CN109749011B

CN109749011B - Ternary random copolymer and ternary random copolymer composition, application thereof and anionic polymerization method

Info

Publication number: CN109749011B
Application number: CN201711058640.8A
Authority: CN
Inventors: 康新贺; 徐林; 王雪; 王妮妮; 刘辉; 孙文娟
Original assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Current assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Priority date: 2017-11-01
Filing date: 2017-11-01
Publication date: 2021-08-03
Anticipated expiration: 2037-11-01
Also published as: CN109749011A

Abstract

The invention discloses a ternary random copolymer, a ternary random copolymer composition, application thereof and an anionic polymerization method, wherein the method comprises the following steps: (1) contacting, under anionic polymerization conditions, in the presence of a polar additive, a polymerized monomer in a solvent with an organolithium initiator, the polymerized monomer containing a conjugated diene and a monovinylarene, the conjugated diene comprising a first conjugated diene and a second conjugated diene, the first conjugated diene being different from the second conjugated diene; (2) optionally, contacting the mixture obtained by the step (1) with a coupling agent under the coupling reaction condition, wherein the polar additive is selected from compounds shown in a formula II. According to the anionic polymerization method of the present invention, by using a polar additive having a specific structure, a ternary random copolymer (composition) having both a low side group content and a low monovinylarene block content can be prepared.

Description

Ternary random copolymer and ternary random copolymer composition, application thereof and anionic polymerization method

Technical Field

The invention relates to a ternary random copolymer and a ternary random copolymer composition, and also relates to application of the ternary random copolymer and the ternary random copolymer composition in tire tread rubber, and further relates to an anionic polymerization method for preparing the ternary random copolymer and the ternary random copolymer composition.

Background

The rubber material is one of three large polymer materials, has unique entropy elasticity, and the tire manufactured by the rubber material bears the operation development of modern industry and society, and is called as a material with strategic position. The fuel-saving and wear-resistant tire has great significance for energy conservation, environmental protection, atmospheric pollution control and the like, and is the future development trend of tire technology and industry. In 1984, Nordsiek et al proposed the concept of styrene-butadiene-isoprene terpolymer (integrated rubber), and hopefully prepared a rubber material integrating the advantages of general rubber by molecular design technology, meeting the use requirements of the high-performance tire tread rubber.

For styrene-butadiene-isoprene terpolymers, the properties of the rubber material are closely related to its sequence composition and microstructure. In the absence of polar regulator, the reactivity ratio of three monomers of styrene, butadiene and isoprene is different, so that the generated copolymer has more styrene blocks, although the copolymer has lower glass transition temperature (T)_g) But is not suitable for use in tire tread rubber. In order to make styrene monomer tend to be randomly distributed in the copolymer, introducing a polarity regulator into the polymerization system so as to control the sequence structure of the polymer is a commonly used technique at present.

US4,367,325 and US4,139,690 mention a process for the synthesis of high vinyl content rubbers by anionic polymerization, which combines ethers and anionic surfactants as polar additives.

U.S. Pat. No. 4,5,008,343 also describes a process for the synthesis of star-shaped high-vinyl rubbers by anionic polymerization, using asymmetric ethers as activators and polar additives for the reaction.

U.S. Pat. No. 5,137,998 describes a process for the synthesis of terpolymer rubbers by anionic polymerization, in which tripiperidine phosphine oxide (TPPO) or alkali metal alkoxides, preferably potassium alkoxides, are used as polar additives, and in which the polymers obtained have a relatively high content of pendant groups.

US5,448,003 describes a process for the synthesis of terpolymer rubbers by anionic polymerization using alkyl tetrahydrofurfuryl ethers as polar additives to obtain copolymers with a high vinyl content.

Through the above reports, it can be found that: when the amount of the polarity modifier is larger, a copolymer with lower styrene block content can be obtained, even the styrene monomers tend to be randomly distributed in the copolymer, but the copolymer obtained by the method tends to have higher side group content and higher T_gThe abrasion resistance of the rubber material is improved; when the amount of the polarity regulator is small, a low T can be obtained_gHowever, the increase of the block styrene content in the copolymer adversely affects the improvement of the overall performance of the rubber.

In summary, while researchers have developed various polar additives to modify the sequence structure and microstructure of synthetic rubbers, such polar additives are primarily used to increase the pendant group content of synthetic rubbers and the preparation of terpolymers having both a low glass transition temperature and a low block styrene content has been the subject of effort in the synthetic rubber art.

Disclosure of Invention

Aiming at the defects of the prior polarity regulator in the preparation of the terpolymer with low glass transition temperature and low styrene content, the inventor of the invention has conducted intensive research and finds a polarity additive with a specific structure, when the polarity additive is used for preparing the ternary random copolymer with lower side group content, the polarity additive still has stronger regulating capacity to the styrene block, and the ternary random copolymer with lower side group content and lower styrene block content can be obtained. The present invention has been completed based on this finding.

According to a first aspect of the present invention, there is provided a ternary random copolymer comprising structural units derived from a conjugated diene and structural units derived from a monovinyl aromatic hydrocarbon, said conjugated diene comprising a first conjugated diene and a second conjugated diene, and said first conjugated diene being different from said second conjugated diene;

the content of structural units derived from the first conjugated diene is from 35 to 65% by weight, the content of structural units derived from the second conjugated diene is from 15 to 50% by weight, and the content of structural units derived from the monovinyl aromatic hydrocarbon is from 10 to 24% by weight, based on the total amount of the ternary random copolymer;

taking the total amount of the ternary random copolymer as a reference, the content of side groups in the ternary random copolymer is 10-25 wt%;

the content of monovinyl aromatic hydrocarbon blocks is not higher than 0.8% by weight, based on the total amount of the ternary random copolymer.

According to a second aspect of the present invention, there is provided a ternary random copolymer composition comprising a first component, and optionally a second component, the first component having a number average molecular weight greater than the number average molecular weight of the second component, wherein the first component and the second component each comprise structural units derived from a conjugated diene comprising a first conjugated diene and a second conjugated diene, and structural units derived from a monovinyl arene, and the first conjugated diene is different from the second conjugated diene;

the content of structural units derived from the first conjugated diene is from 35 to 65% by weight, the content of structural units derived from the second conjugated diene is from 15 to 50% by weight, and the content of structural units derived from the monovinyl aromatic hydrocarbon is from 10 to 24% by weight, based on the total amount of the ternary random copolymer composition;

the side group content is 10-25 wt% based on the total weight of the ternary random copolymer composition;

the content of monovinylarene blocks is not higher than 0.8 wt.% based on the total amount of the ternary random copolymer composition.

According to a third aspect of the present invention, there is provided an anionic polymerisation process comprising:

(1) under the condition of anionic polymerization, in the presence of a polar additive, contacting a polymerization monomer with an anionic polymerization initiator in a solvent to obtain a ternary random copolymer, wherein the polymerization monomer contains conjugated diene and monovinyl aromatic hydrocarbon, the conjugated diene comprises a first conjugated diene and a second conjugated diene, and the first conjugated diene is different from the second conjugated diene;

(2) optionally, under the coupling reaction condition, contacting the mixture obtained by the step (1) with a coupling agent,

wherein the polar additive is selected from compounds represented by formula II,

in the formula II, R₂、R₃、R₄、R₅、R₆And R₇Are the same or different and are each C₁-C₅Alkyl or hydrogen atom, and R₂、R₃And R₄At least one of them is C₁-C₅Alkyl radical, R₅、R₆And R₇At least one of them is C₁-C₅An alkyl group.

According to a fourth aspect of the present invention there is provided a ternary random copolymer or ternary random copolymer composition produced by the process of the third aspect of the present invention.

According to a fifth aspect of the present invention, there is provided a ternary random copolymer according to the first aspect of the present invention, a ternary random copolymer composition according to the second aspect of the present invention, a ternary random copolymer or ternary random copolymer composition according to the fourth aspect of the present invention for use in a tread rubber for a tire.

According to the anionic polymerization method of the present invention, by using a polar additive having a specific structure, a monovinylarene-conjugated diene ternary random copolymer (composition) having both a lower content of pendant groups and a lower content of monovinylarene blocks can be prepared.

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.

In the present invention, the term "monovinylarene" refers to a compound formed by substituting one hydrogen on an aromatic ring with a vinyl group, for example: the monovinylarene can be one or more than two compounds selected from the compounds shown in the formula I,

in the formula I, R₁Is C₆-C₂₀Substituted or unsubstituted aryl of (a). Said C is₆-C₂₀Specific examples of the substituted or unsubstituted aryl group of (a) may include, but are not limited to: phenyl, o-tolyl, m-tolyl, p-tolyl, o-ethylphenyl, m-ethylphenyl, p-ethylphenyl, o-tert-butylphenyl, m-tert-butylphenyl, p-dodecylphenyl, 2, 4-di-n-butylphenyl, n-propylphenyl and 2, 4-diethylphenyl.

Preferably, the monovinyl aromatic hydrocarbon is one or more selected from the group consisting of styrene, 2-methylstyrene, 4-tert-butylstyrene, 2-ethylstyrene, 4-ethylstyrene, 3, 5-dimethylstyrene, 3, 5-diethylstyrene, 3, 5-di-n-butylstyrene, 4-n-propylstyrene and 4-dodecylstyrene.

More preferably, the monovinylarene is one or more selected from styrene, 2-methylstyrene and 4-methylstyrene.

Further preferably, the monovinylarene is styrene.

In the present invention, the term "conjugated diene" refers to an unsaturated chain hydrocarbon having a conjugated double bond (i.e., -C-) in its molecular structure, and may be any of various conjugated dienes commonly used in the art, and is not particularly limited. For example: the conjugated diene may be selected from C₄-C₈One or more than two of the conjugated diolefins (2).

Preferably, the conjugated diene is one or more selected from butadiene, isoprene, 1, 3-hexadiene and 2, 3-dimethylbutadiene.

In the present invention, the first conjugated diene and the second conjugated diene may each be one or two or more selected from the above conjugated dienes as long as the first conjugated diene and the second conjugated diene are different conjugated dienes. In a preferred embodiment, the first conjugated diene is butadiene and the second conjugated diene is isoprene.

In the present invention, "structural unit derived from xxx" means that the structural unit is a structural unit formed by addition polymerization of "xxx", for example: the structural unit derived from a monovinylarene refers to a structural unit formed by addition polymerization of a monovinylarene.

In the present invention, the term "side group content" refers to the content of structural units derived from a conjugated diene containing ethylenic side groups (i.e., side groups containing C ═ C bonds) in the copolymer (composition) based on the total amount of the copolymer (composition). The pendant ethylenic groups are typically derived from units of conjugated diolefins formed by 1, 2-polymerization and units of conjugated diolefins formed by 3, 4-polymerization. For example, when the conjugated diene is butadiene and isoprene, the pendant group content may be a percentage of the total amount of the structural units formed in a 1, 2-polymerization manner and the structural units formed in a 3, 4-polymerization manner of the conjugated diene to the total amount of the structural units derived from the conjugated diene.

In the present invention, the term "monovinylarene block content" means that the structural units in the block are all derived from monovinylarenes and the number of structural units in the block is 5 or more. For example, "styrene block" means that the structural units in the block are all derived from styrene, and the number of structural units in the block is 5 or more. In the present invention, the content of monovinylarene blocks was determined using an AVANCE DRX 400MHz NMR spectrometer from Bruker, Switzerland, which has a detection sensitivity of greater than 220 (defined by the signal-to-noise ratio (S/N) of the NMR signal measured on the spectrometer using a standard sample) when it is subjected to a hydrogen spectroscopy test.

In the present invention, "coupling efficiency" means the weight percentage of the number of molecular chains to be coupled to the total number of molecular chains, that is, the coupling efficiency means the content of the polymer formed by coupling based on the total amount of the ternary random copolymer composition, and the balance is the content of the uncoupled ternary random polymer.

In the present invention, the term "at least one" means one or two or more. In the present invention, the term "optional" means optional, and may be understood as "including or not including" and "containing or not containing".

According to a first aspect of the present invention, there is provided a ternary random copolymer comprising structural units derived from a conjugated diene and structural units derived from a monovinyl aromatic hydrocarbon, said conjugated diene comprising a first conjugated diene and a second conjugated diene, and said first conjugated diene being different from said second conjugated diene.

In a preferred embodiment, the first conjugated diene is butadiene, the second conjugated diene is isoprene, and the monovinylarene is styrene.

The content of structural units derived from the first conjugated diene may be 35 to 65% by weight, preferably 40 to 63% by weight, the content of structural units derived from the second conjugated diene may be 15 to 50% by weight, preferably 19 to 45% by weight, and the content of structural units derived from the monovinyl aromatic hydrocarbon may be 10 to 24% by weight, preferably 14 to 22% by weight, based on the total amount of the ternary random copolymer. In the invention, the composition of the ternary random copolymer is determined by adopting a nuclear magnetic resonance hydrogen spectrum.

According to the ternary random copolymer of the present invention, the total amount of the structural units formed by 1, 2-polymerization and the structural units formed by 3, 4-polymerization of the conjugated diene is low (i.e., the side group content of the ternary random copolymer according to the present invention is low). Generally, the pendant groups may be present in the random terpolymer in an amount of from 10 to 25 weight percent, preferably from 11 to 22 weight percent, based on the total amount of the random terpolymer. In one embodiment, the pendant group content of the random terpolymer is from 11 to 14 weight percent, such as from 11.5 to 12.5 weight percent, and according to this embodiment, the structural units derived from the monovinyl aromatic hydrocarbon are preferably present in an amount of from 19 to 22 weight percent, based on the total amount of the random terpolymer. In another embodiment, the content of side groups in the random terpolymer is from 15 to 22% by weight, and according to this embodiment the content of structural units derived from the monovinyl aromatic hydrocarbon is preferably from 14 to 18% by weight, based on the total amount of the random terpolymer.

The content of monovinylarene blocks in the ternary random copolymer according to the present invention is not higher than 0.8 wt.%, preferably not higher than 0.7 wt.%, and may for example be between 0.2 and 0.7 wt.%.

According to the ternary random copolymer of the present invention, the molecular weight of the ternary random copolymer may be appropriately selected depending on the specific use of the ternary random copolymer. In a preferred embodiment, the number average molecular weight (M) of the ternary random copolymer_n) From 7 to 36 million, preferably from 9 to 32 million, the ternary random copolymer according to this preferred embodiment is particularly suitable as a tread rubber for a tire. According to the inventionThe molecular weight distribution of the ternary random copolymer of (1) is narrow, and generally, the molecular weight distribution index (M) of the ternary random copolymer is narrow_w/M_n) May be 1.05 to 1.2, preferably 1.09 to 1.17.

In the present invention, the number average molecular weight and the molecular weight distribution index are measured by Gel Permeation Chromatography (GPC) using monodisperse polystyrene as a standard.

According to a second aspect of the present invention, there is provided a ternary random copolymer composition comprising a first component, and optionally a second component, the first component having a number average molecular weight greater than the number average molecular weight of the second component, wherein the first component and the second component each comprise structural units derived from a conjugated diene comprising a first conjugated diene and a second conjugated diene, and structural units derived from a monovinyl arene, and the first conjugated diene is different from the second conjugated diene.

In a preferred embodiment of the ternary random copolymer composition according to the present invention, said first conjugated diene is butadiene, said second conjugated diene is isoprene and said monovinyl arene is styrene.

The content of structural units derived from the first conjugated diene may be 35 to 65% by weight, preferably 40 to 63% by weight, the content of structural units derived from the second conjugated diene may be 15 to 50% by weight, preferably 19 to 45% by weight, and the content of structural units derived from the monovinyl aromatic hydrocarbon may be 10 to 24% by weight, preferably 14 to 22% by weight, based on the total amount of the ternary random copolymer composition.

According to the ternary random copolymer composition of the present invention, the total amount of the structural unit formed by 1, 2-polymerization of the conjugated diene and the structural unit formed by 3, 4-polymerization is low. Generally, the pendant group content in the ternary random copolymer composition is from 10 to 25% by weight, preferably from 11 to 22% by weight, based on the total amount of structural units derived from the conjugated diene. In one embodiment, the pendant groups are present in the random terpolymer composition in an amount of from 11 to 14 weight percent, such as from 11.5 to 12.5 weight percent, and according to this embodiment, the structural units derived from the monovinyl aromatic hydrocarbon are preferably present in an amount of from 19 to 22 weight percent, based on the total amount of the random terpolymer composition. In another embodiment, the random terpolymer composition has a pendant group content of 15 to 22 weight percent, and according to this embodiment, the structural units derived from the monovinyl aromatic hydrocarbon are preferably present in an amount of 14 to 18 weight percent, based on the total amount of the random terpolymer composition.

According to the ternary random copolymer composition of the present invention, the content of monovinylarene blocks is not higher than 0.8 wt%, preferably not higher than 0.7 wt%, for example, may be 0.2 to 0.7 wt%.

According to the ternary random copolymer composition of the present invention, the number average molecular weight of the first component is greater than the number average molecular weight of the second component. In a preferred embodiment, the number average molecular weight of the first component may be from 30 to 100, preferably from 32 to 95, more preferably from 33 to 76, ten thousand, and the number average molecular weight of the second component may be from 7 to 36, preferably from 9 to 32, ten thousand. The molecular weight distribution index of the first component may be from 1.08 to 1.17, preferably from 1.1 to 1.15; the molecular weight distribution index of the second component may be 1.05 to 1.2, preferably 1.09 to 1.17.

The content of the first component in the ternary random copolymer composition according to the present invention may be 40 to 100% by weight, preferably 45 to 90% by weight, more preferably 48 to 70% by weight, based on the total amount of the composition; the second component may be present in an amount of 0 to 60 wt%, preferably 10 to 55 wt%, more preferably 30 to 52 wt%. In the present invention, the contents of the first component and the second component are measured by gel permeation chromatography.

The ternary random copolymers and ternary random copolymer compositions according to the present invention have a low glass transition temperature. Generally, the glass transition temperature of the ternary random copolymer composition according to the present invention may be between-60 ℃ and-70 ℃. Also, the ternary random copolymer and ternary copolymer composition according to the present invention can obtain a significantly reduced tan delta value of 60 ℃ while maintaining the tan delta value at 0 ℃ at a higher level. At the same time, the rubbers prepared from the inventive ternary random copolymers or ternary random copolymer compositions have a significantly reduced DIN abrasion value. Thus, the ternary random copolymer or ternary random copolymer composition according to the present invention is suitable as a tire tread rubber.

(1) contacting, under anionic polymerization conditions, in the presence of a polar additive, a polymeric monomer in a solvent with an anionic polymerization initiator, the polymeric monomer comprising a conjugated diene and a monovinylarene, the conjugated diene comprising a first conjugated diene and a second conjugated diene, the first conjugated diene being different from the second conjugated diene;

(2) optionally, contacting the mixture obtained by contacting step (1) with a coupling agent under coupling reaction conditions.

According to the process of the invention, the polar additive is selected from the group consisting of compounds of formula II,

In the formula II, C₁-C₅Specific examples of alkyl groups may include, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl.

According to the process of the present invention, the polar additive is preferably 2, 2-bis (3,4, 5-trimethyl-2-tetrahydrofuryl) propane and/or 2, 2-bis (4-methyl-2-tetrahydrofuryl) propane.

In a preferred embodiment, in formula II, R₂、R₃、R₄、R₅、R₆And R₇Each is C₁-C₅An alkyl group. According to this preferred embodiment, the polar additive is preferably 2, 2-bis (3,4, 5-trimethyl-2-tetrahydrofuryl) propane.

The polar additive is commercially available or can be synthesized by conventional methods, and is not described in detail herein.

The polar additive may be added to the polymerization system in a conventional manner. For example, the polar additive may be added together with or separately from the anionic polymerization initiator to a polymerization system containing a monovinylarene and a conjugated diene, and contacted with the monovinylarene and the conjugated diene to perform polymerization. When the polar additive and the anionic polymerization initiator are added to the polymerization system separately, the order of adding the polar additive and the anionic polymerization initiator is not particularly limited, and the polar additive may be added first and then the anionic polymerization initiator may be added, or the anionic polymerization initiator may be added first and then the polar additive may be added. In a preferred embodiment, the polar additive is added first, followed by the anionic polymerization initiator.

According to the process of the present invention, the molar ratio of the polar additive to the anionic polymerization initiator may be 0.01 to 10: 1, the anionic polymerization initiator being, in terms of the amount of the initiation active center which the anionic polymerization initiator is capable of forming, for example: when the anionic polymerization initiator is an organic monolithium compound, the amount is based on the amount of lithium element in the organic monolithium compound. Preferably, the molar ratio of the polar additive to the anionic polymerization initiator is from 0.02 to 6: 1. more preferably, the molar ratio of the polar additive to the anionic polymerization initiator is from 0.03 to 3: 1. further preferably, the molar ratio of the polar additive to the anionic polymerization initiator is from 0.04 to 1.5: 1, for example: 0.04-1: 1. 0.04-0.8: 1. 0.04-0.6: 1. 0.04-0.3: 1. or 0.04-0.2: 1. the molar ratio of the polar additive to the anionic polymerization initiator is more preferably 0.05 to 0.15 from the viewpoint of further reducing the content of monovinylaromatic hydrocarbon blocks in the finally prepared ternary random copolymer, on the premise that the intended content of side groups can be obtained: 1.

according to the method of the present invention, the anionic polymerization initiator may be an initiator generally used in anionic polymerization. In a preferred embodiment of the present invention, the anionic polymerization initiator is selected from at least one organolithium compound. The organic lithium compound may be one or more of organic mono-lithium, organic di-lithium and organic poly-lithium.

The organic single lithium refers to an organic compound which contains a lithium element in a molecular structure and can form an active center to initiate polymerization. Specifically, the organic mono-lithium can be a compound shown in formula III,

R⁸li (formula III)

In the formula III, R⁸Is C₁-C₆Alkyl of (C)₃-C₁₂Cycloalkyl of, C₇-C₁₄Aralkyl or C₆-C₁₂Aryl group of (1).

Said C is₁-C₆Alkyl of (2) includes C₁-C₆Straight chain alkyl of (2) and C₃-C₆Specific examples thereof may include, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl and n-hexyl.

Said C is₃-C₁₂Specific examples of the cycloalkyl group of (a) may include, but are not limited to: cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl and 4-n-butylcyclohexyl.

Said C is₇-C₁₄Specific examples of the aralkyl group of (a) may include, but are not limited to: phenylmethyl, phenylethyl, phenyl-n-propyl, phenyl-n-butyl, phenyl-tertButyl, phenylisopropyl, phenyl-n-pentyl and phenyl-n-hexyl.

Said C is₆-C₁₂Specific examples of the aryl group of (a) may include, but are not limited to: phenyl, naphthyl, 4-methylphenyl and 4-ethylphenyl.

Specific examples of the organic monolithium may include, but are not limited to: ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, n-pentyllithium, n-hexyllithium, cyclohexyllithium, phenyllithium, 2-naphthyllithium, 4-butylphenyl lithium, 4-methylphenyl lithium and 4-butylcyclohexyl lithium.

Preferably, the organo monolithium is butyllithium, such as n-butyllithium and/or sec-butyllithium. More preferably, the organo monolithium is n-butyllithium.

The organic dilithium refers to an organic compound which contains two lithium elements in a molecular structure and can form two active centers to initiate polymerization. Specifically, the organic dilithium can be a compound shown as a formula IV,

Li-R⁹-Li (formula IV)

In the formula IV, R⁹Is C₁-C₁₂Alkylene and C₃-C₁₂A cycloalkylene group of (a).

Said C is₁-C₁₂Alkylene of (A) includes C₁-C₁₂Linear alkylene of (A) and (C)₃-C₁₂Specific examples thereof may include, but are not limited to: methylene, ethylene, propylene, butylene, pentylene, hexylene, octylene, nonylene, decylene, undecylene, and dodecylene.

Said C is₃-C₁₂Specific examples of the cycloalkylene group of (a) may include, but are not limited to: cyclobutyl, cyclopentyl and cyclohexyl.

Specific examples of the organic dilithium may include, but are not limited to: dilithiomethane, 1, 4-dilithiobutane, 1, 10-dilithidecane, and 1, 4-dilithiocyclohexane.

The organic multi-lithium is an organic compound which contains more than three lithium elements in a molecular structure and can form more than three active centers to initiate polymerization. Specifically, the organic poly-lithium may be selected from the group consisting of a compound represented by formula V and a compound represented by formula VI,

R¹⁰Li_n(formula V)

In the formula V, R¹⁰Can be C₄-C₂₀N is the functionality of the initiator and may be an integer from 3 to 30, preferably an integer from 3 to 20, more preferably an integer from 3 to 10;

T(R¹¹Li)_m(formula VI)

In the formula VI, R¹¹Can be C₄-C₂₀A hydrocarbon group of (a); t is Sn, Si, Pb, Ti or Ge; m is dependent on the valence of T.

The organo-polylithium of formula V may also be a polychelant type organo-lithium initiator such as the various polychelant type organo-lithium initiators obtained by reacting Divinylbenzene (DVB) with alkyllithium as described in GB2,124,228A, U.S. Pat. No. 3,280,084, EP0,573,893A2, CN1,197,806A, and the like, which prior art documents are specifically incorporated herein by reference.

In addition, the organolithiums may be other organolithiums having a functionality of not less than 3 that can be used to initiate polymerization of conjugated dienes such as butadiene, isoprene, and styrenic monomers, such as the various polyfunctional organolithiums mentioned in US5,262,213 and US5,595,951, which prior art documents are specifically incorporated herein by reference.

Preferably, the anionic polymerization initiator is organic mono-lithium and/or organic dilithium, more preferably organic mono-lithium, even more preferably butyl lithium such as n-butyl lithium and/or sec-butyl lithium, even more preferably n-butyl lithium.

The amount of the anionic polymerization initiator to be used may be selected depending on the molecular weight of the intended ternary random copolymer. In a preferred embodiment, the anionic polymerization initiator is preferably used in an amount such that the number average molecular weight of the finally prepared ternary random copolymer is from 7 to 36 ten thousand. The amount of the anionic polymerization initiator is more preferably such that the number average molecular weight of the finally produced ternary random copolymer is from 9 to 32 ten thousand. Methods for determining the amount of initiator to be used based on the desired molecular weight of the polymer are well known to those skilled in the art and will not be described in detail herein. The molecular weight distribution index of the ternary random copolymer prepared by the process of the present invention is generally in the range of 1.05 to 1.2, preferably in the range of 1.09 to 1.17. In the invention. "in the range of X to X" includes both endpoints. In the present invention, the amount of the anionic polymerization initiator used is the amount of the anionic polymerization initiator added for initiating the polymerization reaction, and does not include the amount of the anionic polymerization initiator added for removing impurities in the polymerization system before the polymerization reaction is carried out.

The amounts of monovinylarene, first conjugated diene and second conjugated diene used in the process according to the present invention may be selected according to the specific application of the finally prepared ternary random copolymer, and are not particularly limited.

In a preferred embodiment, the monovinylarene may be used in an amount of from 10 to 25 wt%, preferably from 14 to 20 wt%, based on the total amount of monovinylarene and conjugated diene; the content of the first conjugated diene may be from 35 to 65% by weight, preferably from 40 to 62% by weight; the second conjugated diene may be present in an amount of from 15 to 50% by weight, preferably from 20 to 45% by weight.

According to this preferred embodiment, in one example, the monovinylarene is present in an amount of 20 wt%, the first conjugated diene is present in an amount of 40 wt%, and the second conjugated diene is present in an amount of 40 wt%, based on the total amount of monovinylarene and conjugated diene. In another example, the monovinylarene is present in an amount of 14 weight percent, the first conjugated diene is present in an amount of 60 weight percent, and the second conjugated diene is present in an amount of 26 weight percent, based on the total amount of monovinylarene and conjugated diene. In yet another example, the monovinylarene is present in an amount of 15 weight percent, the first conjugated diene is present in an amount of 40 weight percent, and the second conjugated diene is present in an amount of 45 weight percent, based on the total amount of monovinylarene and conjugated diene. In yet another example, the monovinylarene is present in an amount of 18 weight percent, the first conjugated diene is present in an amount of 62 weight percent, and the second conjugated diene is present in an amount of 20 weight percent, based on the total amount of monovinylarene and conjugated diene.

The ternary random copolymer (composition) prepared according to this preferred embodiment is particularly suitable for the preparation of tire tread rubber.

In a preferred embodiment of the process according to the invention, the first conjugated diene is butadiene, the second conjugated diene is isoprene and the monovinylarene is styrene.

According to the process of the present invention, the polymerization is preferably carried out by solution polymerization. The monovinylarene, the first conjugated diene and the second conjugated diene may be contacted with the anionic polymerization initiator and the polar additive in at least one solvent. The solvent may be a common solvent capable of dissolving the monovinylarene, the first conjugated diene, the second conjugated diene, the polar additive and the anionic polymerization initiator as well as the resulting polymer. The solvent may be a non-polar hydrocarbon solvent. Preferably, the solvent is one or more of cycloalkane, aromatic hydrocarbon and alkane. Specifically, the solvent may be one or more of benzene, toluene, hexane, cyclohexane, pentane, heptane, and raffinate oil. The raffinate oil is the distillate oil left after the aromatic hydrocarbon is extracted from the catalytic reforming product rich in the aromatic hydrocarbon in the petroleum refining process. Preferably, the solvent is a mixed solvent of cyclohexane and n-hexane, wherein the weight ratio of cyclohexane to n-hexane is preferably 4-9: 1.

the amount of the solvent used may be selected depending on the amount of the monomer to be polymerized. Generally, the solvent is used in an amount such that the monomer (i.e., monovinylarene, first conjugated diene, and second conjugated diene) concentration is in the range of 5 to 30 weight percent, preferably in the range of 10 to 20 weight percent.

According to the process of the present invention, the contacting of the monovinylarene and the conjugated diene with the anionic polymerization initiator and the polar additive may be carried out under conventional anionic polymerization conditions, without particular limitation. In general, the reaction temperature and the reaction pressure can be selected and varied within wide limits. In order to more favorably carry out the polymerization reaction, the addition temperature of the anionic polymerization initiator (i.e., initiation temperature) is preferably 20 to 75 ℃, more preferably 40 to 70 ℃. During the polymerization reaction, the heat of reaction may be removed either without or with the exception of the heat of reaction. The polymerization temperature can be controlled to 40 to 95 ℃ by heat exchange with the polymerization system through a heat exchange medium while the heat of reaction is removed, preferably to not higher than 90 ℃ such as 45 to 90 ℃. The polymerization reaction is preferably carried out at a pressure of 0.05 to 1MPa, more preferably 0.1 to 0.3MPa, the pressure being a gauge pressure. The time for the polymerization reaction can be selected depending on the polymerization temperature, and may be generally 10 to 120min, preferably 30 to 90 min.

According to the process of the present invention, step (2) is an optional operation, and step (2) may or may not be carried out to couple at least part of the polymer chains formed by the polymerization of step (1). When organic mono-lithium and/or organic di-lithium is used as the anionic polymerization initiator in step (1), step (2) is preferably performed to couple at least part of the polymer chains.

The coupling agent may be of conventional choice. Generally, the coupling agent may be one or more than two of polyvinyl compounds, halides, ethers, aldehydes, ketones, and esters. Specific examples of the coupling agent may include, but are not limited to: one or more than two of divinylbenzene, dimethyldichlorosilane, methyltrichlorosilane, tetravinylsilane, tetrachloromethane, silicon tetrachloride, stannic chloride, diethyl adipate, dimethyl adipate and dimethyl terephthalate. Preferably, the coupling agent is one or more than two of divinylbenzene, silicon tetrachloride and tin tetrachloride. More preferably, the coupling agent is silicon tetrachloride and/or tin tetrachloride.

The amount of coupling agent may be selected according to the desired coupling efficiency. Generally, the coupling agent is used in an amount such that the coupled polymer content of the coupled ternary random copolymer is from 40 to 100% by weight, preferably from 45 to 90% by weight, more preferably from 48 to 70% by weight; the content of the uncoupled polymer is from 0 to 60% by weight, preferably from 10 to 55% by weight, more preferably from 30 to 52% by weight. That is, the coupling agent is used in an amount such that the coupling efficiency is 40 to 100%, preferably 45 to 90%, more preferably 48 to 70%.

In the step (2), the coupling agent and the coupling reaction conditions are preferably such that the number average molecular weight of the coupled polymer is from 30 to 100 ten thousand, more preferably such that the number average molecular weight of the coupled polymer is from 32 to 95 ten thousand, and further preferably such that the number average molecular weight of the coupled polymer is from 33 to 76 ten thousand. The polymers before and after coupling may be subjected to gel permeation chromatography to determine the content of coupled and uncoupled polymers.

Methods for determining the specific amount of coupling agent based on the desired coupling polymer content and the type of coupling agent used are well known to those skilled in the art and will not be described in detail herein.

In step (2), the mixture obtained by contacting in step (1) and the coupling agent may be contacted under conditions sufficient to react the coupling agent with the polymer chains. Generally, the mixture obtained by the contacting in step (1) and the coupling agent may be contacted at a temperature of 20 to 70 ℃, preferably 25 to 65 ℃.

According to the method of the invention, the polymerization and optionally the coupling reaction are carried out in an atmosphere formed by an inert gas. The inert gas refers to a gas that does not chemically interact with the reactants, the reaction products, and the solvent, for example: nitrogen and/or a group zero gas (e.g., argon).

According to the process of the present invention, after the contact reaction of the monovinylarene and the conjugated diene with the anionic polymerization initiator and the polar additive, and optionally the coupling reaction, is completed, at least one polymerization terminator may be added to the resulting mixture to inactivate the living end groups.

The polymerization terminator may be any of various substances capable of terminating a living chain, which are generally used in the field of anionic polymerization, and may be, for example, water and/or an alcohol. The amount of the polymerization terminator used in the present invention is not particularly limited as long as the amount of the polymerization terminator is sufficient to deactivate the active center. In the actual operation, the amount of the polymerization terminator to be used may be determined depending on the amount of the anionic polymerization initiator to be used. In general, the molar ratio of the polymerization terminator to the anionic polymerization initiator may be from 0.1 to 2: 1, preferably 0.2 to 1.5: 1.

according to the method of the present invention, after the polymerization reaction is terminated by adding the polymerization terminator, one or more than two kinds of auxiliaries may be added to the resulting mixture according to specific needs, so as to impart new properties to the finally prepared ternary random copolymer and/or improve the properties of the finally prepared ternary random copolymer.

In particular, the auxiliary agent may include an anti-aging agent. The type of the antioxidant in the present invention is not particularly limited, and various antioxidants conventionally used in the art may be used. For example, the antioxidant may be a phenolic and/or an aminic antioxidant. Specifically, the antioxidant may be one or more of 4, 6-dioctylthiomethyl-o-cresol, pentaerythritol tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], tris (2, 4-di-tert-butylphenyl) phosphite, octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 2, 6-di-tert-butyl-p-cresol, tert-butyl catechol, and 2, 2' -methylene-bis (4-methyl-6-tert-butylphenol). When pentaerythritol tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] is used in a mixture with tris (2, 4-di-tert-butylphenyl) phosphite, the content of tris (2, 4-di-tert-butylphenyl) phosphite is preferably not more than 50% by weight; when octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and tris (2, 4-di-tert-butylphenyl) phosphite are used in combination, the content of tris (2, 4-di-tert-butylphenyl) phosphite is preferably not more than 50% by weight.

The amount of the antioxidant may be an amount conventionally used in the art. For example, the antioxidant may be used in an amount of 0.005 to 2 parts by weight, preferably 0.1 to 1 part by weight, based on 100 parts by weight of the copolymer.

According to the method of the present invention, the mixture obtained by the polymerization reaction or the coupling reaction may be purified and separated by a conventional method to obtain a ternary random copolymer or a ternary random copolymer composition. Specifically, the resulting mixture may be subjected to centrifugal separation, filtration, decantation or hot water coagulation to obtain a ternary random copolymer or a ternary random copolymer composition; the resulting mixture may also be stripped to remove the solvent therefrom to provide a ternary random copolymer or ternary random copolymer composition.

The process of the present invention may be carried out by a batch polymerization method or a continuous polymerization method, and is not particularly limited.

According to the method of the invention, when the monovinylarene and the conjugated diene are subjected to random copolymerization under the condition of anionic polymerization, the compound shown in the formula II is used as a polar additive, the microstructure of the copolymer can be effectively adjusted, and the content of the monovinylarene block can still be controlled in a lower range on the premise of obtaining lower side group content.

The ternary random copolymers and ternary random copolymer compositions according to the present invention exhibit lower glass transition temperatures. In the case of a ternary random copolymer composition, the glass transition temperature may be between-60 ℃ and-70 ℃. Also, the ternary random copolymer and ternary random copolymer composition according to the present invention can obtain a significantly reduced tan delta value at 60 ℃ while maintaining the tan delta value at 0 ℃ at a higher level. At the same time, the rubbers prepared from the inventive ternary random copolymers or ternary random copolymer compositions have a significantly reduced DIN abrasion value. Thus, the ternary random copolymers and ternary random copolymer compositions according to the present invention are suitable as tire tread compounds.

Thus, according to a fifth aspect of the present invention, there is provided the use of a terpolymer according to the first aspect of the present invention, a terpolymer composition according to the second aspect of the present invention, a terpolymer according to the fourth aspect of the present invention or a terpolymer composition according to the fourth aspect of the present invention in a tread rubber for a tire.

The present invention will be described in detail with reference to examples, but the scope of the present invention is not limited thereto.

In the following examples and comparative examples, the number average molecular weight (M)_n) Molecular weight distribution index (M)_w/M_n) Andcoupling efficiency was determined by ALLIANCE 2690 Gel Permeation Chromatography (GPC) using Tetrahydrofuran (THF) as the mobile phase, 25 ℃ column temperature and narrow polystyrene as the standard.

In the following examples and comparative examples, the microstructure of the polymer before coupling was determined using an AVANCE DRX 400MHz NMR spectrometer from Bruker, Switzerland, using deuterated chloroform as solvent.

In the following examples and comparative examples, the glass transition temperature (T)_g) Measured using a differential thermal analyzer commercially available from TA corporation of America under the model number TA 2910DSC with a temperature rise rate of 10 ℃/min and a scanning temperature range of-100 ℃ to 100 ℃.

In the following examples and comparative examples, the loss factor (tan. delta.) was measured using a model DMA-2980 viscoelastic spectrometer manufactured by TA of USA, with a frequency of 2Hz, a temperature rise rate of 5 ℃/min, a test temperature range of-120 ℃ to 100 ℃, and a sample size of 40mm × 5mm × 1mm, using a three-point bending mode. The half-width is the difference between the two temperatures at which tan δ is half the maximum.

In the following examples and comparative examples, the mechanical properties were measured by the method specified in GB/T528-1998 using Shimadzu AG-20KNG tensile machine, and the samples used were type I samples.

In the following examples and comparative examples, DIN abrasion was measured according to the method specified in Chinese national Standard GB/T9867-2008 for the measurement of abrasion resistance of vulcanized rubber (rotating drum abrader method).

In the following examples and comparative examples, the samples used for the determination of the dissipation factor, mechanical properties and Mooney viscosity were prepared by vulcanization according to the A series of formulations in GB/T8656-1998, under vulcanization conditions comprising: mixing raw rubber by using an open mill, and mixing at the roll temperature of 50 +/-5 ℃; the vulcanization temperature is 145 ℃, the pressure is more than 10MPa, and the vulcanization time is 35 minutes.

In the following examples and comparative examples, the polymerization monomers and the reaction solvent were refined by a conventional method before use, and the polymerization system was sterilized by a conventional method before initiation of polymerization; the pressures are gauge pressures.

Examples 1-7 serve to illustrate the invention.

Example 1

The polymerization was carried out in a 5 liter stainless steel stirred tank reactor, as follows.

(1) Under the protection of high-purity nitrogen, 2288g of a mixed solvent (a mixed solution of cyclohexane and n-hexane, the mass ratio of cyclohexane/n-hexane is 82/18), 62.4g of styrene (ST, the same below), 124.8g of butadiene (BD, the same below) and 124.8g of isoprene (IP, the same below) were added, 2-bis (3,4, 5-trimethyl-2-tetrahydrofuryl) propane (DTMTP, the amount thereof is shown in Table 1) was added, and the reaction kettle was opened to stir (the rotation speed was set to 200rpm) to uniformly mix the materials. And then heating the reaction materials by using a circulating water bath, killing impurities by using an n-butyl lithium initiator when the temperature in the reaction kettle rises to 50 ℃, adding 3.33mmol of n-butyl lithium to initiate polymerization, controlling the polymerization reaction temperature below 90 ℃ and the pressure within the range of 0.1-0.3MPa in the polymerization reaction process, and reacting for 60min (the conversion rate of styrene, butadiene and isoprene is about 100 percent by detection).

(2) 0.73mmol of silicon tetrachloride is added for coupling reaction at 65 ℃, and after coupling for 30min, 3.99mmol of isopropanol is added once to terminate the reaction. Then 3.12g of an antioxidant 1520 (commercially available from Ciba, Switzerland) was added and mixed well to obtain a ternary random copolymer composition of the present invention, the molecular weight, microstructure, physical mechanical properties and dynamic mechanical properties data of which are shown in Table 1.

Examples 2 to 4

A ternary random copolymer composition was prepared in the same manner as in example 1, except that polymerization was carried out under the polymerization conditions shown in Table 1.

Comparative example 1

A ternary random copolymer composition was prepared in the same manner as in example 1, except that 2, 2-bis (3,4, 5-trimethyl-2-tetrahydrofuryl) propane was used in an amount of 0 (i.e., 2, 2-bis (3,4, 5-trimethyl-2-tetrahydrofuryl) propane was not used).

Comparative example 2

A ternary random copolymer composition was prepared in the same manner as in example 1, except that 2, 2-bis (3,4, 5-trimethyl-2-tetrahydrofuryl) propane was replaced with an equimolar amount of Tetrahydrofuran (THF).

Comparative example 3

A ternary random copolymer composition was prepared in the same manner as in example 1, except that 2, 2-bis (3,4, 5-trimethyl-2-tetrahydrofuryl) propane was replaced with tetrahydrofuran in the amount shown in Table 2.

Comparative example 4

A ternary random copolymer composition was prepared in the same manner as in example 1, except that 2, 2-bis (3,4, 5-trimethyl-2-tetrahydrofuryl) propane was replaced with an equimolar amount of tetrahydrofurfuryl ethyl ether (ETE).

Comparative example 5

A ternary random copolymer composition was prepared in the same manner as in example 1, except that 2, 2-bis (3,4, 5-trimethyl-2-tetrahydrofuryl) propane was replaced with tetrahydrofurfuryl ethyl ether (ETE) in the amount shown in Table 2.

Comparative example 6

A ternary random copolymer composition was prepared in the same manner as in example 1, except that 2, 2-bis (3,4, 5-trimethyl-2-tetrahydrofuryl) propane was replaced with an equimolar amount of bistetrahydrofurfuryl propane (DTHFP).

Comparative example 7

A ternary random copolymer composition was prepared in the same manner as in example 1, except that 2, 2-bis (3,4, 5-trimethyl-2-tetrahydrofuryl) propane was replaced with bistetrahydrofurfuryl propane (DTHFP) in the amount shown in Table 2.

Comparative example 8

A ternary random copolymer composition was prepared in the same manner as in example 1, except that 2, 2-bis (3,4, 5-trimethyl-2-tetrahydrofuryl) propane was replaced with ditetrahydrofurfuryl propane (DTHFP) and Sodium Dodecylbenzenesulfonate (SDBS), and the amounts thereof were as shown in Table 2.

TABLE 1

TABLE 2

¹: due to the high styrene block content in the terpolymer, samples for measuring physical and mechanical properties and dynamic mechanical properties cannot be prepared.

Comparing example 1 with comparative examples 1-8, it can be seen that the ternary random copolymer (composition) prepared by the anionic polymerization process of the present invention not only has a low side group content, but also can maintain the styrene block content at a low level. Rubber samples prepared from the ternary random copolymer composition according to the present invention, showing a significantly lower glass transition temperature, are able to obtain a significantly reduced tan delta value of 60 ℃ while keeping the tan delta value of 0 ℃ at a higher level.

Comparative examples 1,2, 4 and 6, while also achieving lower pendant group content, did not allow for effective control of styrene block content, resulting in the production of terpolymers having too high a styrene micro-block content. Comparative examples 3,5, 7 and 8, although the styrene block content was effectively controlled to a low level, the side group content of the prepared terpolymer was too high.

Meanwhile, as can be seen from the physical and mechanical property data of Table 1, DIN abrasion values of rubber samples prepared from the terpolymer composition according to the present invention are significantly reduced, indicating that the rubber samples prepared from the terpolymer composition according to the present invention have significantly improved abrasion resistance.

Example 5

(1) 2288g of a mixed solvent (a mixed solution of cyclohexane and n-hexane, the cyclohexane/n-hexane mass ratio being 82/18), 43.7g of styrene, 187.2g of butadiene and 81.1g of isoprene were added under the protection of high-purity nitrogen gas, and then 2, 2-bis (3,4, 5-trimethyl-2-tetrahydrofuryl) propane (DTMTP, the amount thereof is shown in table 3) was added, and the reaction vessel was opened and stirred (the rotation speed was set at 200rpm) to uniformly mix the materials. And then heating the reaction materials by using a circulating water bath, killing impurities by using an n-butyl lithium initiator when the temperature in the reaction kettle rises to 45 ℃, adding 1.55mmol of n-butyl lithium to initiate polymerization, controlling the polymerization temperature below 90 ℃ and the pressure within the range of 0.1-0.3MPa in the polymerization reaction process, and reacting for 60min (the conversion rate of styrene, butadiene and isoprene is about 100 percent by detection).

(2) 0.34mmol of silicon tetrachloride is added for coupling reaction at 25 ℃, and after coupling for 30min, 1.86mmol of isopropanol is added once to terminate the reaction. Then 3.12g of anti-aging agent 1520 (commercially available from Ciba, Switzerland) was added and mixed well to obtain a ternary random copolymer composition of the present invention, the molecular weight, microstructure, physical mechanical properties and dynamic mechanical properties data of which are shown in Table 3.

Example 6

A ternary random copolymer composition was prepared in the same manner as in example 5, except that 2, 2-bis (3,4, 5-trimethyl-2-tetrahydrofuryl) propane was replaced with an equimolar amount of 2, 2-bis (4-methyl-2-tetrahydrofuryl) propane (DMTP), and polymerization was carried out under the conditions shown in Table 3.

Comparative example 9

A ternary random copolymer composition was prepared in the same manner as in example 5, except that 2, 2-bis (3,4, 5-trimethyl-2-tetrahydrofuryl) propane was replaced with an equimolar amount of bistetrahydrofurfuryl propane (DTHFP).

Comparative example 10

A ternary random copolymer composition was prepared in the same manner as in example 5, except that 2, 2-bis (3,4, 5-trimethyl-2-tetrahydrofuryl) propane was used in an amount of 0 (i.e., 2, 2-bis (3,4, 5-trimethyl-2-tetrahydrofuryl) propane was not used).

Example 7

(1) 2288g of a mixed solvent (a mixed solution of cyclohexane and n-hexane, the cyclohexane/n-hexane mass ratio being 90/10), 56.2g of styrene, 193.4g of butadiene and 62.4g of isoprene were added under the protection of high-purity nitrogen gas, 2-bis (3,4, 5-trimethyl-2-tetrahydrofuryl) propane (DTMTP, used in the amount shown in table 3) was added, and the reaction vessel was opened and stirred (the rotation speed was set at 200rpm) to uniformly mix the materials. And then heating the reaction materials by using a circulating water bath, killing impurities by using an n-butyl lithium initiator when the temperature in the reaction kettle rises to 41 ℃, adding 1.98mmol of n-butyl lithium to initiate polymerization, controlling the polymerization reaction temperature below 85 ℃ and the pressure within the range of 0.1-0.3MPa in the polymerization reaction process, and reacting for 60min (the conversion rate of styrene, butadiene and isoprene is about 100 percent by detection).

(2) 0.44mmol of silicon tetrachloride is added for coupling reaction at 25 ℃, and 2.38mmol of isopropanol is added once after coupling for 30min to terminate the reaction. Then 3.12g of anti-aging agent 1520 (commercially available from Ciba, Switzerland) was added and mixed well to obtain a ternary random copolymer composition of the present invention, the molecular weight, microstructure, physical mechanical properties and dynamic mechanical properties data of which are shown in Table 3.

Comparative example 11

A ternary random copolymer composition was prepared in the same manner as in example 7, except that 2, 2-bis (3,4, 5-trimethyl-2-tetrahydrofuryl) propane was replaced with an equimolar amount of bistetrahydrofurfuryl propane (DTHFP).

Comparative example 12

A ternary random copolymer composition was prepared in the same manner as in example 7, except that 2, 2-bis (3,4, 5-trimethyl-2-tetrahydrofuryl) propane was used in an amount of 0 (i.e., 2, 2-bis (3,4, 5-trimethyl-2-tetrahydrofuryl) propane was not used).

TABLE 3

The results of examples 5-7 demonstrate that the use of the process of the present invention to produce a ternary random copolymer not only results in a lower pendant group content, but also allows the styrene block content of the polymer to be controlled at a lower level. Also, the rubber samples prepared from the inventive terpolymer composition exhibited significantly lower glass transition temperatures, and significantly reduced tan delta values at 60 ℃ were obtained while maintaining the tan delta values at 0 ℃ at higher levels, while the DIN abrasion values were significantly reduced, indicating that the rubber samples prepared from the inventive terpolymer composition had significantly improved abrasion 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

1. A ternary random copolymer comprising structural units derived from a conjugated diene and structural units derived from a monovinyl aromatic hydrocarbon, said conjugated diene comprising a first conjugated diene and a second conjugated diene, and said first conjugated diene being different from said second conjugated diene;

taking the total amount of the ternary random copolymer as a reference, the content of a side group in the ternary random copolymer is 10-25 wt%, wherein the side group content refers to the content of a structural unit which contains an ethylenic side group and is derived from conjugated diene in the ternary random copolymer by taking the total amount of the ternary random copolymer as the reference;

2. The ternary random copolymer according to claim 1, wherein the content of structural units derived from the first conjugated diene is from 40 to 63% by weight, the content of structural units derived from the second conjugated diene is from 19 to 45% by weight, and the content of structural units derived from the monovinyl aromatic hydrocarbon is from 14 to 22% by weight, based on the total amount of the ternary random copolymer.

3. The random terpolymer according to claim 1, wherein the random terpolymer has a pendant group content of from 11 to 22 wt.%, based on the total amount of the random terpolymer.

4. The ternary random copolymer according to claim 1, wherein the content of monovinylarene blocks is from 0.2 to 0.7 wt%, based on the total amount of the ternary random copolymer.

5. The random terpolymer according to claim 1, wherein the random terpolymer has a number average molecular weight of 7 to 36 ten thousand.

6. The random terpolymer according to claim 1, wherein the random terpolymer has a number average molecular weight of 9 to 32 ten thousand.

7. The ternary random copolymer according to any one of claims 1, 5 and 6, wherein the molecular weight distribution index of the ternary random copolymer is from 1.05 to 1.2.

8. The ternary random copolymer according to any one of claims 1, 5 and 6, wherein the molecular weight distribution index of the ternary random copolymer is from 1.09 to 1.17.

9. The ternary random copolymer according to any of claims 1 to 6, wherein the first conjugated diene and the second conjugated diene are each selected from butadiene, isoprene, 1, 3-hexadiene and 2, 3-dimethylbutadiene;

the monovinylarene is selected from a compound shown in a formula I,

in the formula I, R₁Is C₆-C₂₀Substituted or unsubstituted aryl of (a).

10. The ternary random copolymer according to any of claims 1 to 6, wherein the first conjugated diene is butadiene, the second conjugated diene is isoprene and the monovinylarene is styrene.

11. A ternary random copolymer composition comprising a first component, and optionally a second component, said first component having a number average molecular weight greater than the number average molecular weight of said second component, characterized in that said first component and said second component each contain structural units derived from a conjugated diene and structural units derived from a monovinyl arene, said conjugated diene comprising a first conjugated diene and a second conjugated diene, and said first conjugated diene being different from said second conjugated diene;

the side group content is 10-25 wt% based on the total amount of the ternary random copolymer composition, and the side group content refers to the content of a structural unit which contains an ethylenic side group and is derived from conjugated diene in the composition based on the total amount of the composition;

12. The random terpolymer composition of claim 11 wherein the structural units derived from the first conjugated diene are present in an amount of from 40 to 63 weight percent, the structural units derived from the second conjugated diene are present in an amount of from 19 to 45 weight percent, and the structural units derived from the monovinyl aromatic hydrocarbon are present in an amount of from 14 to 22 weight percent, based on the total amount of the random terpolymer composition.

13. The random terpolymer composition of claim 11 wherein the pendant group content is from 11 to 22 weight percent, based on the total amount of the random terpolymer composition.

14. The random terpolymer composition of claim 11 wherein the monovinylarene block is present in an amount of from 0.2 to 0.7 weight percent, based on the total amount of the random terpolymer composition.

15. The random terpolymer composition of claim 11, wherein the first component has a number average molecular weight of 30 to 100 ten thousand and the second component has a number average molecular weight of 7 to 36 ten thousand.

16. The random terpolymer composition of claim 11, wherein the first component has a number average molecular weight of 32 to 95 ten thousand and the second component has a number average molecular weight of 9 to 32 ten thousand.

17. The ternary random copolymer composition of claim 11, wherein the number average molecular weight of the first component is from 33 to 76 ten thousand.

18. The random terpolymer composition of any of claims 11 and 15-17, wherein the molecular weight distribution index of the first component is from 1.08 to 1.17 and the molecular weight distribution index of the second component is from 1.05 to 1.2.

19. The ternary random copolymer composition of any of claims 11 and 15-17, wherein the first component has a molecular weight distribution index of from 1.1 to 1.15 and the second component has a molecular weight distribution index of from 1.09 to 1.17.

20. The random terpolymer composition according to any of claims 11 and 15-17, wherein the first component is present in an amount of 40-100 wt% and the second component is present in an amount of 0-60 wt%, based on the total amount of the random terpolymer composition.

21. The random terpolymer composition according to any of claims 11 and 15-17, wherein the first component is present in an amount of 45-90 wt% and the second component is present in an amount of 10-55 wt%, based on the total amount of the random terpolymer composition.

22. The random terpolymer composition according to any of claims 11 and 15-17, wherein the first component is present in an amount of 48-70 wt% and the second component is present in an amount of 30-52 wt%, based on the total amount of the random terpolymer composition.

23. The ternary random copolymer composition according to any of claims 11 to 17, wherein the first component is a coupled polymer.

24. The ternary random copolymer composition of any of claims 11-17, wherein the first conjugated diene and the second conjugated diene are each selected from butadiene, isoprene, 1, 3-hexadiene, and 2, 3-dimethylbutadiene;

the monovinylarene is selected from a compound shown in a formula I,

in the formula I, R₁Is C₆-C₂₀Substituted or unsubstituted aryl of (a).

25. The ternary random copolymer composition of any of claims 11-17, wherein the first conjugated diene is butadiene, the second conjugated diene is isoprene, and the monovinyl arene is styrene.

26. An anionic polymerization process for preparing the ternary random copolymer of claim 1, comprising:

characterized in that the polar additive is selected from compounds represented by formula II,

27. An anionic polymerization process for preparing the ternary random copolymer composition of claim 11, comprising:

(2) under the condition of coupling reaction, contacting the mixture obtained by contacting in the step (1) with a coupling agent,

28. The method of claim 26 or 27, wherein, in formula II, R₂、R₃、R₄、R₅、R₆And R₇Each is C₁-C₅An alkyl group.

29. The process according to claim 26 or 27, wherein the polar additive is 2, 2-bis (3,4, 5-trimethyl-2-tetrahydrofuryl) propane and/or 2, 2-bis (4-methyl-2-tetrahydrofuryl) propane.

30. The method of claim 26 or 27, wherein the polar additive is 2, 2-bis (3,4, 5-trimethyl-2-tetrahydrofuryl) propane.

31. The process according to claim 26 or 27, wherein the molar ratio of the polar additive to the anionic polymerization initiator is from 0.01 to 10: 1, the anionic polymerization initiator being based on the amount of the initiation active center which the anionic polymerization initiator is capable of forming.

32. The process according to claim 26 or 27, wherein the molar ratio of the polar additive to the anionic polymerization initiator is from 0.02 to 6: 1, the anionic polymerization initiator being based on the amount of the initiation active center which the anionic polymerization initiator is capable of forming.

33. The process according to claim 26 or 27, wherein the molar ratio of the polar additive to the anionic polymerization initiator is from 0.03 to 3: 1, the anionic polymerization initiator being based on the amount of the initiation active center which the anionic polymerization initiator is capable of forming.

34. The process according to claim 26 or 27, wherein the molar ratio of the polar additive to the anionic polymerization initiator is from 0.05 to 0.15: 1, the anionic polymerization initiator being based on the amount of the initiation active center which the anionic polymerization initiator is capable of forming.

35. The process according to claim 26 or 27, wherein the anionic polymerization initiator is used in an amount such that the number average molecular weight of the ternary random copolymer is from 7 to 36 ten thousand.

36. The process according to claim 26 or 27, wherein the anionic polymerization initiator is used in an amount such that the number average molecular weight of the ternary random copolymer is from 9 to 32 ten thousand.

37. The method according to claim 26 or 27, wherein the anionic polymerization initiator is selected from compounds of formula III,

R⁸li (formula III)

38. The process of claim 26 or 27, wherein the anionic polymerization initiator is butyl lithium.

39. The process according to claim 26 or 27, wherein the anionic polymerization initiator is n-butyllithium.

40. The process of claim 26 or 27, wherein the first conjugated diene is present in an amount of from 35 to 65 wt%, the second conjugated diene is present in an amount of from 15 to 50 wt%, and the monovinyl aromatic hydrocarbon is present in an amount of from 10 to 25 wt%, based on the total amount of polymerized monomers.

41. The process of claim 26 or 27, wherein the first conjugated diene is present in an amount of 40 to 62 weight percent, the second conjugated diene is present in an amount of 20 to 45 weight percent, and the monovinylarene is present in an amount of 14 to 20 weight percent, based on the total amount of polymerized monomers.

42. The process of claim 26 or 27, wherein the first and second conjugated dienes are each selected from butadiene, isoprene, 1, 3-hexadiene, and 2, 3-dimethylbutadiene;

the monovinylarene is selected from a compound shown in a formula I,

in the formula I, R₁Is C₆-C₂₀Substituted or unsubstituted aryl of (a).

43. The process of claim 26 or 27, wherein the first conjugated diene is butadiene, the second conjugated diene is isoprene, and the monovinylarene is styrene.

44. The process of claim 26 or 27, wherein the anionic polymerization conditions comprise: the initiation temperature is 20-75 ℃; removing reaction heat or not removing the reaction heat in the polymerization reaction process, and controlling the polymerization temperature to be 40-95 ℃ when the reaction heat is removed; the polymerization is carried out at a pressure of from 0.05 to 1MPa, said pressure being a gauge pressure.

45. The method of claim 44, wherein the anionic polymerization conditions comprise: the initiation temperature is 40-70 ℃.

46. The process as claimed in claim 44, wherein the polymerization temperature is controlled to 45-90 ℃ while the heat of reaction is removed.

47. The process of claim 44, wherein the polymerization is carried out at a pressure of 0.1 to 0.3MPa, said pressure being gauge pressure.

48. The method of claim 27, wherein in step (2), the contacting is at a level such that the coupling efficiency is from 40 to 100%.

49. The method of claim 27, wherein in step (2), the contacting is at a level such that the coupling efficiency is 45-90%.

50. The method of claim 27, wherein in step (2), the contacting is at a level such that the coupling efficiency is 48-70%.

51. The method of any of claims 27 and 48-50, wherein the coupling agent is one or more selected from divinylbenzene, dimethyldichlorosilane, methyltrichlorosilane, tetravinylsilane, tetrachloromethane, silicon tetrachloride, tin tetrachloride, diethyl adipate, dimethyl adipate, and dimethyl terephthalate.

52. The method of any of claims 27 and 48-50, wherein the coupling agent is tin tetrachloride and/or silicon tetrachloride.

53. Use of the ternary random copolymer according to any one of claims 1 to 10, or the ternary random copolymer composition according to any one of claims 11 to 25, in a tread band for a tire.