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CN114716598B - Preparation method of butadiene-isoprene copolymer, butadiene-isoprene copolymer and tread rubber - Google Patents

Preparation method of butadiene-isoprene copolymer, butadiene-isoprene copolymer and tread rubber Download PDF

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CN114716598B
CN114716598B CN202110002352.0A CN202110002352A CN114716598B CN 114716598 B CN114716598 B CN 114716598B CN 202110002352 A CN202110002352 A CN 202110002352A CN 114716598 B CN114716598 B CN 114716598B
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butadiene
isoprene
rubber
copolymer
butyl
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CN114716598A (en
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王润国
侯舜皓
张立群
鲁建民
韩丙勇
辛明泽
赵帅男
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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    • 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
    • C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F136/02—Homopolymers 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
    • C08F136/04—Homopolymers 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
    • C08F136/08—Isoprene
    • 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
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/04—Polymerisation in solution
    • C08F2/06—Organic solvent
    • 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
    • C08F236/06—Butadiene
    • 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
    • C08F236/08—Isoprene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00—Compositions of natural rubber
    • 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
    • C08L9/06—Copolymers with styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
    • Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction 

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  • 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)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Tires In General (AREA)

Abstract

The invention discloses a preparation method of a butadiene-isoprene copolymer, the butadiene-isoprene copolymer and tread rubber. The preparation method comprises the following steps: (1) Adding cyclohexane, isoprene and butadiene into a polymerization kettle, and uniformly stirring; (2) Adding n-butyllithium and a structure regulator, and reacting while stirring at 60-80 ℃; (3) terminating the reaction by using a polymerization inhibitor after the reaction is finished; washing and drying to obtain polyisoprene and polyisoprene-butadiene copolymer. The butadiene-isoprene copolymer elastomer has a random structure, does not crystallize at low temperature, and can still keep high elasticity at low temperature. The butadiene-isoprene copolymer can be used in the formula of winter tyre tread rubber to improve the cold resistance of the rubber.

Description

Preparation method of butadiene-isoprene copolymer, butadiene-isoprene copolymer and tread rubber
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a preparation method of a butadiene-isoprene copolymer, the butadiene-isoprene copolymer and tread rubber.
Background
With the development of technology, the requirements of rubber materials are increasingly stringent. In the field of winter tyres, tread rubber materials are required to have excellent cold resistance. The cold resistance of the rubber material is mainly determined in two aspects: the magnitude of the glass transition temperature and whether crystallization occurs at low temperatures. The low glass transition temperature (Tg) and the absence of crystallization at low temperatures indicate that the rubber material is excellent in cold resistance.
Winter tyres are widely used in cold areas because of their ability to better maintain the steering of the vehicle over ice and snow covered surfaces. The excellent anti-ice performance is an important indicator for measuring the performance of winter tyres, and the anti-ice performance of tyres has a close relationship with the composition of the tread band material of winter tyres.
At present, the common tread rubber materials mainly comprise styrene-butadiene rubber, natural rubber and butadiene rubber, but because the Tg of the styrene-butadiene rubber is higher, the natural rubber and the butadiene rubber are easy to crystallize at low temperature, and the anti-ice performance is poor, so that the rubber is not suitable for the tread rubber materials of winter tyres.
Therefore, developing a new tread rubber material is a technical problem to be solved at present.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method of a butadiene-isoprene copolymer, the butadiene-isoprene copolymer and tread rubber.
Since the butyl-pentyl copolymer itself has a low glass transition temperature, the factor determining the low temperature resistance is whether crystallization occurs at low temperature. The crystallinity of rubber is determined by the structural randomness of the rubber material. The randomness is the randomness degree of the butadiene and isoprene copolymer on the copolymerization main chain, and the symmetry and regularity of the butadiene-isoprene copolymer are reduced by a proper synthesis method, so that the crystallization capability of the copolymer is reduced or even completely lost, and the low-temperature cold-resistant performance of the material is improved.
The butadiene-isoprene copolymer elastomer disclosed by the invention is random in structure, does not crystallize at low temperature, and can be applied to a low-temperature-resistant rubber composition of winter tire tread rubber. The invention mainly adopts a method of anionic solution polymerization to inhibit the crystallization behavior of the butadiene-isoprene copolymer by adopting a structure regulation method from the aspect of a base material, and synthesizes the butadiene-isoprene copolymer with cis-1, 4, trans-1, 4, 3, 4-structure, and the copolymer can still keep high elasticity at low temperature. The use of a butadiene-isoprene copolymer in the formulation of a winter tyre tread band can improve the cold resistance of the rubber.
The invention aims at providing a preparation method of a butadiene-isoprene copolymer.
The method comprises the following steps:
(1) Adding cyclohexane, isoprene and butadiene into a polymerization kettle, and uniformly stirring;
(2) N-butyllithium and a structure regulator, and reacting while stirring at 60-80 ℃;
The structure regulator is tetrahydrofuran, diethyl ether, anisole, triethylamine or tetramethyl vinyl diamine;
(3) After the reaction is finished, stopping the reaction by using a polymerization inhibitor; washing and drying to obtain polyisoprene and polyisoprene-butadiene copolymer;
The polymerization inhibitor is methanol or ethanol.
In a preferred embodiment of the present invention,
In the step (1), the step of (a),
The isoprene accounts for 50-100 wt%, preferably 50-less than 100wt%, more preferably 50-80wt% of the total mass of the isoprene and butadiene monomers;
butadiene accounts for 0-50wt%, preferably more than 0-50wt%, more preferably 20% -50wt% of the total mass of isoprene and butadiene monomers;
In a preferred embodiment of the present invention,
In the step (2), the step of (C),
The butyl lithium accounts for 0.01 to 5 weight percent of the total mass of the isoprene and butadiene monomers;
The consumption of the structure regulator accounts for 4-6wt% of the total mass of the isoprene and butadiene monomers;
In a preferred embodiment of the present invention,
In the step (2), the step of (C),
The butyl lithium accounts for 0.01 to 3 weight percent of the total mass of the isoprene and butadiene monomers;
the consumption of the structure regulator accounts for 4-6wt% of the total mass of the isoprene and butadiene monomers.
In a preferred embodiment of the present invention,
In the step (2), the reaction time is 30-60min; and/or the number of the groups of groups,
The structure regulator of the invention is tetrahydrofuran, diethyl ether, anisole, triethylamine or tetramethyl vinyl diamine. The structure regulator can regulate the content of butadiene and isoprene chain segment structure in the product, and has best low temperature resistance when the content of cir-1, 4-in the butadiene and isoprene chain segments is between 30% and 70%. The specific results are shown in a nuclear magnetic spectrum chart of FIG. 1 and a low-temperature crystallization chart of the expanding agent of FIG. 2. Wherein in FIG. 2, the higher the ordinate, the better the crystallization property, the worse the cold resistance, and wherein the cold resistance of commercially available high cis-isoprene is the worst, the better the cold resistance of Ding Wujiao adjusted by the structure regulator, due to the increase of the crystallization density of the rubber, the decrease of the volume.
Another object of the present invention is to provide a butyl-pentyl copolymer.
The butyl-pentyl copolymer comprises: isoprene structural units and butadiene structural units;
The content of the isoprene structural unit is 50-100 wt% based on 100% of the total mass of the isoprene structural unit and the butadiene structural unit in the butadiene-isoprene copolymer; preferably 50% to less than 100%;
Butadiene structural unit content is 0-50wt%; preferably greater than 0 to 50%.
The number average molecular weight of the butyl-pentyl copolymer is 10-20 ten thousand; the molecular weight distribution is 1.0-3.0.
In a preferred embodiment of the present invention,
The content of the isoprene structural unit is 50-80 wt% based on 100% of the total mass of the isoprene structural unit and the butadiene structural unit in the butadiene-isoprene copolymer;
The butadiene structural unit content is 20-50 wt%.
The invention further provides tread rubber.
The tread rubber is prepared from the following raw materials in parts by weight:
100 parts by weight of the total weight of the rubber raw rubber and the butyl-pentyl copolymer; wherein, the butadiene-pentane copolymer is 1 to 50 weight parts, preferably 10 to 30 weight parts;
The rubber raw rubber is one or more selected from natural rubber raw rubber, styrene-butadiene rubber raw rubber and butadiene rubber raw rubber;
The liquid rubber is liquid rubber containing butadiene chain segments; liquid isoprene rubber and liquid styrene-butadiene rubber are preferred.
The liquid rubber is used as a compatilizer, so that the compatibility can be improved, and the processability and mechanical properties of the tread rubber are improved. Wherein the NR/BR system is mixed with commercial liquid isoprene rubber, and the SBR/BR system is mixed with commercial liquid styrene butadiene rubber to improve the compatibility.
The reinforcing auxiliary agent is carbon black, or white carbon black and a coupling agent; the coupling agent is silicon 69 and/or PEG4000 (polyethylene glycol 4000), and the dosage of the coupling agent can be determined by a technician according to practical situations.
The processing aid may be any processing aid commonly used in the art, such as: zinc oxide and stearic acid, and may further include an anti-aging agent and microcrystalline wax; the skilled person can determine this according to the actual situation.
The vulcanizing agent may be a vulcanizing agent commonly used in the art, such as: sulfur; the amount thereof is a conventional amount, and in the present invention, it may be preferably 0.5 to 5 parts by weight, more preferably 1 to 3 parts by weight.
The accelerator may be any accelerator commonly used in the art, such as: accelerator NS, accelerator D, accelerator CZ; the amount thereof is a conventional amount, and in the present invention, it may be preferably 1 to 8 parts by weight, more preferably 2 to 5 parts by weight.
The invention provides a preparation method of tread rubber.
The method comprises the following steps:
and mixing and vulcanizing the components according to the amount to obtain the tread rubber.
The method comprises the following specific steps:
step 1, plasticating raw rubber;
step 2, mixing the random butyl-pentyl copolymer, a compatilizer and a reinforcing auxiliary agent to obtain a filling system;
and 3, adding a processing aid into the raw rubber plasticated in the step 1, and then mixing the raw rubber on an open mill for 5 minutes.
And step 4, finally adding the accelerator and the vulcanizing agent, mixing for 8min on an open mill, and carrying out thin-pass for 3-5 times.
In a preferred embodiment, in step 1, when two or more kinds of raw rubber are used, after the raw rubber is plasticated, the various plasticated raw rubber is mixed and then subjected to an open mill, preferably by passing through a roll 3 to 5 times.
In a preferred embodiment, in step 3, the mill treatment is carried out for 0.5 to 6 minutes, preferably 1 to 5 minutes, more preferably 1 to 2 minutes.
In the invention, butadiene and isoprene are used as main monomers, and the structure is controlled by an anionic solution polymerization method to ensure that the synthesized polymer is a random copolymer, so that the crystallization behavior of the polymer at low temperature can be inhibited, and the cold resistance of the polymer is improved, so that the polymer can be applied to tread rubber materials of winter tyres. The incorporation of a certain butadiene segment can lower the glass transition temperature of the polymer, thereby further improving the cold resistance.
Compared with the prior art, the invention has the following beneficial effects:
(1) The low-temperature-resistant random butadiene-isoprene copolymer improves the processing performance and the vulcanized rubber performance of the rubber material;
(2) The low temperature resistant random butyl-pentyl copolymer has the structure regulated by anionic polymerization, and is changed into a random copolymer, so that the crystallization behavior at low temperature is inhibited, and the cold resistance is improved.
(3) The low temperature resistant random butyl-pentyl copolymer can be used as a low temperature resistant rubber composition of winter tyre tread rubber;
(4) The low-temperature-resistant random butyl-pentyl copolymer can be used as a compatilizer, and the mechanical property of rubber products is improved.
Drawings
FIG. 1 shows a nuclear magnetic resonance hydrogen spectrum of example 1.
From FIG. 1, it can be seen that the peak at 4.78ppm is derived from the methylene proton of isoprene of 3, 4-structure. Peaks at 5.12ppm are from protons of methylene groups of cis 1, 4-and trans 1, 4-structure isoprene, and peaks at 2.04,1.67,1.56ppm are from protons of cis 1,4-, trans 1,4-,3, 4-structure methyl groups.
Fig. 2 shows nuclear magnetic hydrogen spectra of example 2 and example 3.
It can be seen from FIG. 2 that the peak at 4.78ppm is from the methylene proton of 3, 4-structure isoprene, the peak at 5.12,5.36ppm is from the protons of cis-1, 4-and trans-1, 4-structure isoprene and the methylene proton of butadiene, and the peak at 2.04,1.67,1.56ppm is from the protons of the methyl groups of isoprene and butadiene.
The structure of the composition can be basically determined according to the nuclear magnetic hydrogen spectrogram.
FIG. 3 shows the low temperature crystallization profile of examples 1,2,3 and commercially available high cis-isoprene rubber measured by the expander method at-25 ℃.
Fig. 4 shows stress-strain curves of the tread rubbers obtained in examples 8 to 11 and comparative example 1.
Fig. 5 shows stress-strain curves of the tread rubbers obtained in examples 12 to 16 and comparative example 2.
Fig. 6 shows stress-strain curves of tread rubbers obtained in examples 17 to 20 and comparative example 3.
Fig. 7 shows stress-strain curves of the tread rubbers obtained in examples 21 to 25 and comparative example 4.
Fig. 8 shows compression cold resistance coefficient versus time curves of the tread rubbers obtained in examples 8 to 11 and comparative example 1.
Fig. 9 shows compression cold resistance coefficient versus time curves of the tread rubbers obtained in examples 12 to 16 and comparative example 2.
Fig. 10 shows compression cold resistance coefficient versus time curves of the tread rubbers obtained in examples 17 to 20 and comparative example 3.
Fig. 11 shows compression cold resistance coefficient versus time curves of the tread rubbers obtained in examples 21 to 25 and comparative example 4.
Wherein, the higher the compression cold resistance coefficient is, the better the cold resistance of the rubber is.
Detailed Description
The present invention is described in detail below with reference to the specific drawings and examples, and it is necessary to point out that the following examples are given for further illustration of the present invention only and are not to be construed as limiting the scope of the present invention, since numerous insubstantial modifications and adaptations of the invention to those skilled in the art will still fall within the scope of the present invention.
The raw materials used in the examples are all commercially available.
Example 1: preparation of Low-Wen Dingwu-resistant copolymer
Adding 2L of cyclohexane into an absorption bottle, adding isoprene and butadiene monomers with the molar ratio of 10:0, adding the mixed solution of the isoprene and the butadiene monomers into a treated 5L polymerization kettle, and uniformly stirring.
Finally, n-butyllithium and THF (structure regulator) are added, wherein the dosage of the n-butyllithium is 1.8wt% of the total mass of the monomer, and the dosage of the tetrahydrofuran is 5wt% of the total mass of the monomer. The reaction was stirred at 60℃for 40min. After the reaction, the polymer is stopped by ethanol, coagulated, cyclohexane solution is washed off, and the like, and the polymer is dried in a vacuum drying oven at 50 ℃. Finally obtaining Polyisoprene (PI) raw rubber. Mn=21.7 thousands of calculated product, mw/mn=1.14.
Example 2: preparation of Low-Wen Dingwu-resistant copolymer
Adding 2L of cyclohexane into an absorption bottle, adding isoprene and butadiene monomers in a molar ratio of 8:2, adding the mixed solution of the isoprene and the butadiene monomers into the treated 5L polymerization kettle, and uniformly stirring.
And finally adding n-butyllithium and THF, wherein the dosage of the n-butyllithium is 1.8wt% of the total mass of the monomer, and the dosage of the tetrahydrofuran is 5wt% of the total mass of the monomer. The reaction was stirred at 60℃for 30 minutes. After the reaction, the polymer is stopped by ethanol, coagulated, cyclohexane solution is washed off, and the like, and the polymer is dried in a vacuum drying oven at 50 ℃. Finally, the crude rubber of the butadiene-isoprene copolymer (isoprene: butadiene-8:2) is obtained. Mn=20.6 tens of thousands of calculated products, mw/mn=1.17.
Example 3: preparation of Low-Wen Dingwu-resistant copolymer
Adding 2L of cyclohexane into an absorption bottle, adding isoprene and butadiene monomers with a molar ratio of 5:5, adding the mixed solution of the isoprene and the butadiene monomers into a treated 5L polymerization kettle, and uniformly stirring. The amount of n-butyllithium was 1.8wt% based on the total mass of the monomer, and tetrahydrofuran was 5wt% based on the total mass of the monomer.
The reaction was stirred at the set temperature (60 ℃) for 40min. After the reaction, the polymer is stopped by ethanol, coagulated, cyclohexane solution is washed off, and the like, and the polymer is dried in a vacuum drying oven at 50 ℃. Finally, the crude rubber of the butyl-pentyl copolymer (SPIBP 5:5) is obtained. Mn=19.2 thousands of calculated product, mw/mn=1.14.
Example 4: preparation of Low-Wen Dingwu-resistant copolymer
Adding 2L of cyclohexane into an absorption bottle, adding isoprene and butadiene monomers in a molar ratio of 5:5, adding the mixed solution of the isoprene and the butadiene monomers into the treated 5L polymerization kettle, and uniformly stirring.
Finally, adding n-butyllithium and THF, wherein the dosage of the n-butyllithium is 0.5wt% of the total mass of the monomer, and the dosage of the tetrahydrofuran is 4wt% of the total mass of the monomer. The reaction was stirred at 80℃for 30 minutes. After the reaction, the polymer is stopped by ethanol, coagulated, cyclohexane solution is washed off, and the like, and the polymer is dried in a vacuum drying oven at 50 ℃. Finally, the crude rubber of the butadiene-isoprene copolymer (isoprene: butadiene-5:5) is obtained. Mn=14.3 ten thousand of calculated product, mw/mn=1.56.
Example 5: preparation of Low-Wen Dingwu-resistant copolymer
Adding 2L of cyclohexane into an absorption bottle, adding isoprene and butadiene monomers in a molar ratio of 5:5, adding the mixed solution of the isoprene and the butadiene monomers into the treated 5L polymerization kettle, and uniformly stirring.
And finally adding n-butyllithium and THF, wherein the dosage of the n-butyllithium accounts for 3wt% of the total mass of the monomer, and tetrahydrofuran accounts for 6wt% of the total mass of the monomer. The reaction was stirred at 60℃for 40 minutes. After the reaction, the polymer is stopped by ethanol, coagulated, cyclohexane solution is washed off, and the like, and the polymer is dried in a vacuum drying oven at 50 ℃. Finally, the crude rubber of the butadiene-isoprene copolymer (isoprene: butadiene-5:5) is obtained. Mn=30.7 tens of thousands of calculated products, mw/mn=1.67.
Example 6: preparation of Low-Wen Dingwu-resistant copolymer
Adding 2L of cyclohexane into an absorption bottle, adding isoprene and butadiene monomers in a molar ratio of 5:5, adding the mixed solution of the isoprene and the butadiene monomers into the treated 5L polymerization kettle, and uniformly stirring.
And finally adding n-butyllithium and diethyl ether, wherein the dosage of the n-butyllithium accounts for 1.8 weight percent of the total mass of the monomer, and the tetrahydrofuran accounts for 5 weight percent of the total mass of the monomer. The reaction was stirred at 60℃for 50 minutes. After the reaction, the polymer is stopped by ethanol, coagulated, cyclohexane solution is washed off, and the like, and the polymer is dried in a vacuum drying oven at 50 ℃. Finally, the crude rubber of the butadiene-isoprene copolymer (isoprene: butadiene-5:5) is obtained. Mn=17.8 million of the calculated product, mw/mn=1.43.
Example 7: preparation of Low-Wen Dingwu-resistant copolymer
Adding 2L of cyclohexane into an absorption bottle, adding isoprene and butadiene monomers in a molar ratio of 5:5, adding the mixed solution of the isoprene and the butadiene monomers into the treated 5L polymerization kettle, and uniformly stirring.
And finally adding n-butyllithium and anisole, wherein the dosage of the n-butyllithium accounts for 1.8 weight percent of the total mass of the monomer, and the tetrahydrofuran accounts for 5 weight percent of the total mass of the monomer. The reaction was stirred at 80℃for 50 minutes. After the reaction, the polymer is stopped by ethanol, coagulated, cyclohexane solution is washed off, and the like, and the polymer is dried in a vacuum drying oven at 50 ℃. Finally, the crude rubber of the butadiene-isoprene copolymer (isoprene: butadiene-5:5) is obtained. Mn=15.4 ten thousand of calculated product, mw/mn=1.48.
Examples 8-25 preparation of winter tyre tread bands
(1) Firstly plasticating raw rubber (natural rubber NR, butadiene rubber BR and synthetic butyl-pentyl copolymer), mixing the raw rubber in step 3, and passing through a roller for 4 times on an open mill;
(2) Carbon black, white carbon black and coupling agent (silicon 69 and PEG 4000) were mixed to obtain a filled system.
(3) Mixing for 5 minutes after adding zinc oxide and stearic acid, adding an accelerator and a vulcanizing machine, mixing for 8 minutes, and carrying out thin-pass on an open mill for 3-5 times.
The specific raw material consumption is shown in tables 1-4, wherein the two raw rubber adopted are BR9000 respectively, NR is commercial rubber, and the sum of the weight of the two raw rubber and the weight of the butyl-pentyl copolymer is 100 parts. In tables 1 to 4 below, one table is a preparation lot.
TABLE 1
TABLE 2
TABLE 3 Table 3
TABLE 4 Table 4
Test of mechanical Properties of Experimental examples 8 to 25
Table 5:
shore A hardness Elongation at break% Tensile Strength/MPa
Comparative example 1 54 627 16
Example 8 58 676 19
Example 9 62 654 20
Example 10 56 648 19
Example 11 62 689 19
Table 6:
shore A hardness Elongation at break% Tensile Strength/MPa
Comparative example 2 65 627 16
Example 12 65 652 18
Example 13 66 689 18
Example 14 69 677 18
Example 15 70 861 19
Example 16 72 844 17
Table 7:
shore A hardness Elongation at break% Tensile Strength/MPa
Comparative example 3 65 345 14
Example 17 64 349 15
Example 18 66 402 17
Example 19 64 371 16
Example 20 63 463 18
Table 8:
shore A hardness Elongation at break% Tensile Strength/MPa
Comparative example 4 65 354 15
Example 21 65 373 16
Example 22 66 382 16
Example 23 69 378 17
Example 24 70 468 18
Example 25 72 485 19
1. The tread rubbers obtained in examples 8 to 11 and comparative example 1 in Table 1 were subjected to mechanical properties, and the results are shown in Table 5 and FIG. 4.
2. The tread rubbers obtained in examples 12 to 16 and comparative example 2 in Table 2 were subjected to mechanical properties, and the results are shown in Table 6 and FIG. 5.
3. The mechanical properties of the tread rubbers obtained in examples 17 to 20 and comparative example 3 in Table 3 were measured, and the results are shown in Table 7 and FIG. 6.
4. The tread rubbers obtained in examples 21 to 25 and comparative example 4 in Table 4 were subjected to mechanical property test, and the results are shown in Table 8 and FIG. 7
From the comparison data: compared with comparative examples 1-4 (with no butadiene-isoprene copolymer added), the mechanical property parameters of the invention examples 4-21 are higher than those of comparative examples, and the mechanical property of the rubber material can be improved by mixing the butadiene-isoprene copolymer.
Test of Cold resistance Properties of Experimental examples 8 to 25
1. The cold resistance properties of the tread rubbers obtained in examples 8 to 11 and comparative example 1 in Table 1 were tested, and the results are shown in FIG. 8.
2. The tread rubbers obtained in examples 12 to 16 and comparative example 2 in Table 2 were subjected to cold resistance test, and the results are shown in FIG. 9.
3. The cold resistance test was performed on the tread rubbers obtained in examples 17 to 20 and comparative example 3 in table 3, and the results are shown in fig. 10.
4. The cold resistance test was conducted on the tread rubbers obtained in examples 21 to 25 and comparative example 4 in Table 4, and the results are shown in FIG. 11
As can be seen from fig. 8 to 11, when the tread rubber is mixed into the butyl-pentyl copolymer, the compression cold resistance coefficient thereof increases, representing an improvement in cold resistance. In conclusion, the low-Wen Dingwu-resistant copolymerized elastomer synthesized by adopting the anionic polymerization process has lower glass transition temperature and no crystallization at low temperature, has excellent low-temperature resistance compared with the common tread rubber sizing material sold in the market, and has great development potential in the field of winter tire tread rubber.

Claims (6)

1. The tread rubber containing the butadiene-isoprene copolymer is characterized by being prepared from the following raw materials in parts by weight:
taking the total weight of the rubber raw rubber and the butyl-pentyl copolymer as 100 weight parts, wherein the butyl-pentyl copolymer is 10-50 weight parts;
3-6 parts by weight of liquid rubber;
60-70 parts by weight of reinforcing auxiliary agent; the reinforcing auxiliary agent is carbon black, or white carbon black and a coupling agent;
3-15 parts of a processing aid; the processing aid is zinc oxide and stearic acid;
1-3 parts of vulcanizing agent;
2-5 parts of an accelerator;
the butyl-pentyl copolymer comprises: isoprene structural units and butadiene structural units;
the content of the isoprene structural unit is 50-80 wt% based on 100% of the total mass of the isoprene structural unit and the butadiene structural unit in the butadiene-isoprene copolymer;
The content of butadiene structural units is 20-50 wt%;
the number average molecular weight of the butadiene-isoprene copolymer is 19.2-20 ten thousand; the molecular weight distribution is 1.0-1.14;
the preparation method of the butyl-pentyl copolymer comprises the following steps:
(1) Adding cyclohexane, isoprene and butadiene into a polymerization kettle, and uniformly stirring;
(2) Adding n-butyllithium and a structure regulator, and reacting while stirring at the temperature of 60-80 ℃;
The structure regulator is tetrahydrofuran, diethyl ether, anisole, triethylamine or tetramethyl vinyl diamine;
(3) After the reaction is finished, stopping the reaction by using a polymerization inhibitor; washing and drying to obtain polyisoprene-butadiene copolymer;
The polymerization inhibitor is methanol or ethanol.
2. The tread rubber containing the butadiene-isoprene copolymer according to claim 1, wherein in the step (2), butyl lithium is used in an amount of 0.01wt% to 5wt% based on the total mass of isoprene and butadiene monomers;
the consumption of the structure regulator accounts for 4-6wt% of the total mass of the isoprene and butadiene monomers.
3. The tread rubber containing the butadiene-isoprene copolymer according to claim 2, wherein in the step (2), butyl lithium is used in an amount of 0.01wt% to 3wt% based on the total mass of isoprene and butadiene monomers.
4. The tread rubber comprising a butyl-pentyl copolymer according to claim 1, wherein the reaction time in the step (2) is 30 to 60 minutes.
5. The tread rubber comprising a butadiene-isoprene copolymer as recited in claim 1, wherein said rubber green is selected from one or more of natural rubber green, styrene-butadiene rubber green and butadiene rubber green;
and/or the liquid rubber is a liquid rubber containing butadiene segments.
6. A method for preparing the tread rubber containing the butyl-pentyl copolymer according to claim 1, comprising the steps of: the tread rubber is prepared by mixing and vulcanizing the raw materials according to the weight parts.
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