CN111217941A - Conjugated diene polymer, preparation method thereof and styrene butadiene rubber - Google Patents

Conjugated diene polymer, preparation method thereof and styrene butadiene rubber Download PDF

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CN111217941A
CN111217941A CN201811421689.XA CN201811421689A CN111217941A CN 111217941 A CN111217941 A CN 111217941A CN 201811421689 A CN201811421689 A CN 201811421689A CN 111217941 A CN111217941 A CN 111217941A
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conjugated diene
monomer
diene polymer
structure provided
styrene
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CN111217941B (en
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王妮妮
孙文娟
康新贺
刘辉
王雪
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/34—Introducing sulfur atoms or sulfur-containing groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L15/00—Compositions of rubber derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • 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 

Abstract

The invention relates to the field of rubber processing aids, in particular to a conjugated diene polymer and a preparation method thereof, styrene butadiene rubber and vulcanized rubber. The conjugated diene polymer contains a structure provided by a conjugated diene monomer and an optional structure provided by a monovinylarene monomer, and a molecular chain of the conjugated diene polymer is connected with a side group provided by a modifier. The conjugated diene polymer provided by the invention can well disperse white carbon black and carbon black in styrene butadiene rubber, and the formed vulcanized rubber has low content of large-particle particles, so that the reinforcing effect of the white carbon black and the carbon black is conveniently provided.

Description

Conjugated diene polymer, preparation method thereof and styrene butadiene rubber
Technical Field
The invention relates to the field of rubber processing aids, in particular to a conjugated diene polymer, a preparation method thereof and styrene butadiene rubber.
Background
The white carbon black is used as a reinforcing agent of the tire tread rubber material instead of carbon black, so that the rolling resistance of the tire can be effectively reduced, the fuel consumption of an automobile is reduced, and the wet skid resistance is improved, but the white carbon black is difficult to disperse in nonpolar rubber, so that the white carbon black is difficult to fill in rubber in large quantities. In order to improve the dispersion of the white carbon black in the rubber, a great deal of work is done, for example, the dispersion of the white carbon black in the rubber is improved by adding a white carbon black dispersing agent, the white carbon black with high dispersibility is adopted to replace the common white carbon black, the chemical surface modification is directly carried out on the white carbon black, and the like, and the purpose is to weaken the agglomeration of the white carbon black and increase the dispersion of the white carbon black in the rubber. However, at present, due to the defects of white carbon black in electrostatic conduction, a proper amount of carbon black must be compounded in the tire, so that the tire still uses the white carbon black and the carbon black to mix and reinforce the rubber matrix, and it is very important to find a processing aid capable of simultaneously promoting the dispersion of the white carbon black and the carbon black in the rubber.
Disclosure of Invention
The invention aims to provide a conjugated diene polymer capable of promoting white carbon black and carbon black to be well dispersed in rubber, a preparation method thereof and styrene butadiene rubber.
In order to achieve the above object, the present invention provides, in one aspect, a conjugated diene polymer having a structure provided by a conjugated diene monomer and optionally a structure provided by a monovinylarene monomer, and having a pendant group provided by a modifier attached to a molecular chain of the conjugated diene polymer;
wherein, based on the total weight of the structure provided by the conjugated diene monomer and the structure provided by the monovinylarene monomer, the content of the structure provided by the conjugated diene monomer is 70-100 wt%, and the content of the structure provided by the monovinylarene monomer is 0-30 wt%;
the content of the structure provided by the conjugated diene monomer containing the unsaturated side group is 10 to 75 weight percent based on the total content of the conjugated diene polymer, and the unsaturated side group is provided by the conjugated diene monomer;
the number average molecular weight of the conjugated diene polymer is 2-5 ten thousand;
the modifier is one or more of the compounds shown in the formula (1);
formula (1)
Figure BDA0001879596530000021
R1-R5Any one of which is mercapto, the remainder each being independently selected from H or C1-C6 alkyl;
or, R1-R3Any one of which is mercapto, the remainder each being independently selected from H or C1-C6 alkyl; r4And R5Cyclizing to form an aromatic ring structure;
or, R1-R3Each independently selected from H or C1-C6 alkyl; r4And R5The ring is synthesized into an aromatic ring structure, and H on at least one skeleton C of the aromatic ring structure is replaced by sulfydryl.
The second aspect of the present invention provides a method for preparing the above conjugated diene polymer, the method comprising:
(1) subjecting said conjugated diene monomer and optionally said monovinylarene monomer to anionic polymerization in an organic solvent in the presence of an organolithium initiator and optionally a structure modifier;
(2) subjecting the product of the anionic polymerization reaction to a radical polymerization reaction with the modifier in the presence of a radical initiator.
The third aspect of the present invention provides a styrene-butadiene rubber containing the above conjugated diene polymer.
The conjugated diene polymer provided by the invention can well disperse white carbon black and carbon black in styrene butadiene rubber, and the formed vulcanized rubber has low content of large-particle particles, so that the reinforcing effect of the white carbon black and the carbon black is conveniently provided.
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.
One aspect of the present invention provides a conjugated diene polymer comprising a structure provided by a conjugated diene monomer and optionally a structure provided by a monovinylarene monomer, wherein a molecular chain of the conjugated diene polymer is linked with a pendant group provided by a modifier;
wherein, based on the total weight of the structure provided by the conjugated diene monomer and the structure provided by the monovinylarene monomer, the content of the structure provided by the conjugated diene monomer is 70-100 wt%, and the content of the structure provided by the monovinylarene monomer is 0-30 wt%;
the content of the structure provided by the conjugated diene monomer containing the unsaturated side group is 10 to 75 weight percent based on the total content of the conjugated diene polymer, and the unsaturated side group is provided by the conjugated diene monomer;
the number average molecular weight of the conjugated diene polymer is 2-5 ten thousand;
the modifier is one or more of the compounds shown in the formula (1);
formula (1)
Figure BDA0001879596530000031
R1-R5Any one of which is mercapto, the remainder each being independently selected from H or C1-C6 alkyl; specifically, R is1-R5Any one of which is mercapto, the remaining 4R substituents each being independently selected from H or C1-C6 alkyl;
or, R1-R3Any one of which is mercapto, the remainder each being independently selected from H or C1-C6 alkyl; specifically, R is1-R3Any one of which is mercapto, the remaining 2R substituents each being independently selected from H or C1-C6 alkyl; r4And R5Cyclizing to form an aromatic ring structure;
or, R1-R3Each independently selected from H or C1-C6 alkyl; r4And R5The ring is synthesized into an aromatic ring structure, and H on at least one skeleton C of the aromatic ring structure is replaced by sulfydryl.
Among them, examples of the alkyl group of C1 to C6 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl and isomers thereof, hexyl and isomers thereof.
According to the invention, the conjugated diene polymer can be used as a dispersing aid of styrene-butadiene rubber to promote the dispersion of reinforcing agents, namely white carbon black and carbon black, added when vulcanized rubber is prepared from styrene-butadiene rubber. The main chain structure of the conjugated diene polymer may be provided by only the conjugated diene monomer, but may be provided by the conjugated diene monomer and the monovinyl aromatic hydrocarbon monomer, and preferably, the content of the structure provided by the conjugated diene monomer is 80 to 100% by weight and the content of the structure provided by the monovinyl aromatic hydrocarbon monomer is 0 to 20% by weight, based on the total weight of the structure provided by the conjugated diene monomer and the structure provided by the monovinyl aromatic hydrocarbon monomer. More preferably, the main chain structure of the conjugated diene polymer is provided by both the conjugated diene monomer and the monovinylarene monomer, and for this reason, it is more preferable that the content of the structure provided by the conjugated diene monomer is 80 to 90% by weight and the content of the structure provided by the monovinylarene monomer is 10 to 20% by weight, based on the total weight of the structure provided by the conjugated diene monomer and the structure provided by the monovinylarene monomer.
According to the present invention, the conjugated diene monomer may be appropriately selected from a plurality of monomers having a conjugated double bond, for example, from conjugated diene monomers of C4 to C6, preferably, the conjugated diene monomer is one or more of butadiene, isoprene, 1, 3-pentadiene, 1, 3-hexadiene and 2, 3-dimethylbutadiene, and more preferably, butadiene and/or isoprene.
In a preferred embodiment of the present invention, the conjugated diene monomer is butadiene (i.e., 1, 3-butadiene). For this reason, the butadiene, when 1, 2-polymerized, provides unsaturated vinyl side groups.
In a preferred embodiment of the invention, the conjugated diene monomer is a combination of butadiene (i.e. 1, 3-butadiene) and isoprene, in particular a combination of butadiene and isoprene in a molar ratio of 1:0.4 to 0.8. To this end, the butadiene, when 1, 2-polymerized, provides unsaturated vinyl side groups; the isoprene, when subjected to 1, 2-polymerization or 3, 4-polymerization, provides pendant unsaturated groups.
Preferably, the monovinyl aromatic hydrocarbon monomer is one or more of styrene, p-vinyl toluene, o-vinyl toluene, m-vinyl toluene, α -methyl styrene, 4-t-butyl styrene, 3, 5-diethyl styrene, 3, 5-di-n-butyl styrene, 4-n-propyl styrene and 4-dodecyl styrene, preferably one or more of styrene, p-vinyl toluene and α -methyl styrene, more preferably styrene.
In a preferred embodiment of the present invention, the conjugated diene monomer is butadiene and the monovinylarene monomer is styrene.
In another preferred embodiment of the present invention, the conjugated diene monomer is a combination of butadiene and isoprene and the monovinylarene monomer is styrene.
According to the invention, the conjugated diene polymer also contains certain unsaturated side groups, which are formed when the conjugated diene monomer is polymerized in a certain polymerization mode. Preferably, the structure provided by the conjugated diene monomer containing pendant unsaturated groups is present in an amount of from 25 to 55 weight percent, based on the total content of the conjugated diene polymer.
According to the invention, the molecular chain of the conjugated diene polymer is also linked with pendant groups provided by a modifier, which are usually obtained by radical-initiated linking of the mercapto group of the modifier with the unsaturated pendant groups of the conjugated diene polymer.
Wherein, in the formula (1), preferably, R1-R5Any one of them is mercapto, the rest is H; or, R1-R3Any one of them is mercapto, the rest is H; r4And R5Synthesizing a benzene ring structure; or, R1-R3Are all H; r4And R5The ring is synthesized into a benzene ring structure, and H on one framework C of the benzene ring structure is substituted by sulfydryl.
More preferably, the modifier is one or more of the compounds represented by the following formula:
Figure BDA0001879596530000051
Figure BDA0001879596530000061
wherein the amount of pendant groups provided by the modifier can vary within wide limits, preferably from 0.01 to 2 mole percent, based on the molar amount of structure provided by the conjugated diene monomer.
According to the invention, the number average molecular weight of the conjugated diene polymer needs to satisfy 2-5 ten thousand, and when the number average molecular weight of the conjugated diene polymer is less than 2 ten thousand, the fluidity is too strong, and the loss is easy to occur in the using process; when the number average molecular weight of the conjugated diene polymer is more than 5 ten thousand, excessive rubber properties are exhibited, and dispersion of the filler is not easy. More preferably, the conjugated diene polymer has a molecular weight distribution index of 1 to 2.
The second aspect of the present invention provides a method for preparing the above conjugated diene polymer, the method comprising:
(1) subjecting said conjugated diene monomer and optionally said monovinylarene monomer to anionic polymerization in an organic solvent in the presence of an organolithium initiator and optionally a structure modifier;
(2) subjecting the product of the anionic polymerization reaction to a radical polymerization reaction with the modifier in the presence of a radical initiator.
According to the present invention, the conjugated diene monomer, monovinylarene monomer and modifier are as described hereinabove, and the present invention is not described herein in detail, wherein the process is such that the resulting conjugated diene polymer is as described hereinabove. The amounts of the conjugated diene monomer and the monovinylarene monomer are such that, in the conjugated diene polymer obtained by the method, the total weight of the structure provided by the conjugated diene monomer and the structure provided by the monovinylarene monomer is taken as a reference, the content of the structure provided by the conjugated diene monomer is 70-100 wt%, and the content of the structure provided by the monovinylarene monomer is 0-30 wt%; preferably, the content of the structure provided by the conjugated diene monomer is 80 to 100% by weight and the content of the structure provided by the monovinylarene monomer is 0 to 20% by weight, based on the total weight of the structure provided by the conjugated diene monomer and the structure provided by the monovinylarene monomer; more preferably, the content of the structure provided by the conjugated diene monomer is 80 to 90% by weight and the content of the structure provided by the monovinylarene monomer is 10 to 20% by weight, based on the total weight of the structure provided by the conjugated diene monomer and the structure provided by the monovinylarene monomer.
Wherein the modifier is used in an amount such that the conjugated diene polymer obtained by the process has a pendant group content preferably in the range of from 0.01 to 2 mole%, based on the molar amount of structure provided by the conjugated diene monomer.
Wherein, the method can lead the number average molecular weight of the obtained conjugated diene polymer to be 2-5 ten thousand; so that the molecular weight distribution index of the obtained conjugated diene polymer is preferably 1 to 2; so that the content of the structure provided by the conjugated diene monomer containing a pendant unsaturated group in the resulting conjugated diene polymer is 10 to 75% by weight, preferably 25 to 55% by weight, based on the total content of the conjugated diene polymer.
According to the present invention, in step (1), the conjugated diene monomer and optionally said monovinylarene monomer are caused to undergo initiated polymerization by anionic polymerization. The initiator used is an organolithium initiator which may be a conventionally employed organolithium initiator for anionic polymerization, for example an organomono-or dilithium initiator, preferably a mono-organolithium initiator. To this end, preferably, the organolithium initiator is represented by the formula RLi, R being selected from alkyl, cycloalkyl or aryl; preferably, the organolithium initiator is one or more of ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, n-pentyllithium, n-hexyllithium, cyclohexyllithium, phenyllithium, benzyllithium, and naphthyllithium, more preferably n-butyllithium and/or sec-butyllithium.
The amount of the initiator can be selected appropriately according to the molecular weight of the conjugated diene polymer, and preferably, the amount of the organolithium initiator is 0.1 to 0.4 mol% based on the total molar amount of the conjugated diene monomer and the monovinyl aromatic hydrocarbon monomer.
According to the present invention, in the step (1), the organic solvent may employ a solvent conventionally used in the art for anionic polymerization, for example, one or more of cycloalkane which may be C5-C7, aromatic hydrocarbon, isoparaffin, etc. Preferably, in the step (1), the organic solvent is one or more of benzene, toluene, n-hexane, cyclohexane, n-pentane and n-heptane. The amount of the organic solvent used in the present invention is not particularly limited as long as the anionic polymerization reaction can be smoothly performed. For example, the organic solvent is used in an amount such that the total content of conjugated diene and monovinylarene monomers is from 5 to 30 wt%, preferably from 8 to 20 wt%.
According to the present invention, the polymerization reaction of step (1) is carried out under an inert atmosphere, and the gas providing such an inert atmosphere may be, for example, one or more of nitrogen, argon, helium, and the like.
According to the present invention, preferably, in step (1), the conditions of the anionic polymerization reaction include: the temperature is 35-80 ℃, preferably 40-50 ℃; the time is 30-120min, preferably 50-100 min.
According to the invention, step (1) is also carried out in the presence of a structure-regulating agent, for which purpose, in a preferred embodiment of the invention, the process of step (1) comprises: the conjugated diene monomer, optional monovinylarene monomer and organic solvent are mixed, then the structure regulator is added, and the anionic polymerization reaction is carried out under the condition of adding the organic lithium initiator.
Wherein the structure modifier may be a structure modifier conventionally used in polymerization reactions in the art, and for example, may include one or more of oxygen-, nitrogen-, sulfur-and phosphorus-containing compounds, preferably one or more selected from the group consisting of diethyl ether, dibutyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dioxane, crown ether, tetrahydrofurfuryl alcohol diethyl ether, tetrahydrofurfuryl alcohol butyl ether, triethylamine, tetramethylethylenediamine, hexamethylphosphoric triamide, potassium tert-butoxide, potassium tert-amylate, potassium laurate, potassium alkylbenzene sulfonate and sodium alkylbenzene sulfonate. The amount of the structure-regulating agent may be, for example, 100-550mg, preferably 120-350mg, based on 1000g of the total weight of the conjugated diene monomer, the monovinyl aromatic hydrocarbon monomer and the organic solvent, for example, in the case of tetrahydrofurfuryl alcohol ethyl ether or tetrahydrofurfuryl alcohol butyl ether.
According to the invention, in step (2), the pendant groups provided by the modifier will be attached to the polymer chains in the product of the anionic polymerization reaction in the presence of a free radical initiator. Wherein the modifier is as hereinbefore described, wherein the process is such that the resulting conjugated diene polymer preferably has a pendant group content provided by the modifier of from 0.01 to 2 mole%, based on the molar amount of structure provided by the conjugated diene monomer.
According to the present invention, the radical initiator may be appropriately selected from a variety of radical initiators, and preferably, the radical initiator is one or more of an azo-based radical initiator and a peroxide-based radical initiator. Specific examples of the azo-based radical initiator may be, for example, one or more of dimethyl azobisisobutyrate, azobisisobutyramidine hydrochloride, azobisformamide, azobisisopropylimidazoline hydrochloride, azobisisobutyronitrile formamide, azobisdicyclohexylcarbonitrile, azobiscyanovaleric acid, azobisisopropylimidazoline, azobisisobutyronitrile, azobisisovaleronitrile, and azobisisoheptonitrile. Specific examples of the peroxide-based radical initiator may be, for example, one or more of hydrogen peroxide, ammonium persulfate, sodium persulfate, potassium persulfate, benzoyl peroxide t-butyl peroxide, and 1, 1-di-t-butylperoxy-3, 3, 5-trimethylcyclohexane. Preferably, the free radical initiator is one or more of benzoyl peroxide, azobisisobutyronitrile and 1, 1-di-tert-butylperoxy-3, 3, 5-trimethylcyclohexane.
Wherein the amount of said free radical initiator may vary within wide limits, preferably said free radical initiator is used in an amount of 0.002 to 0.1 mol%, based on the total molar amount of said conjugated diene monomers.
According to the present invention, preferably, the conditions of the radical polymerization reaction include: the temperature is 0-130 ℃, the pressure is 0.05-0.5MPa, and the time is 0.5-24 h; preferably, the conditions of the radical polymerization reaction include: the temperature is 50-100 ℃, the pressure is 0.1-0.3MPa, and the time is 2-5 h.
The third aspect of the present invention provides a polymer comprising the above conjugated diene polymer.
According to the present invention, the conjugated diene polymer of the present invention is incorporated in styrene-butadiene rubber as a dispersion aid, which can contribute to the dispersion of the reinforcing agent when the vulcanized rubber is prepared using styrene-butadiene rubber as a base rubber. The styrene-butadiene rubber can be various styrene-butadiene rubbers which are conventional in the field, and can be prepared by a conventional method in the field, and for example, the preparation process of the styrene-butadiene rubber comprises the following steps: styrene, butadiene and optionally isoprene are polymerized in an inert atmosphere in an organic solvent and in the presence of an organolithium initiator and a structure modifier. Wherein the organic solvent, organolithium initiator and structure modifier are as described hereinbefore. The organolithium initiator may be used, for example, in an amount of 0.02 to 0.1 weight percent, based on the total weight of butadiene and optionally isoprene. The amount of the structure-regulating agent may be, for example, 100-800mg, preferably 180-550mg, based on 1000g of the total weight of the styrene, butadiene, optionally isoprene and organic solvent, for example, using tetrahydrofurfuryl alcohol ethyl ether or tetrahydrofurfuryl alcohol butyl ether. The styrene may be used, for example, in an amount of 20 to 30 wt%, based on the total weight of butadiene and isoprene. The conditions of the polymerization reaction may include: the temperature is 40-80 deg.C, and the time is 40-120 min.
According to the present invention, the number average molecular weight of the styrene-butadiene rubber is preferably 10 to 20 ten thousand.
According to the invention, the styrene-butadiene rubber can also be a coupled rubber, for example, the preparation process comprises: styrene, butadiene and optionally isoprene are polymerized in an inert atmosphere in an organic solvent and in the presence of an organolithium initiator and a structure modifier, and the reaction product is then coupled with a coupling agent. The types and amounts of the organic solvent, organolithium initiator and structure modifier are as described above. Wherein, the coupling agent can be one or more of polyvinyl compounds, halides, ethers, aldehydes, ketones, esters and the like, and is preferably one or more selected from divinylbenzene, tetravinylsilane, tetrachloromethane, silicon tetrachloride, tin tetrachloride and dimethyl terephthalate.
According to the present invention, the coupling ratio of the styrene-butadiene rubber is preferably 30 to 70%.
According to the present invention, the conjugated diene polymer may be mixed with the product after polymerization or after coupling reaction in the case of including the coupling reaction, and then the styrene-butadiene rubber product is obtained by coagulation. Wherein the content of the conjugated diene polymer is preferably 1 to 10% by weight, more preferably 2 to 5% by weight, based on the total weight of the styrene-butadiene rubber.
When the styrene-butadiene rubber of the present invention is used as a base rubber of a vulcanized rubber, a rubber composition may be prepared according to a conventional method in the art, and the rubber composition may contain styrene-butadiene rubber, a vulcanizing agent, a vulcanization accelerator, a reinforcing agent, an activator, and the like. The selection of the ingredients in the rubber composition and the method of mixing and vulcanizing the rubber composition may be conventional in the art, and will be known to those skilled in the art and will not be described herein.
The present invention will be described in detail below by way of examples.
Preparation example 1
2320g of cyclohexane, 60.6g of styrene and 245.8g of butadiene are mixed under the protection of high-purity nitrogen, then tetrahydrofurfuryl alcohol ether (the dosage of the tetrahydrofurfuryl alcohol ether is 445mg relative to 1000g of the total amount of the cyclohexane, the styrene and the butadiene) is added, 1.6mmol of n-butyl lithium is added at 50 ℃ for initiation, the reaction is carried out for 60 minutes at 50 ℃, half weight of glue solution is taken as styrene butadiene rubber base solution A1 after the reaction is finished, and the residual glue solution is subjected to water vapor condensation to obtain a styrene butadiene rubber sample B1.
Preparation example 2
2320g of cyclohexane, 61.6g of styrene, 116.3g of isoprene and 126.2g of butadiene are mixed under the protection of high-purity nitrogen, then tetrahydrofurfuryl alcohol butyl ether (the dosage of the tetrahydrofurfuryl alcohol butyl ether is 210mg relative to 1000g of the total amount of the cyclohexane, the styrene, the isoprene and the butadiene) is added, 2.11mmol of n-butyl lithium is added at 60 ℃ for initiation, the reaction is carried out for 60 minutes at 60 ℃, 0.22mmol of tin tetrachloride is added, the reaction is carried out for 20 minutes at 60 ℃, after the reaction is finished, a part of glue solution with half weight is taken as a styrene-butadiene rubber base solution A2, and the residual glue solution is subjected to condensation by water vapor to obtain a styrene-butadiene rubber sample B2.
Example 1
This example illustrates a conjugated diene polymer, a method for preparing the same, and styrene butadiene rubber.
(1) 2110g of cyclohexane, 42g of styrene and 214g of butadiene were mixed under high-purity nitrogen protection, and then tetrahydrofurfuryl alcohol ether (155 mg relative to 1000g of the total amount of cyclohexane, styrene and butadiene) was added, and 6.9mmol of n-butyllithium was added at 50 ℃ to initiate a reaction for 60 minutes;
(2) adding 0.092mmol of azobisisobutyronitrile and 4.5mmol of 2-mercaptopyridine into the reaction product obtained in the step (1), and reacting at 75 ℃ for 3 hours to obtain a glue solution A3;
and adding part of the glue solution A3 into a styrene butadiene rubber base solution A1 in an amount such that the weight of the conjugated diene polymer in the glue solution A3 is 3 wt% of the weight of styrene butadiene rubber in the A1, and then condensing with absolute ethyl alcohol to obtain a styrene butadiene rubber sample B3.
Example 2
This example illustrates a conjugated diene polymer, a method for preparing the same, and styrene butadiene rubber.
(1) 2110g of cyclohexane, 51g of styrene and 203g of butadiene were mixed under the protection of high-purity nitrogen, and then tetrahydrofurfuryl alcohol butyl ether (the amount of tetrahydrofurfuryl alcohol butyl ether used is 350mg relative to 1000g of the total amount of cyclohexane, styrene and butadiene) was added, and 9.2mmol of sec-butyllithium was added at 45 ℃ to initiate a reaction for 80 minutes;
(2) adding 0.18mmol of benzoyl peroxide and 6.7mmol of 2-mercaptobenzopyridine into the reaction product obtained in the step (1), and reacting at 70 ℃ for 2.5 hours to obtain a glue solution A4;
and adding part of the glue solution A4 into a styrene butadiene rubber base solution A1 in an amount such that the weight of the conjugated diene polymer in the glue solution A4 is 3 wt% of the weight of styrene butadiene rubber in the A1, and then condensing with absolute ethyl alcohol to obtain a styrene butadiene rubber sample B4.
Example 3
This example illustrates a conjugated diene polymer, a method for preparing the same, and styrene butadiene rubber.
(1) 1998g of cyclohexane, 49.4g of styrene, 97.8g of isoprene and 111.9g of butadiene were mixed under protection of high purity nitrogen, and then tetrahydrofurfuryl alcohol butyl ether (used in an amount of 180mg relative to 1000g of the total amount of cyclohexane, styrene, isoprene and butadiene) was added, and 7.3mmol of n-butyllithium was added at 60 ℃ to initiate a reaction for 70 minutes;
(2) adding 0.122mmol of azobisisobutyronitrile and 6.1mmol of 4-mercaptopyridine into the reaction product obtained in the step (1), and reacting at 80 ℃ for 3 hours to obtain a glue solution A5;
and adding part of the glue solution A5 into a styrene butadiene rubber base solution A2 in an amount such that the weight of the modified conjugated diene polymer in the glue solution A5 is 5 wt% of the weight of styrene butadiene rubber in the A2, and then condensing with absolute ethyl alcohol to obtain a styrene butadiene rubber sample B5.
Comparative example 1
According to the method of the embodiment 1, except that in the step (1), the amount of the added initiator n-butyllithium is 19mmol, and the glue solution DA1 is finally obtained;
and adding part of the glue solution DA1 into the styrene butadiene rubber base solution A1 in an amount which enables the weight of the conjugated diene polymer in the glue solution DA1 to be 3 weight percent of the weight of the styrene butadiene rubber in A1, and then condensing through absolute ethyl alcohol to obtain a styrene butadiene rubber sample DB 1.
Comparative example 2
According to the method described in the embodiment 1, except that in the step (1), the amount of the added initiator n-butyllithium is 3.5mmol, and a glue solution DA2 is finally obtained;
and adding part of the glue solution DA2 into the styrene butadiene rubber base solution A1 in an amount which enables the weight of the conjugated diene polymer in the glue solution DA2 to be 3 weight percent of the weight of the styrene butadiene rubber in A1, and then condensing through absolute ethyl alcohol to obtain a styrene butadiene rubber sample DB 2.
Comparative example 3
According to the method of the embodiment 1, except that in the step (2), 2-mercaptopyridine is not added, and a glue solution DA3 is finally obtained;
and adding part of the glue solution DA3 into the styrene butadiene rubber base solution A1 in an amount which enables the weight of the conjugated diene polymer in the glue solution DA3 to be 3 weight percent of the weight of the styrene butadiene rubber in A1, and then condensing through absolute ethyl alcohol to obtain a styrene butadiene rubber sample DB 3.
Test example
The microstructure of the obtained polymer (a polymer sample was obtained by coagulating a part of each gel) was measured by an AVANCE DRX 400MHz NMR spectrometer of Bruker, Switzerland, and the solvent was deuterated chloroform, thereby obtaining the data of the content of the structural unit in Table 1. Wherein the butadiene structure content (wt%), the isoprene structure content (wt%) and the styrene structure content (wt%) are based on the butadiene structure content, the isoprene structure content and the styrene structure content. The unsaturated side group content (% by weight) means the content of the structure provided by the conjugated diene monomer containing an unsaturated side group, based on the total content of the conjugated diene polymer. By modifier pendant group content is meant the content of pendant groups provided by the modifier, based on the molar amount of structure provided by the conjugated diene monomer.
The molecular weight and coupling efficiency of the resulting polymer (a sample of the polymer obtained by coagulation of a portion of each dope) were determined using a WATERS ALLIANCE model 2690 Gel Permeation Chromatograph (GPC) with THF as the mobile phase, narrow distribution polystyrene as the standard and at a temperature of 25 ℃ to obtain the molecular weight data in Table 1.
The filler dispersion in the vulcanizate (vulcanizate was obtained from raw rubber by mixing in an internal mixer) of the obtained rubber sample was evaluated according to GB/T6030-2006 Rapid comparison method for evaluation of dispersion of carbon black and carbon black/silica in rubber, using the Disper' GRADER carbon black Dispersion tester, Alpha, USA, wherein the particle size distribution in the vulcanizate is shown in Table 2.
Wherein the vulcanized rubber comprises the following components: 100g of raw rubber, 15g of high-wear-resistance carbon black, 55g of white carbon black, 2.5g of zinc oxide, 1g of stearic acid, 2g of an anti-aging agent 4020 (purchased from Shandong Shengao chemical Co., Ltd., the same below), 1.4g of an accelerator CZ (purchased from Shanghai Kai chemical Co., Ltd., the same below), 0.75g of 2, 3-diphosphoglyceric acid (DPG), 6g of a silane coupling agent KH-Si69 (purchased from Hangzhou Jecca chemical Co., Ltd.), and 1.4g of sulfur; after the filler is added, Haake heat treatment is adopted, and the period conditions comprise: the temperature is 150 ℃, the rotating speed is 30rpm, and the time is 7 min; then carrying out vulcanization under the conditions comprising: the temperature is 145 ℃, the pressure is more than 10MPa, and the time is 35 min; wherein when the crude rubber adopts B1, vulcanized rubber DS1 is obtained; when the raw rubber adopts B3, obtaining vulcanized rubber S1; when the raw rubber adopts B4, obtaining vulcanized rubber S2; when the raw rubber adopts DB1, obtaining vulcanized rubber DS 2; when the raw rubber adopts DB2, obtaining vulcanized rubber DS 3; when the raw rubber adopts DB3, obtaining vulcanized rubber DS 4;
and the composition of the vulcanized rubber is as follows: 100g of raw rubber (B2 or B4), 15g of aromatic oil (purchased from Heishikang chemical Co., Ltd.), 35g of 8# reference carbon black, 15g of white carbon black, 4.8g of silane coupling agent KH-Si69, 1.5g of sulfur, 1g of accelerator D (purchased from Shandong Shengao chemical Co., Ltd.), 1.5g of accelerator TBBS (purchased from Shandong Shengao chemical Co., Ltd.), 2g of stearic acid, 2g of antioxidant 4020 and 3g of zinc oxide. Then carrying out vulcanization under the conditions comprising: the temperature is 145 ℃, the pressure is more than 10MPa, and the time is 35 min; wherein when the crude rubber adopts B2, vulcanized rubber DS5 is obtained; when B5 was used as the raw rubber, vulcanizate S3 was obtained.
TABLE 1
Figure BDA0001879596530000151
TABLE 2
Particle diameter/. mu.m 2.9-8.6 11.5-17.2 20.1-28.7 31.6-51.7
S1 76.6％ 21.6％ 1.8％ 0.0％
DS1 46.0％ 36.1％ 16.1％ 1.8％
DS2 61.9％ 31.9％ 6.0％ 0.2％
DS3 59.9％ 33.1％ 6.2％ 0.8％
DS4 64.7％ 28.9％ 6.0％ 0.4％
S2 76.3％ 26.6％ 2.9％ 0.0％
S3 74.8％ 23.4％ 1.8％ 0.0％
DS5 41.4％ 35.9％ 19.8％ 2.9％
As can be seen from the data in Table 2, the conjugated diene polymer of the present invention can well disperse the white carbon black and the carbon black in the styrene-butadiene rubber, and the formed vulcanized rubber has a low content of large particles, which is convenient for providing the reinforcing effect of the white carbon black and the carbon black.
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 (15)

1. A conjugated diene polymer, characterized in that the conjugated diene polymer comprises a structure provided by a conjugated diene monomer and optionally a structure provided by a monovinylarene monomer, and that the molecular chain of the conjugated diene polymer has pendant groups provided by a modifier attached;
wherein, based on the total weight of the structure provided by the conjugated diene monomer and the structure provided by the monovinylarene monomer, the content of the structure provided by the conjugated diene monomer is 70-100 wt%, and the content of the structure provided by the monovinylarene monomer is 0-30 wt%;
the content of the structure provided by the conjugated diene monomer containing the unsaturated side group is 10 to 75 weight percent based on the total content of the conjugated diene polymer, and the unsaturated side group is provided by the conjugated diene monomer;
the number average molecular weight of the conjugated diene polymer is 2-5 ten thousand;
the modifier is one or more of the compounds shown in the formula (1);
formula (1)
Figure FDA0001879596520000011
R1-R5Any one of which is mercapto, the remainder each being independently selected from H or C1-C6 alkyl;
or, R1-R3Any one of which is mercapto, the remainder each being independently selected from H or C1-C6 alkyl; r4And R5Cyclizing to form an aromatic ring structure;
or, R1-R3Each independently selected from H or C1-C6 alkyl; r4And R5The ring is synthesized into an aromatic ring structure, and H on at least one skeleton C of the aromatic ring structure is replaced by sulfydryl.
2. The conjugated diene polymer of claim 1, wherein the content of the structure provided by the conjugated diene monomer is 80 to 100% by weight and the content of the structure provided by the monovinylarene monomer is 0 to 20% by weight, based on the total weight of the structure provided by the conjugated diene monomer and the structure provided by the monovinylarene monomer;
preferably, the content of the structure provided by the conjugated diene monomer is 80 to 90% by weight and the content of the structure provided by the monovinylarene monomer is 10 to 20% by weight, based on the total weight of the structure provided by the conjugated diene monomer and the structure provided by the monovinylarene monomer.
3. The conjugated diene polymer according to claim 1 or 2, wherein the conjugated diene monomer is one or more of butadiene, isoprene, 1, 3-pentadiene, 1, 3-hexadiene and 2, 3-dimethylbutadiene, preferably butadiene and/or isoprene;
preferably, the monovinylarene monomer is one or more of styrene, p-vinyltoluene, o-vinyltoluene, m-vinyltoluene, α -methylstyrene, 4-tert-butylstyrene, 3, 5-diethylstyrene, 3, 5-di-n-butylstyrene, 4-n-propylstyrene and 4-dodecylstyrene, preferably one or more of styrene, p-vinyltoluene and α -methylstyrene, more preferably styrene.
4. The conjugated diene polymer of any one of claims 1-3, wherein the content of structures provided by conjugated diene monomers containing pendant unsaturated groups is from 25 to 55 weight percent, based on the total content of the conjugated diene polymer.
5. The conjugated diene polymer of any one of claims 1-4, wherein the pendant groups provided by the modifier are present in an amount of from 0.01 to 2 mole percent, based on the moles of structure provided by the conjugated diene monomer.
6. The conjugated diene polymer according to claim 1 or 5, wherein,
R1-R5any one of them is mercapto, the rest is H;
or, R1-R3Any one of them is mercapto, the rest is H; r4And R5Synthesizing a benzene ring structure;
or, R1-R3Are all H; r4And R5Synthesizing a benzene ring structure by a ring, wherein H on a skeleton C of the benzene ring structure is substituted by sulfydryl;
preferably, the modifier is one or more of the compounds represented by the following formula:
Figure FDA0001879596520000031
7. the conjugated diene polymer according to any one of claims 1 to 6, wherein the conjugated diene polymer has a molecular weight distribution index of 1 to 2.
8. A process for preparing a conjugated diene polymer according to any one of claims 1 to 7, comprising:
(1) subjecting said conjugated diene monomer and optionally said monovinylarene monomer to anionic polymerization in an organic solvent in the presence of an organolithium initiator and optionally a structure modifier;
(2) subjecting the product of the anionic polymerization reaction to a radical polymerization reaction with the modifier in the presence of a radical initiator.
9. The process of claim 8, wherein the organolithium initiator is of the formula RLi, R is selected from alkyl, cycloalkyl or aryl; preferably, the organolithium initiator is one or more of ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, n-pentyllithium, n-hexyllithium, cyclohexyllithium, phenyllithium, benzyllithium, and naphthyllithium, more preferably n-butyllithium and/or sec-butyllithium;
preferably, the organolithium initiator is used in an amount of 0.1 to 0.4 mol% based on the total molar amount of the conjugated diene monomer and the monovinylarene monomer.
10. The process of claim 8 or 9, wherein the organic solvent is one or more of benzene, toluene, n-hexane, cyclohexane, n-pentane, and n-heptane;
preferably, the organic solvent is used in an amount such that the total content of the conjugated diene monomer and the monovinylarene monomer is from 5 to 30 weight percent, preferably from 8 to 20 weight percent.
11. The method of any one of claims 8-10, wherein the anionic polymerization conditions comprise: the temperature is 35-80 ℃, preferably 40-50 ℃; the time is 30-120min, preferably 50-100 min.
12. The method according to any one of claims 8 to 11, wherein the radical initiator is one or more of an azo-based radical initiator and a peroxide-based radical initiator;
preferably, the azo-based radical initiator is one or more of dimethyl azobisisobutyrate, azobisisobutyramidine hydrochloride, azobisformamide, azobisisopropylimidazoline hydrochloride, azobisisobutyronitrile formamide, azobiscyclohexylcarbonitrile, azobiscyanovaleric acid, azobisdiisopropylimidazoline, azobisisobutyronitrile, azobisisovaleronitrile, and azobisisoheptonitrile; the peroxide free radical initiator is one or more of hydrogen peroxide, ammonium persulfate, sodium persulfate, potassium persulfate, benzoyl peroxide tert-butyl peroxide and 1, 1-di-tert-butyl peroxide-3, 3, 5-trimethylcyclohexane;
preferably, the free radical initiator is one or more of benzoyl peroxide, azobisisobutyronitrile and 1, 1-di-tert-butylperoxy-3, 3, 5-trimethylcyclohexane;
preferably, the free radical initiator is used in an amount of 0.002 to 0.1 mol% based on the total molar amount of the conjugated diene monomer.
13. The method of any one of claims 8-12, wherein the conditions of the free radical polymerization reaction comprise: the temperature is 0-130 ℃, the pressure is 0.05-0.5MPa, and the time is 0.5-24 h.
14. A styrene-butadiene rubber comprising the conjugated diene polymer according to any one of claims 1 to 7.
15. The styrene-butadiene rubber according to claim 14, wherein the conjugated diene polymer is contained in the styrene-butadiene rubber in an amount of 1 to 10% by weight, preferably 2 to 5% by weight.
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