CN114478917A - Styrene butadiene rubber and preparation method and application thereof - Google Patents
Styrene butadiene rubber and preparation method and application thereof Download PDFInfo
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- CN114478917A CN114478917A CN202011147700.5A CN202011147700A CN114478917A CN 114478917 A CN114478917 A CN 114478917A CN 202011147700 A CN202011147700 A CN 202011147700A CN 114478917 A CN114478917 A CN 114478917A
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- styrene
- butadiene rubber
- butadiene
- weight ratio
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- 229920003048 styrene butadiene rubber Polymers 0.000 title claims abstract description 142
- 238000002360 preparation method Methods 0.000 title abstract description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 107
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000000463 material Substances 0.000 claims abstract description 31
- 238000006116 polymerization reaction Methods 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 28
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 26
- 239000000178 monomer Substances 0.000 claims description 20
- 229920000642 polymer Polymers 0.000 claims description 19
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 18
- 230000000977 initiatory effect Effects 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 17
- 239000002270 dispersing agent Substances 0.000 claims description 16
- 239000003999 initiator Substances 0.000 claims description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 13
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- VUFKMYLDDDNUJS-UHFFFAOYSA-N 2-(ethoxymethyl)oxolane Chemical compound CCOCC1CCCO1 VUFKMYLDDDNUJS-UHFFFAOYSA-N 0.000 claims description 11
- 239000003963 antioxidant agent Substances 0.000 claims description 11
- 230000003078 antioxidant effect Effects 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 10
- 239000004215 Carbon black (E152) Substances 0.000 claims description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 9
- 150000005215 alkyl ethers Chemical class 0.000 claims description 9
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 9
- 239000000920 calcium hydroxide Substances 0.000 claims description 9
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 9
- 239000001569 carbon dioxide Substances 0.000 claims description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 9
- 229930195733 hydrocarbon Natural products 0.000 claims description 9
- 150000002430 hydrocarbons Chemical class 0.000 claims description 9
- -1 polyoxyethylene Polymers 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 7
- 125000000129 anionic group Chemical group 0.000 claims description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical group CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- FZLHAQMQWDDWFI-UHFFFAOYSA-N 2-[2-(oxolan-2-yl)propan-2-yl]oxolane Chemical compound C1CCOC1C(C)(C)C1CCCO1 FZLHAQMQWDDWFI-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- PGZISVXTYZWYPK-UHFFFAOYSA-N 2-(butoxymethyl)oxolane Chemical compound CCCCOCC1CCCO1 PGZISVXTYZWYPK-UHFFFAOYSA-N 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 3
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 2
- CCZVEWRRAVASGL-UHFFFAOYSA-N lithium;2-methanidylpropane Chemical compound [Li+].CC(C)[CH2-] CCZVEWRRAVASGL-UHFFFAOYSA-N 0.000 claims description 2
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229920002857 polybutadiene Polymers 0.000 abstract description 33
- 239000005063 High cis polybutadiene Substances 0.000 abstract description 25
- 238000012360 testing method Methods 0.000 description 34
- 230000000052 comparative effect Effects 0.000 description 12
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 229920001971 elastomer Polymers 0.000 description 7
- 239000005060 rubber Substances 0.000 description 7
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 239000005064 Low cis polybutadiene Substances 0.000 description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical group [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- 238000005345 coagulation Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 239000005066 High trans polybutadiene Substances 0.000 description 1
- 239000005065 High vinyl polybutadiene Substances 0.000 description 1
- 241001441571 Hiodontidae Species 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B13/00—Soles; Sole-and-heel integral units
- A43B13/02—Soles; Sole-and-heel integral units characterised by the material
- A43B13/04—Plastics, rubber or vulcanised fibre
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to the technical field of styrene butadiene rubber, and discloses styrene butadiene rubber, a preparation method and application thereof, wherein the weight ratio of styrene structural units to butadiene structural units in the styrene butadiene rubber is 0.65-1.05: 1; the weight ratio of the 1, 2-structural unit to the 1, 4-structural unit in the styrene butadiene rubber is 0.33-0.54: 1; the styrene-butadiene rubber has a block styrene structureThe weight ratio of the component to the non-block styrene structural unit is 0.27-0.57: 1; and the number average molecular weight of the styrene butadiene rubber is 8-11 ten thousand; the molecular weight distribution index of the styrene butadiene rubber is 1.0-1.2; the Mooney viscosity ML of the styrene-butadiene rubber at 100 DEG C1+4Is 40-60. The styrene butadiene rubber and the high cis-polybutadiene rubber provided by the invention have good compatibility, and the styrene butadiene rubber and the high cis-polybutadiene rubber are compounded to obtain the sole material with good transparency and wet skid resistance.
Description
Technical Field
The invention relates to the technical field of styrene butadiene rubber, in particular to styrene butadiene rubber, a method for preparing styrene butadiene rubber and application of styrene butadiene rubber in preparing shoe materials.
Background
With the upgrading and upgrading of consumption concept, people have higher and higher requirements on the comprehensive performance of the sole material, and the sole material with high added value is required to have cold resistance, wet skid resistance and good transparency.
In order to obtain a sole material with better comprehensive performance, the mainstream technology is to use different types of rubber together so that different rubber components can act synergistically, thereby realizing integration of different rubber performances and improving the comprehensive performance of the sole material.
The polybutadiene rubber has a flexible molecular chain, low glass transition temperature and wide material sources, and is a cold-resistant rubber which is preferably selected. Polybutadiene rubber is further classified into high cis-polybutadiene rubber, high trans-polybutadiene rubber, low cis-polybutadiene rubber, medium vinyl polybutadiene rubber and high vinyl polybutadiene rubber; among them, the high cis-polybutadiene rubber and the low cis-polybutadiene rubber have the lowest glass transition temperature and better cold resistance. The cis-trans of the low cis-polybutadiene rubber molecular chain is randomly distributed, the strength is lower, and the high cis-polybutadiene rubber molecular chain has a regular structure and a crystallization tendency under stress, so that the cold-resistant sole material is the first choice. However, the high cis-polybutadiene rubber has low glass transition temperature, flexible molecular chain and poor wet skid resistance.
In order to improve the wet skid resistance of the high cis-polybutadiene rubber, the styrene-butadiene rubber which has high glass transition temperature and good compatibility with the high cis-polybutadiene rubber is required to be used. However, the existing styrene butadiene rubber and high cis-polybutadiene rubber in the market are compounded, so that the wet skid resistance and the transparency of the shoe material cannot be considered at the same time.
Therefore, it is required to provide a new styrene-butadiene rubber to be compounded with high cis-polybutadiene rubber to obtain a shoe material having both good wet skid resistance and good transparency.
Disclosure of Invention
The invention aims to overcome the defect that the wet skid resistance and the transparency of a shoe material cannot be considered when styrene-butadiene rubber and high cis-polybutadiene rubber are compounded in the prior art.
In view of the above problems, the inventors of the present invention have conducted intensive studies on the correlation between the structure and performance of styrene-butadiene rubber, and found that by reasonably controlling the structural parameters of styrene-butadiene rubber, particularly the ratio of block styrene to non-block styrene in the molecular chain sequence of styrene-butadiene rubber and the content of 1, 2-structural units in butadiene structural units, a shoe sole material having excellent wet skid resistance and good compatibility with high cis-polybutadiene rubber can be obtained, and the two are compounded to obtain a shoe sole material having good transparency and having both cold resistance and wet skid resistance, thereby completing the present invention.
In order to achieve the above object, a first aspect of the present invention provides a styrene-butadiene rubber, wherein the content weight ratio of styrene structural units to butadiene structural units in the styrene-butadiene rubber is 0.65 to 1.05: 1; the weight ratio of the 1, 2-structural unit to the 1, 4-structural unit in the styrene butadiene rubber is 0.33-0.54: 1; the content weight ratio of the block styrene structural unit to the non-block styrene structural unit in the styrene-butadiene rubber is 0.27-0.57: 1; and the number of the first and second groups,
the number average molecular weight of the styrene butadiene rubber is 8-11 ten thousand; the molecular weight distribution index of the styrene butadiene rubber is 1.0-1.2; the Mooney viscosity ML of the styrene-butadiene rubber at 100 DEG C1+4Is 40-60.
In a second aspect, the present invention provides a method for preparing styrene-butadiene rubber according to the first aspect, comprising:
(1) in a nonpolar hydrocarbon solvent, in the presence of a structure regulator and an initiator, under the condition of initiating polymerization reaction, carrying out anion solution polymerization reaction on a 1, 3-butadiene monomer and a styrene monomer to obtain a styrene-butadiene rubber polymer solution;
(2) mixing the styrene butadiene rubber polymer solution with water, carbon dioxide, an antioxidant and a dispersant in sequence;
wherein, in the step (1), the structure regulator is selected from at least one of tetrahydrofuran, tetrahydrofurfuryl ethyl ether, tetrahydrofurfuryl butyl ether, N-2-methyl-tetrahydrofurfuryl amine and 2, 2-bis (2-tetrahydrofuryl) propane;
the conditions for initiating the polymerization are at least: the initiation temperature is 35-55 ℃; the conditions of the anionic solution polymerization are at least as follows: the maximum polymerization temperature is 90-110 ℃.
The third aspect of the invention provides the use of the styrene-butadiene rubber of the first aspect in the preparation of shoe materials.
Compared with the prior art, the method provided by the invention at least has the following advantages:
the styrene butadiene rubber and the high cis-polybutadiene rubber provided by the invention have good compatibility, and the styrene butadiene rubber and the high cis-polybutadiene rubber are compounded to obtain the sole material with excellent transparency and wet skid resistance.
Additional features and advantages of the invention will be described in detail in the detailed description which follows.
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 numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.
In the present invention, the block styrene structural unit means six or more continuous styrene structural units in the styrene-butadiene rubber molecular chain.
In the present invention, the term "1, 2-structural unit" means a corresponding structural unit formed by 1, 2-polymerization of butadiene; "1, 4-structural unit" means the corresponding structural unit of butadiene formed in a 1, 4-polymerization manner.
As described above, the first aspect of the present invention provides a styrene-butadiene rubber in which the content weight ratio of styrene structural units to butadiene structural units is 0.65 to 1.05: 1; the weight ratio of the 1, 2-structural unit to the 1, 4-structural unit in the styrene butadiene rubber is 0.33-0.54: 1; the content weight ratio of the block styrene structural unit to the non-block styrene structural unit in the styrene-butadiene rubber is 0.27-0.57: 1; and the number of the first and second groups,
the number average molecular weight of the styrene butadiene rubber is 8-11 ten thousand; the molecular weight distribution index of the styrene butadiene rubber is 1.0-1.2; the Mooney viscosity ML of the styrene-butadiene rubber at 100 DEG C1+4Is 40-60.
In the invention, the styrene structural unit and butadiene structural unit content, the 1, 2-structural unit content and the 1, 4-structural unit content, the block styrene structural unit content and the non-block styrene structural unit content of the styrene-butadiene rubber are all Bruker AVANCE400 type superconducting nuclear magnetic resonance wave apparatus (a)1H-NMR), test conditions including:1the resonance frequency of H nucleus is 300.13MHz, the spectrum width is 2747.253Hz, the pulse width is 5.0 mus, the data point is 16K, the diameter of the sample tube is 5mm, and the solvent is deuterated chloroform CDCl3The sample concentration was 15 weight% (W/V), the test temperature was normal temperature (25. + -. 2 ℃ C.), the number of scanning times was 16, and calibration was made with a chemical shift of tetramethylsilane of 0 ppm.
In the invention, the molecular weight and the molecular weight distribution index of the styrene-butadiene rubber are measured by adopting an HLC-8320 type gel permeation chromatograph of Tosoh corporation in Japan, wherein the test conditions comprise: the chromatographic column was TSKgelSuperMultipolypore HZ-N, the standard column was TSKgelSuperMultipolypore HZ, the solvent was chromatographically pure THF, the calibration standard was polystyrene, the sample mass concentration was 1mg/ml, the sample amount was 10.00. mu.l, the flow rate was 0.35ml/min, and the test temperature was 40.0 ℃.
In the invention, the Mooney viscosity of the styrene butadiene rubber is measured according to GB/T1232.1 standard by adopting a GT-7080-S2 Mooney viscometer manufactured by Gotech company of Taiwan, wherein the preheating time is 1min, the rotating time is 4min, and the testing temperature is 100 ℃.
Preferably, the content weight ratio of the styrene structural unit to the butadiene structural unit in the styrene-butadiene rubber is 0.75-0.95: the inventors found that, in particular, the weight ratio of styrene structural units to butadiene structural units in styrene-butadiene rubber is controlled in the range of 0.75 to 0.95: 1, the wet skid resistance and the transparency of the shoe material can be better considered when the rubber is compounded with the high cis-polybutadiene rubber.
Preferably, the content weight ratio of the 1, 2-structural unit to the 1, 4-structural unit in the styrene-butadiene rubber is 0.36-0.5: 1, the styrene butadiene rubber and the high cis-polybutadiene rubber are compounded, so that the wet skid resistance and the transparency of the shoe material can be better considered.
In order to better compromise the transparency of the composite when compounded with the high-cis polybutadiene rubber, the styrene-butadiene rubber preferably has a content weight ratio of the block styrene structural unit to the non-block styrene structural unit of 0.32-0.47: 1.
preferably, the number average molecular weight of the styrene-butadiene rubber is 8.5-10.5 ten thousand, so that the styrene-butadiene rubber has better processing performance and better final product performance.
Preferably, the styrene-butadiene rubber has a molecular weight distribution index of 1.0 to 1.1.
Preferably, the Mooney viscosity ML of the styrene-butadiene rubber at 100 DEG C1+443 to 53, thereby the styrene-butadiene rubber has better processing property, and when the styrene-butadiene rubber is compounded with high cis-polybutadiene rubber, a compound used for shoe materials with better transparency can be obtained.
The styrene butadiene rubber provided by the invention has the advantages of high styrene structural unit content, moderate block styrene content, lower 1, 2-structural unit content and good compatibility with high cis-polybutadiene rubber, and when the styrene butadiene rubber is compounded with the high cis-polybutadiene rubber to be used as a sole material, the sole material with good transparency, cold resistance and wet skid resistance can be obtained.
As described above, the second aspect of the present invention provides a process for producing a styrene-butadiene rubber according to the first aspect, which comprises:
(1) in a nonpolar hydrocarbon solvent, in the presence of a structure regulator and an initiator, under the condition of initiating polymerization reaction, carrying out anion solution polymerization reaction on a 1, 3-butadiene monomer and a styrene monomer to obtain a styrene-butadiene rubber polymer solution;
(2) mixing the styrene butadiene rubber polymer solution with water, carbon dioxide, an antioxidant and a dispersant in sequence;
wherein, in the step (1), the structure regulator is selected from at least one of tetrahydrofuran, tetrahydrofurfuryl ethyl ether, tetrahydrofurfuryl butyl ether, N-2-methyl-tetrahydrofurfuryl amine and 2, 2-bis (2-tetrahydrofuryl) propane;
the conditions for initiating the polymerization are at least: the initiation temperature is 35-55 ℃; the conditions of the anionic solution polymerization are at least as follows: the maximum polymerization temperature is 90-110 ℃.
According to the present invention, the method is capable of obtaining the styrene-butadiene rubber according to the first aspect of the present invention, and for this reason the method is defined as a method capable of obtaining the styrene-butadiene rubber according to the present invention.
In the present invention, the inventors have found that the initiation temperature and the maximum polymerization temperature are critical, and that when the initiation temperature is too low (e.g., below 35 ℃), the weight ratio of block styrene to non-block styrene content is below the targeted lower limit; when the initiation temperature is too high (e.g., above 55 ℃), the control of the maximum polymerization temperature is difficult, and the weight ratio of the block styrene to the non-block styrene content is higher than the target upper limit. And when the maximum polymerization temperature is too low (e.g., the maximum polymerization temperature is less than 90 ℃), the weight ratio of the block styrene to the non-block styrene content is less than the target lower limit; when the maximum polymerization temperature is too high (e.g., the maximum polymerization temperature is greater than 110 ℃), the weight ratio of block styrene to non-block styrene content is above the upper target limit.
In order to obtain styrene-butadiene rubber with better performance, preferably, in the step (1), the conditions for initiating the polymerization reaction at least satisfy the following conditions: the initiation temperature is 40-50 deg.C, more preferably 40-49 deg.C.
In order to obtain styrene-butadiene rubber with better performance, preferably, in the step (1), the conditions of the anionic solution polymerization reaction at least satisfy the following conditions: the maximum polymerization temperature is 95 to 105 ℃ and more preferably 95 to 100 ℃.
Preferably, in step (1), the non-polar hydrocarbon solvent is selected from at least one of alkane solvents including naphthenic solvents.
More preferably, the non-polar hydrocarbon solvent is selected from at least one of cyclohexane, cyclopentane, n-pentane, n-hexane, n-heptane and isooctane.
In the present invention, in the step (1), the weight ratio of the amount of the nonpolar hydrocarbon solvent to the total amount of the 1, 3-butadiene monomer and the styrene monomer is 100: 10-30.
Preferably, in step (1), the styrene monomer and the 1, 3-butadiene monomer are used in a weight ratio of 0.65 to 1.05: 1, more preferably 0.75 to 0.95: 1.
according to the present invention, in the anionic solution polymerization reaction, the monomer is converted to nearly 100% by weight, that is, the total amount of the styrene monomer and the 1, 3-butadiene monomer is substantially the same as the dry weight of the styrene-butadiene rubber in the resulting styrene-butadiene rubber polymer solution.
In order to better control the structural parameters of the styrene-butadiene rubber, particularly the content of the block styrene structural units and the non-block styrene structural units, and the content weight ratio of the 1, 2-structural units to the 1, 4-structural units in the styrene-butadiene rubber, preferably, in the step (1), the structure regulator is tetrahydrofuran and/or tetrahydrofurfuryl ethyl ether.
According to a preferred embodiment of the present invention, the structure-regulating agent is tetrahydrofuran, and the tetrahydrofuran is used in an amount of 11 to 19g based on 1kg of the total amount of the 1, 3-butadiene monomer and the styrene monomer. Namely, the weight ratio of the total usage amount of the 1, 3-butadiene monomer and the styrene monomer to the usage amount of the tetrahydrofuran is 1000: 11-19.
According to another preferred embodiment of the present invention, the structural regulator is tetrahydrofurfurylethyl ether, and the amount of tetrahydrofurfurylethyl ether used is 4 to 7g, based on 10kg of the total amount of the 1, 3-butadiene monomer and the styrene monomer, i.e. the weight ratio of the total amount of the 1, 3-butadiene monomer and the styrene monomer to the amount of tetrahydrofurfurylethyl ether is 10000: 4-7.
Preferably, the initiator is selected from at least one of n-butyllithium, sec-butyllithium, iso-butyllithium and tert-butyllithium, preferably n-butyllithium and/or sec-butyllithium, more preferably n-butyllithium.
Preferably, in the step (1), the amount of the initiator is 0.05 to 0.09g based on 100g of the total amount of the 1, 3-butadiene monomer and the styrene monomer.
In order to obtain better solvent removal effect and obtain better performance of styrene-butadiene rubber, in the step (2), the weight ratio of the water to the styrene-butadiene rubber polymer solution based on the styrene-butadiene rubber contained in the water is preferably 1-10: 1, more preferably 4 to 8: 1.
preferably, in the step (2), the molar ratio of the carbon dioxide to the initiator is 0.6-3: 1.
preferably, in the step (2), the antioxidant is selected from at least one of hindered phenols, and more preferably, octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (antioxidant 1076).
Preferably, in the step (2), the weight ratio of the antioxidant to the styrene-butadiene rubber polymer solution based on the styrene-butadiene rubber contained therein is 0.002-0.006: 1, preferably 0.003 to 0.005: 1.
according to a preferred embodiment of the present invention, in the step (2), the dispersant is a mixture of polyoxyethylene alkyl ether and calcium hydroxide.
Preferably, in the step (2), the dispersant is a mixture of polyoxyethylene alkyl ether and calcium hydroxide, and the content weight ratio of the polyoxyethylene alkyl ether to the calcium hydroxide in the dispersant is 1-9: 1, for example, the weight ratio of the polyoxyethylene alkyl ether to the calcium hydroxide is 5:5, 6:4, 7:3, 8:2, 9: 1.
Preferably, in the step (2), the weight ratio of the dispersant to the styrene-butadiene rubber polymer solution based on the styrene-butadiene rubber contained therein is 2 to 10: 10000.
preferably, step (1) and step (2) are each independently carried out under a protective atmosphere.
Preferably, the protective atmosphere is provided by at least one substance selected from nitrogen and an inert gas. More preferably, the protective atmosphere is provided by at least one substance selected from the group consisting of nitrogen, helium, and argon.
In the present invention, the apparatus for carrying out the method is not particularly limited, and the polymerization can be carried out by using an apparatus for carrying out the polymerization reaction which is conventionally used in the art.
According to a preferred embodiment of the present invention, the method is performed in a polymerization reactor, wherein the nonpolar hydrocarbon solvent, the 1, 3-butadiene monomer and the styrene monomer are added from a polymerization line, the initiator and the structure modifier are added from the top of a polymerization vessel by using an injector, and after the polymerization is completed, the coagulation drying treatment is performed by using steam to obtain the styrene-butadiene rubber.
In the method according to the second aspect of the present invention, in order to extract the styrene-butadiene rubber from the reaction product mixed with the dispersant, a post-treatment operation step known in the art of subjecting the reaction product to a steam coagulation treatment to remove a solvent, and drying to remove water, etc. may be further included, and the present invention is not particularly limited to this specific operation, and may be performed in an operation manner existing in the art, and a person skilled in the art should not be construed as limiting the present invention.
As mentioned above, the third aspect of the present invention provides the use of the styrene-butadiene rubber of the first aspect in the preparation of shoe materials.
The present invention has no particular limitation on the specific operation of the application, and can be performed by using the method for preparing the shoe sole by using the styrene butadiene rubber existing in the art, for example, the shoe sole is prepared by compounding the styrene butadiene rubber and the high cis-polybutadiene rubber to form a composite material, which is not described in detail in the present invention, and the present invention is described in detail hereinafter as a specific operation, and those skilled in the art should not understand the limitation of the present invention.
The present invention will be described in detail below by way of examples.
In the following examples, all the raw materials used are commercially available ones unless otherwise specified.
Non-polar hydrocarbon solvent: cyclohexane, purchased from national reagent company, with a purity of > 99.9% by weight, and molecular weight sieves soaked for 15 days with a water content of less than 5 ppm;
styrene monomer: polymer grade, yanshan petrochemical;
1, 3-butadiene monomer: polymer grade, yanshan petrochemical;
initiator: n-butyl lithium (Li), 100ml specification, 1.6 mol.L from carbofuran reagent-1Cyclohexane solution, diluted to 0.4 mol. L-1A cyclohexane solution;
a structure regulator: tetrahydrofuran (THF), available from carbofuran reagents, 500g scale, chromatographically pure; tetrahydrofurfuryl Ethyl ether (ETE), available from carbofuran reagent, 500g, analytically pure, diluted to 0.1 mol.L-1A cyclohexane solution; 2, 2-bis (2-tetrahydrofuryl) propane (DTHFP) available from carbofuran reagent, Inc., 500g specification, analytically pure; diethylene glycol Dimethyl Ether (DEDM) national reagent, Inc., 500g standard, analytically pure;
antioxidant: antioxidant 1076, available from inokay reagent, inc;
dispersing agent: examples 1-12 are combinations of polyoxyethylene alkyl ether and calcium hydroxide (8: 1 polyoxyethylene alkyl ether to calcium hydroxide by weight) and example 13 is sodium oleate, available from qingkaihuafeng reagent, inc.
In the following examples, reference is made to the properties of styrene-butadiene rubber as measured by the foregoing methods.
The wet skid resistance of the shoe material is as follows: the measurement is carried out by adopting a DMA-2980 type viscoelastic spectrometer of TA company of America, wherein the frequency is 2Hz, the heating rate is 5 ℃/min, the temperature is increased from minus 120 ℃ to minus 100 ℃, and the size of a sample is 40mm multiplied by 5mm multiplied by 1 mm.
In the following examples, the experimental set-up and the process involved are as follows:
the method comprises the steps of carrying out polymerization in a 5L polymerization reactor, wherein a solvent, a 1, 3-butadiene monomer and a styrene monomer are added from a polymerization pipeline, an initiator and a structure regulator are added from the top of a polymerization kettle by an injector, transferring the polymerization kettle to a termination kettle after the polymerization is finished, adding carbon dioxide and water from the pipeline, adding an antioxidant and a dispersant in designed amount from the top of the termination kettle by the injector after the termination is finished, and then carrying out steam condensation drying treatment to obtain the styrene-butadiene rubber.
Example 1
This example illustrates styrene-butadiene rubber of the present invention and its preparation.
(1) Under the protection of nitrogen, adding a cyclohexane solvent and a structure regulator (types and dosage are shown in table 1) into a 5L polymerization reactor, controlling the initiation temperature to be 45 ℃, adding an initiator (n-butyllithium, dosage is shown in table 1) into the reactor, carrying out anionic solution polymerization on a 1, 3-butadiene monomer and a styrene monomer (dosage is shown in table 1), controlling the maximum polymerization temperature of the polymerization reaction to be 101 ℃, and obtaining a styrene butadiene rubber polymer solution, wherein the content of styrene butadiene rubber in the styrene butadiene rubber polymer solution is 15.1 wt%;
(2) after the polymerization reaction is completed, the styrene butadiene rubber polymer solution is sequentially mixed with water, carbon dioxide, an antioxidant 1076 and a dispersant (the combination of polyoxyethylene alkyl ether and calcium hydroxide) (the using amounts of the water, the carbon dioxide, the antioxidant 1076 and the dispersant are shown in table 2), then steam coagulation drying is carried out to obtain styrene butadiene rubber, and the structure and performance measurement is carried out, and the result is shown in table 3.
In the other examples, a similar process to that of example 1 was carried out except that the reaction conditions and/or the amounts of the reaction raw materials used were different from those of example 1, as shown in tables 1 and 2, respectively, to obtain styrene-butadiene rubbers, and the results of the structure and properties were measured, as shown in table 3.
Comparative example
Comparative example styrene-butadiene rubbers were obtained and subjected to structure and property measurements, respectively, as shown in Table 3, in a similar manner to example 1 except that the reaction conditions and/or the amounts of the reaction raw materials used were different from those of example 1, as shown in tables 1 and 2.
TABLE 1
Note: the amounts used in table 1 are all based on pure compound.
TABLE 2
| Numbering | Amount of water/g | Amount of carbon dioxide/mmol | Antioxidant 1076 dosage/g | Amount of dispersant used per gram |
| Example 1 | 2500 | 6.5 | 1.6 | 0.25 |
| Example 2 | 2500 | 6.5 | 1.6 | 0.25 |
| Example 3 | 2500 | 6.5 | 1.6 | 0.25 |
| Example 4 | 2500 | 6.5 | 1.6 | 0.25 |
| Example 5 | 2500 | 6.5 | 1.6 | 0.25 |
| Example 6 | 2500 | 6.5 | 1.6 | 0.25 |
| Example 7 | 2500 | 6.5 | 1.6 | 0.25 |
| Example 8 | 2500 | 6.5 | 1.6 | 0.25 |
| Example 9 | 2500 | 6.5 | 1.6 | 0.25 |
| Example 10 | 2500 | 6.5 | 1.6 | 0.25 |
| Example 11 | 2500 | 6.5 | 1.6 | 0.25 |
| Example 12 | 2500 | 6.5 | 1.6 | 0.25 |
| Example 13 | 2500 | 6.5 | 1.6 | 0.25 |
| Comparative example 1 | 2500 | 6.5 | 1.6 | 0.25 |
| Comparative example 2 | 2500 | 0 | 1.6 | 0.25 |
| Comparative example 3 | 2500 | 6.5 | 1.6 | 0 |
| Comparative example 4 | 2500 | 6.5 | 1.6 | 0.25 |
Note: the amounts used in table 2 are all based on pure compound.
TABLE 3
Note: in Table 3, Mn/104Represents the number average molecular weight of styrene-butadiene rubber; Mw/Mn represents the molecular weight distribution index of styrene-butadiene rubber;
PB-1, 2% represents the content of 1, 2-structural units, in% by weight, based on the total weight of butadiene structural units in the styrene-butadiene rubber;
PB-1,2/PB-1,4 represents the content weight ratio of 1, 2-structural units to 1, 4-structural units in styrene butadiene rubber;
st% represents the content of styrene structural units in styrene-butadiene rubber, based on the total weight of styrene-butadiene rubber;
St/Bd represents the content weight ratio of a styrene structural unit to a butadiene structural unit in styrene-butadiene rubber;
st-block% represents the content of a block styrene structural unit in styrene-butadiene rubber, based on the total weight of styrene-butadiene rubber, in wt%;
St-block/non-St-block represents the content weight ratio of the block styrene structural unit to the non-block styrene structural unit in the styrene-butadiene rubber;
the color in the remark refers to the color of styrene butadiene rubber, the white represents that the colloidal particle dispersibility is good and the metal residue is low in the gelation process; the yellow color indicates that the rubber particles in the rubber have poor dispersity, the catalyst has residue and is difficult to terminate, and the non-terminated active species and the antioxidant have color reaction.
As can be seen from the above, the styrene-butadiene rubber prepared by the invention has high styrene content, moderate block styrene structure content, lower 1, 2-structural unit content and moderate Mooney viscosity, and is suitable for being used as a sole material with higher requirements on wet skid resistance.
Test example 1
The test example is used for illustrating the application of the styrene butadiene rubber prepared by the invention in the transparent sole material.
A composite material of the styrene-butadiene rubber of example 1 and high-cis polybutadiene rubber BR9000 (wherein the weight ratio of the styrene-butadiene rubber to the high-cis polybutadiene rubber BR9000 is 3:7) was added with white carbon black and benzoyl peroxide (wherein the amount of white carbon black was 20 parts by weight and the amount of benzoyl peroxide was 0.1 part by weight per 100 parts by weight of the styrene-butadiene rubber), and vulcanization was carried out at 150 ℃ to obtain a shoe sole material S1, the performance results of which are shown in Table 4.
The other test examples were conducted in a similar manner to test example 1 except that the type of styrene-butadiene rubber used was different from test example 1.
Specifically, the same weight of styrene-butadiene rubber prepared in examples 2 to 13 was used in place of the styrene-butadiene rubber in test example 1, and the rest was the same as in test example 1 to obtain sole materials, and the properties of the obtained sole materials were measured, respectively, and the specific results are shown in table 4.
Comparative test example
In a similar manner to test example 1 except that the kind of styrene-butadiene rubber used was different from test example 1.
Specifically, the styrene-butadiene rubbers prepared in comparative examples 1 to 4 were used in place of the styrene-butadiene rubber in test example 1 in the same weight, and the remainder was the same as in test example 1 to obtain sole materials, and the properties of the obtained sole materials were respectively tested, and the specific results are shown in table 4.
TABLE 4
| Numbering | Transparency of | Wet skid resistance (Tan. delta., 0 ℃ C.) |
| Test example 1 | A | 0.4716 |
| Test example 2 | A | 0.4823 |
| Test example 3 | A | 0.4754 |
| Test example 4 | A | 0.4619 |
| Test example 5 | A | 0.4658 |
| Test example 6 | A | 0.3973 |
| Test example 7 | B | 0.3726 |
| Test example 8 | B | 0.4637 |
| Test example 9 | C | 0.3604 |
| Test example 10 | C | 0.4482 |
| Test example 11 | C | 0.4765 |
| Test example 12 | C | 0.3368 |
| Test example 13 | C | 0.4724 |
| Comparative test example 1 | E | 0.5024 |
| Comparative test example 2 | E | 0.4917 |
| Comparative test example 3 | D | 0.2984 |
| Comparative test example 4 | D | 0.2728 |
In the present invention, the transparency was evaluated by the criteria shown in the following table.
Table 5: transparency of
The results show that the styrene-butadiene rubber provided by the invention has good compatibility with the high-cis polybutadiene rubber, and the sole material prepared by compounding the styrene-butadiene rubber and the high-cis polybutadiene rubber BR9000 has excellent transparency and good wet skid resistance.
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 (16)
1. Styrene-butadiene rubber, characterized in that the weight ratio of styrene structural units to butadiene structural units in the styrene-butadiene rubber is 0.65-1.05: 1; the weight ratio of the 1, 2-structural unit to the 1, 4-structural unit in the styrene butadiene rubber is 0.33-0.54: 1; the content weight ratio of the block styrene structural unit to the non-block styrene structural unit in the styrene-butadiene rubber is 0.27-0.57: 1; and the number of the first and second groups,
the number average molecular weight of the styrene butadiene rubber is 8-11 ten thousand; the molecular weight distribution index of the styrene butadiene rubber is 1.0-1.2; the Mooney viscosity ML of the styrene-butadiene rubber at 100 DEG C1+4Is 40-60.
2. The styrene-butadiene rubber according to claim 1, wherein the content weight ratio of the styrene structural unit to the butadiene structural unit in the styrene-butadiene rubber is from 0.75 to 0.95: 1;
preferably, the content weight ratio of the 1, 2-structural unit to the 1, 4-structural unit in the styrene-butadiene rubber is 0.36-0.5: 1;
preferably, the content weight ratio of the block styrene structural units to the non-block styrene structural units in the styrene-butadiene rubber is 0.32-0.47: 1.
3. the styrene-butadiene rubber according to claim 1 or 2, wherein the number average molecular weight of the styrene-butadiene rubber is 8.5 to 10.5 ten thousand;
preferably, the styrene-butadiene rubber has a molecular weight distribution index of 1.0 to 1.1;
preferably, the styrene-butadiene rubber has a Mooney viscosity ML at 100 ℃1+4Is 43-53.
4. A method for preparing styrene-butadiene rubber according to any one of claims 1 to 3, comprising:
(1) in a nonpolar hydrocarbon solvent, in the presence of a structure regulator and an initiator, under the condition of initiating polymerization reaction, carrying out anion solution polymerization reaction on a 1, 3-butadiene monomer and a styrene monomer to obtain a styrene-butadiene rubber polymer solution;
(2) mixing the styrene butadiene rubber polymer solution with water, carbon dioxide, an antioxidant and a dispersant in sequence;
wherein, in the step (1), the structure regulator is selected from at least one of tetrahydrofuran, tetrahydrofurfuryl ethyl ether, tetrahydrofurfuryl butyl ether, N-2-methyl-tetrahydrofurfuryl amine and 2, 2-bis (2-tetrahydrofuryl) propane;
the conditions for initiating the polymerization are at least: the initiation temperature is 35-55 ℃; the conditions of the anionic solution polymerization are at least as follows: the maximum polymerization temperature is 90-110 ℃.
5. The method according to claim 4, wherein in step (1), the conditions for initiating the polymerization reaction at least satisfy: the initiation temperature is 40-50 ℃;
preferably, in step (1), the conditions of the anionic solution polymerization reaction at least satisfy: the maximum polymerization temperature is 95-105 ℃.
6. The process according to claim 4 or 5, wherein, in step (1), the non-polar hydrocarbon solvent is selected from at least one of n-pentane, cyclopentane, n-hexane, cyclohexane, n-heptane and isooctane;
preferably, in step (1), the styrene monomer and the 1, 3-butadiene monomer are used in a weight ratio of 0.65 to 1.05: 1, preferably 0.75 to 0.95: 1.
7. the method according to any one of claims 4 to 6, wherein, in step (1), the structure-regulating agent is tetrahydrofuran and/or tetrahydrofurfuryl ethyl ether.
8. The method according to claim 7, wherein the structure-regulating agent is tetrahydrofuran, and the tetrahydrofuran is used in an amount of 11 to 19g, based on 1kg of the total amount of the 1, 3-butadiene monomer and the styrene monomer.
9. The method according to claim 7, wherein the structure-regulating agent is tetrahydrofurfurylethyl ether, and the amount of the tetrahydrofurfurylethyl ether is 4-7g, based on 10kg of the total amount of the 1, 3-butadiene monomer and the styrene monomer.
10. The process of any one of claims 4-9, wherein, in step (1), the initiator is selected from at least one of n-butyllithium, sec-butyllithium, iso-butyllithium, and tert-butyllithium;
preferably, in the step (1), the amount of the initiator is 0.05 to 0.09g based on 100g of the total amount of the 1, 3-butadiene monomer and the styrene monomer.
11. The process according to any one of claims 4 to 10, wherein in the step (2), the weight ratio of the water to the styrene-butadiene rubber polymer solution based on the styrene-butadiene rubber contained therein is from 1 to 10: 1, preferably 4 to 8: 1.
12. the process according to any one of claims 4 to 11, wherein in step (2), the molar ratio of the carbon dioxide to the initiator is from 0.6 to 3: 1.
13. the method according to any one of claims 4 to 12, wherein, in step (2), the antioxidant is selected from at least one of hindered phenols;
preferably, the antioxidant is n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate;
preferably, in the step (2), the weight ratio of the antioxidant to the styrene-butadiene rubber polymer solution based on the styrene-butadiene rubber contained therein is 0.002-0.006: 1.
14. the method according to any one of claims 4 to 13, wherein, in the step (2), the dispersant is a mixture of polyoxyethylene alkyl ether and calcium hydroxide;
preferably, in the dispersant, the content weight ratio of the polyoxyethylene alkyl ether to the calcium hydroxide is 1 to 9: 1;
preferably, in the step (2), the dispersant is used in an amount of 2 to 10g, relative to 10kg of the styrene-butadiene rubber polymer solution, wherein the weight of the styrene-butadiene rubber polymer solution is based on the styrene-butadiene rubber contained therein.
15. The method of any one of claims 4-14, wherein step (1) and step (2) are each independently performed under a protective atmosphere;
preferably, the protective atmosphere is provided by at least one substance selected from the group consisting of nitrogen, helium, and argon.
16. Use of the styrene-butadiene rubber according to any one of claims 1 to 3 for the production of shoe materials.
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