltd., Qingzhou city) is 15 weight portions, zinc oxide (chemical reagent Co., Ltd., China medicine group) is 3.0 weight portions, stearic acid (chemical reagent Co., Ltd., China medicine group) is 2.0 weight portions, sulfur (chemical reagent Co., Ltd., China medicine group) is 1.5 weight portions, anti-aging agent 4020 (Gaoyi and chemical Co., Ltd., Gaoyi, chemical industry Co., Ltd., 1.5 weight portions, accelerator D (Shijia Chengxian chemical industry Co., Ltd., accelerator TBBS (New Material science and technology Co., Guangdouba City) is 1.5 weight portions, and the polymer sources in the tests of the examples and comparative examples are different, and the rest are the same Banbury mixer is 1600 Meifa Lai type BR, the volume of the die cavity is 1.5L; the plate vulcanizing machine is produced by Pan stone oil pressure industry (Anhui) limited and has the model of P-50-PCD-3L (the vulcanizing temperature is 150 ℃, the vulcanizing pressure is 20MPa, and the vulcanizing time is 50 min). Obtaining the vulcanized rubber.
The properties of the resulting vulcanized rubber are shown in Table 1.
TABLE 1
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 | |
| Tensile strength/MPa | 25.1 | 24.7 | 25.5 | 22.3 | 24.3 | 20.0 |
| 100% definite elongation/MPa | 5.3 | 5.1 | 5.5 | 5.0 | 4.9 | 4.7 |
| 300% definite elongation/MPa | 21.3 | 20.9 | 22.3 | 18.9 | 21.6 | 17.2 |
| Elongation/percent | 400 | 398 | 411 | 351 | 403 | 323 |
| Tear 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 |
From the above results, it can be seen that the polymer provided by the present invention contains ultrahigh molecular weight high polymer with moderate content, and gives excellent strength and dynamic performance to the polymer.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (36)
1. A monovinylarene-conjugated diene polymer comprises an oligomer obtained by coupling and 1-10 wt% of a high polymer, wherein the number average molecular weight of the high polymer is more than 120 ten thousand, the molecular weight distribution coefficient is 1.0-1.5, the content of a monovinylarene structural unit in the polymer is 10-50 wt%, the content of a conjugated diene structural unit in the polymer is 50-90 wt%, the coupling efficiency of the oligomer obtained by coupling is 30-80%, and the number average molecular weight of basic peaks before coupling is 8-25 ten thousand.
2. The polymer according to claim 1, wherein the polymer is contained in an amount of 3 to 8% by weight, and the polymer has a number average molecular weight of 120 to 200 ten thousand and a molecular weight distribution coefficient of 1.05 to 1.25.
3. The polymer according to claim 2, wherein the number average molecular weight of the polymer is 130 to 180 ten thousand.
4. The polymer according to any one of claims 1 to 3, wherein the content of monovinylarene structural units and conjugated diene structural units in the polymer is from 20 to 30 wt% and from 70 to 80 wt%.
5. The polymer according to any one of claims 1 to 3, wherein the monovinyl aromatic hydrocarbon is selected from at least one of styrene, vinyltoluene, α -methylstyrene, 4-tert-butylstyrene, 4-methylstyrene, 3, 5-diethylstyrene, 3, 5-di-n-butylstyrene, 4-n-propylstyrene and 4-dodecylstyrene.
6. The polymer of claim 5, wherein the monovinylarene is styrene.
7. The polymer of any of claims 1-3, wherein the conjugated diene is selected from at least one of butadiene, isoprene, 1, 3-pentadiene, 1, 3-hexadiene, and 2, 3-dimethylbutadiene.
8. The polymer of claim 7, wherein the conjugated diene is butadiene or isoprene.
9. The polymer of claim 1, wherein the oligomer obtained by coupling has a coupling efficiency of 45 to 65 wt.%.
10. A process for preparing the monovinylarene-conjugated diene polymer of any one of claims 1 to 9, comprising:
(1) in the presence of a non-polar solvent, adding a monovinylarene monomer, a conjugated diene monomer, a third monomer, a polarity regulator and an anionic initiator to perform a first polymerization reaction, wherein the third monomer is divinylbenzene;
(2) after the monomer in the step (1) is completely converted, adding the monovinylarene monomer, the conjugated diene monomer and the anionic initiator again to carry out a second polymerization reaction;
(3) and (3) after the monomer in the step (2) is completely converted, sequentially adding a coupling agent, a terminating agent and an anti-aging agent into the reaction system.
11. The process of claim 10, wherein the third monomer is p-divinylbenzene and/or m-divinylbenzene.
12. The method of claim 11, wherein the third monomer is a mixture of p-divinylbenzene and m-divinylbenzene.
13. The process of claim 12, wherein the p-divinylbenzene and m-divinylbenzene are present in the mixture in a molar ratio of 1: (0.5-2.5).
14. The method according to claim 10, wherein the molar amount of the third monomer is 3 to 20 times that of the anionic initiator in the step (1).
15. The method according to claim 14, wherein the molar amount of the third monomer is 4 to 10 times that of the anionic initiator in the step (1).
16. The method as claimed in any one of claims 10 to 15, wherein the non-polar solvent is used in an amount such that the initial content of the polymerized monomer in the reaction system of step (1) is 0.1 to 1.5% by weight.
17. The method of claim 10, wherein the conditions of the first polymerization reaction and the second polymerization reaction each independently comprise: the temperature is 30-100 ℃.
18. The method of claim 17, wherein the conditions of the first polymerization reaction and the second polymerization reaction each independently comprise: the temperature is 50-70 ℃.
19. The process according to claim 10 or 17, wherein the time of the first polymerization reaction is 0.2 to 2 hours.
20. The process of claim 19, wherein the first polymerization reaction time is 0.5 to 1 hour.
21. The process according to claim 10 or 17, wherein the time of the second polymerization reaction is 0.2 to 2 hours.
22. The process according to claim 21, wherein the second polymerization reaction is carried out for a period of 0.8 to 1.5 hours.
23. The method according to claim 10 or 17, wherein the time for adding the coupling agent to carry out the coupling reaction in the step (3) is 0.3-2 h.
24. The method according to claim 23, wherein the time for adding the coupling agent to carry out the coupling reaction in the step (3) is 0.5 to 1 hour.
25. The process of claim 10, wherein the anionic initiator is a compound having the structure RLi, wherein R is C1-C10Linear or branched alkyl.
26. The method of claim 25, wherein R is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, and n-decyl.
27. The method of claim 10, wherein the polarity modifier is selected from the group consisting of diethyl ether, dibutyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofurfuryl alcohol ether, dioxane, crown ether, triethylamine, tetramethylethylenediamine, hexamethylphosphoric triamide, potassium tert-butoxide, potassium tert-pentoxide, potassium lauryl, potassium alkyl benzene sulfonate, and sodium alkyl benzene sulfonate.
28. The method as claimed in claim 27, wherein the amount of the polarity modifier is such that the initial weight concentration of the polarity modifier in the reaction system of step (1) is 100 to 1000 ppm.
29. The method as claimed in claim 28, wherein the amount of the polarity modifier is such that the initial weight concentration of the polarity modifier in the reaction system of step (1) is 300 to 500 ppm.
30. The process of claim 10, wherein the ratio of the total amount of monovinylarene monomer and conjugated diene monomer added in step (1) to the total weight of monovinylarene monomer and conjugated diene monomer added in step (2) is 1: (5-50).
31. The process of claim 30, wherein the ratio of the total amount of monovinylarene monomer and conjugated diene monomer added in step (1) to the total weight of monovinylarene monomer and conjugated diene monomer added in step (2) is 1: (10-35).
32. The process of claim 10, wherein the ratio of the molar amount of coupling agent to the molar amount of anionic initiator in step (2) is 1: (1.2-10).
33. The process of claim 32, wherein the ratio of the molar amount of coupling agent to the molar amount of anionic initiator in step (2) is 1: (2.5-6).
34. The method according to claim 10, wherein the molar ratio of the used amount of the anionic initiator in the step (2) to the used amount of the anionic initiator in the step (1) is (1-30): 1.
35. the method according to claim 34, wherein the molar ratio of the used amount of the anionic initiator in the step (2) to the used amount of the anionic initiator in the step (1) is (2-20): 1.
36. use of a monovinylarene-conjugated diene polymer according to any one of claims 1 to 9 in a tire tread rubber.
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