CN114516929A - Ethylene copolymer, process for producing the same, composition, crosslinked polymer, and tire - Google Patents
Ethylene copolymer, process for producing the same, composition, crosslinked polymer, and tire Download PDFInfo
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- CN114516929A CN114516929A CN202011311765.9A CN202011311765A CN114516929A CN 114516929 A CN114516929 A CN 114516929A CN 202011311765 A CN202011311765 A CN 202011311765A CN 114516929 A CN114516929 A CN 114516929A
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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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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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
- C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
- C08F2410/03—Multinuclear procatalyst, i.e. containing two or more metals, being different or not
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
Abstract
The invention discloses an ethylene copolymer and a preparation method thereof, and a composition, a cross-linked polymer and a tire containing the ethylene copolymer, wherein the ethylene copolymer contains an ethylene structural unit derived from ethylene and a conjugated diene structural unit derived from conjugated diene, the content of the conjugated diene structural unit is 25-45 mol% based on the total amount of the ethylene copolymer, the content of a 1, 2-polymerized vinyl structural unit formed by a 1, 2-polymerization mode and having a side chain double bond is 20-40 mol%, the total amount of the 1, 2-polymerized structural unit is more than 95 mol% based on the total amount of the conjugated diene structural unit in the ethylene copolymer, and the weight average molecular weight of the ethylene copolymer is 20,000-300,000. The ethylene copolymer according to the present invention has good crosslinking properties.
Description
Technical Field
The present invention relates to an ethylene copolymer and a method for preparing the same, and more particularly, to an ethylene copolymer containing a structural unit derived from ethylene and a structural unit derived from a conjugated diene and a method for preparing the same; the invention also relates to a composition comprising said ethylene copolymer and to a crosslinked polymer comprising units derived from said ethylene copolymer; the invention further relates to a tyre, at least one constituent element of which comprises said ethylene copolymer, said composition or said crosslinked polymer.
Background
Ethylene is widely used in the plastics industry as a monomer which is used in large quantities and is readily available. Conjugated dienes, particularly butadiene and isoprene, are the most important monomers for the synthesis of rubber. Butadiene, a by-product of the petroleum route to ethylene, was once at a price similar to ethylene. Recently, the price of butadiene has increased dramatically due to the decrease in the production of butadiene resulting from the change in the ethylene production route. In contrast, the price of ethylene is reduced. Therefore, the use of ethylene as a raw material for the production of rubber for tires is attractive, and the raw material cost can be greatly saved.
However, copolymerization is difficult due to the different polymerization mechanisms of the conjugated diene and the α -olefin. Therefore, the copolymerization of ethylene and conjugated diene by using the same catalytic system is a very challenging subject, and the realization of the copolymerization of ethylene and conjugated diene is always the direction of the academic and industrial efforts.
The existing method for copolymerizing ethylene and conjugated diene mainly has the problems that the content of conjugated diene structural units in the prepared polymer is not high, and the content of unsaturated bonds in the main chain of the prepared polymer is high, so that the physical properties of the copolymer, such as weather resistance, heat resistance, ozone resistance and the like, are improved.
Therefore, it is highly desirable to develop a polymerization process suitable for copolymerizing ethylene and conjugated diene to improve the catalytic activity, the molecular weight of the polymer and the content of the conjugated diene structural units in the polymer.
Disclosure of Invention
The invention aims to provide an ethylene copolymer containing conjugated diene structural units derived from conjugated diene, which has a high content of conjugated diene structural units, and also has a high content of 1, 2-polymerized vinyl structural units of the conjugated diene formed in a 1, 2-polymerization manner and having side-chain double bonds, and simultaneously has a low content of unsaturated bonds in the main chain of the copolymer.
According to a first aspect of the present invention, there is provided an ethylene copolymer comprising an ethylene structural unit derived from ethylene and a conjugated diene structural unit derived from a conjugated diene, the content of the conjugated diene structural unit being 25 to 45 mol% based on the total amount of the ethylene copolymer, the content of a 1, 2-polymerized vinyl structural unit formed by 1, 2-polymerization and having a side chain double bond being 20 to 40 mol%, the total amount of the 1, 2-polymerized structural unit being 95 mol% or more based on the total amount of the conjugated diene structural unit in the ethylene copolymer, the weight average molecular weight of the ethylene copolymer being 20,000 to 300,000.
According to a second aspect of the present invention, there is provided a process for producing an ethylene copolymer, which comprises contacting ethylene with a conjugated diene in the presence of a polymerization catalyst comprising component A and component B,
the component A is selected from metal compounds shown in a formula 1,
in formula 1, M is a metal atom selected from group IVB,
X1and X2Identical or different, each independently a halogen atom,
rb is a divalent group containing a group IVA element,
L1and L2The same or different, each independently selected from the group represented by formula 3 to formula 6,
in the formula 3, RA 1、RA 2、RA 3、RA 4And RA 5Are the same or different and are each independently a hydrogen atom or C1-C20The alkyl group of (a) is,
in the formula 4, RB 1、RB 2、RB 3、RB 4And RB 5Are the same or different and are each independently a hydrogen atom or C1-C20The alkyl group of (a) is,
in the formula 5, RC 1、RC 2、RC 3And RC 4Are the same or different and are each independently a hydrogen atom or C1-C20The alkyl group of (a) is,
in the formula 6, RD 1、RD 2、RD 3And RD 4Are the same or different and are each independently a hydrogen atom or C1-C20Alkyl groups of (a);
the component B is aluminoxane.
According to a third aspect of the present invention there is provided an ethylene copolymer produced by the process of the second aspect of the present invention.
According to a fourth aspect of the present invention there is provided a composition comprising an ethylene copolymer according to the first or third aspects of the present invention and a cross-linking agent.
According to a fifth aspect of the present invention, there is provided a crosslinked polymer comprising units derived from the ethylene copolymer according to the first or third aspect of the present invention.
According to a sixth aspect of the present invention, there is provided a tire having at least one constituent element comprising the ethylene copolymer according to the first or third aspect of the present invention, the composition according to the fourth aspect of the present invention, or the crosslinked polymer according to the fifth aspect of the present invention.
The ethylene copolymer has high content of conjugated diene structural units, high content of 1, 2-polymerized vinyl structural units and low content of unsaturated double bonds in the main chain of the copolymer. The ethylene copolymer according to the present invention has good crosslinking properties, and the crosslinked product is good in weatherability, heat resistance and ozone resistance. The ethylene copolymer has wide application prospect in the field of rubber, in particular to the field of vehicle tire rubber.
According to the preparation method of the ethylene copolymer, not only can the ethylene copolymer be prepared, but also the improved catalytic activity can be obtained, so that the production efficiency is improved, and the preparation method is suitable for industrial scale application.
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.
According to a first aspect of the present invention, there is provided an ethylene copolymer comprising ethylene structural units derived from ethylene and conjugated diene structural units derived from a conjugated diene.
In the present invention, "structural unit derived from ethylene" means that the structural unit is formed of ethylene, and the atomic species and the number of each atom are the same as compared with ethylene except that the electronic structure is changed; "structural unit derived from a conjugated diene" means that the structural unit is formed of a conjugated diene, and the atomic species and the number of each atom are the same as compared with the conjugated diene except that the electronic structure is changed.
According to the ethylene copolymer of the present invention, the conjugated diene refers to a compound having a conjugated double bond in a molecular structure. The conjugated diene may be one or more compounds selected from the group consisting of compounds represented by formula 11,
in formula 11, R3、R4And R5Same or different, each selected from hydrogen and C1-C5Linear or branched alkyl.
Specific examples of the conjugated diene according to the ethylene copolymer of the present invention may include, but are not limited to, butadiene and/or isoprene. Preferably, the conjugated diene is butadiene.
The ethylene copolymer according to the present invention may contain the conjugated diene structural unit in an amount of 25 to 45 mol%, for example, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44 or 45 mol% based on the total amount of the ethylene copolymer. Preferably, the content of the conjugated diene structural unit is 25 to 40 mol% based on the total amount of the ethylene copolymer. More preferably, the content of the conjugated diene structural unit is 30 to 35 mol% based on the total amount of the ethylene copolymer.
According to the ethylene copolymer of the present invention, the conjugated diene structural unit is substantially a 1, 2-polymerized structural unit of a conjugated diene formed by 1, 2-polymerization, and therefore, the ethylene copolymer according to the present invention has a high content of the 1, 2-polymerized structural unit and a low content of unsaturated double bonds in the main chain of the copolymer. The ethylene copolymer according to the present invention has a total amount of the 1, 2-polymerized structural unit of 95 mol% or more, preferably 98 mol% or more, and more preferably 100 mol% based on the total amount of the conjugated diene units in the ethylene copolymer. The ethylene copolymer according to the present invention has a double bond content in the main chain of the ethylene copolymer of generally 5 mol% or less, preferably 2 mol% or less, more preferably 0 mol%. The double bond in the main chain of the ethylene copolymer may be derived from a structural unit formed by 1, 4-polymerization or 1, 3-polymerization of a conjugated diene, for example.
In the present invention, the 1, 2-polymerized structural unit means a structural unit in which a conjugated diene is polymerized in a 1, 2-manner (i.e., 1, 2-addition manner), the 1, 4-polymerized structural unit means a structural unit in which a conjugated diene is polymerized in a 1, 4-manner (i.e., 1, 4-addition manner), and the 1, 3-polymerized structural unit means a structural unit in which a conjugated diene is polymerized in a 1, 3-manner (i.e., 1, 3-addition manner).
According to the ethylene copolymer of the present invention, the 1, 2-polymerized structural unit includes a 1, 2-polymerized vinyl structural unit in which the conjugated diene is formed in a 1, 2-polymerization manner and which has a side chain double bond, a 1, 2-cyclopropane ring structural unit in which the conjugated diene is formed in a 1, 2-polymerization manner and which has a cyclopropane ring, and a 1, 5-cyclopentane ring structural unit in which the conjugated diene is formed in a 1, 2-polymerization manner and which has a cyclopentane ring.
Taking butadiene as an example, the 1, 2-polymerized vinyl structural unit is shown as a formula 14, the 1, 2-cyclopropane ring structural unit is shown as a formula 15, and the 1, 5-cyclopentane ring structural unit is shown as a formula 16:
according to the ethylene copolymer of the present invention, the conjugated diene is formed in a 1, 2-polymerization manner and the 1, 2-polymerized vinyl structural unit having a side chain double bond is high. The content of 1, 2-polymerized vinyl structural units (i.e. the vinyl content) is from 20 to 40 mol%, based on the total amount of the ethylene copolymer according to the invention, and may be, for example, 20, 20.5, 21, 21.5, 22, 22.5, 23, 23.5, 24, 24.5, 25, 25.5, 26, 26.5, 27, 27.5, 28, 28.5, 29, 29.5, 30, 30.5, 31, 31.5, 32, 32.5, 33, 33.5, 34, 34.5, 35, 35.5, 36, 36.5, 37, 37.5, 38, 38.5, 39, 39.5 or 40 mol%. Preferably, the content of the 1, 2-polymerized vinyl structural units is from 20 to 35 mol%, based on the total amount of the ethylene copolymer according to the invention. More preferably, the content of the 1, 2-polymerized vinyl structural units is from 21 to 30 mol%, based on the total amount of the ethylene copolymer according to the invention.
The ethylene copolymer according to the present invention may have a content of the 1, 2-polymerized vinyl structural unit of 55% or more, preferably 55 to 90%, based on the total amount of the conjugated diene structural units in the ethylene copolymer, for example: 55. 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, or 90%. Preferably, the content of the 1, 2-polymerized vinyl structural unit is 60 to 88% based on the total amount of the conjugated diene structural units in the ethylene copolymer. More preferably, the content of the 1, 2-polymerized vinyl structural unit is 63 to 85% based on the total amount of the conjugated diene structural units in the ethylene copolymer.
The ethylene copolymer according to the present invention has a molar ratio of 1, 2-cyclopentane ring structural units to 1, 2-cyclopropane ring structural units in conjugated diene structural units of 0.1 to 3: 1, preferably 0.3 to 2.5: 1, more preferably 0.4 to 2: 1, more preferably 0.5 to 1.8: 1.
in the present invention, the microstructure composition of the ethylene copolymer is measured by a nuclear magnetic resonance spectroscopy.
The ethylene copolymer according to the present invention has not only a higher content of 1, 2-polymerized vinyl structural units but also a higher molecular weight. The weight average molecular weight (M) of the ethylene copolymers according to the inventionw) Is 20,000 to 300,000, preferably 25,000 to 250,000, more preferably 30,000 to 200,000, further preferably 40,000 to 150,000. The ethylene copolymer according to the present invention, the molecular weight distribution index (M) of the ethylene copolymerw/Mn) Is 3.5 or less, preferably 3.2 or less, more preferably 1.5 to 3.
In the present invention, the molecular weight (in g/mol) and the molecular weight distribution index are measured by Gel Permeation Chromatography (GPC) using monodisperse polystyrene as a standard.
Ethylene copolymers according to the invention, the glass transition temperature (T) of the ethylene copolymersg) May be in the range of-50 ℃ to-15 ℃, preferably in the range of-40 ℃ to-20 ℃.
In the present invention, the glass transition temperature is measured by Differential Scanning Calorimetry (DSC).
According to a second aspect of the present invention, there is provided a process for preparing an ethylene copolymer, which comprises contacting ethylene with a conjugated diene in the presence of a polymerization catalyst.
According to the preparation method of the present invention, the conjugated diene refers to a compound having a conjugated double bond in a molecular structure. The conjugated diene may be one or more compounds selected from the group consisting of compounds represented by formula 11,
in the formula 11, R3、R4And R5Same or different, each selected from hydrogen and C1-C5Linear or branched alkyl.
Specific examples of the conjugated diene according to the preparation method of the present invention may include, but are not limited to, butadiene and/or isoprene. Preferably, the conjugated diene is butadiene.
According to the production method of the present invention, the polymerization catalyst contains component a and component B.
The component A is selected from metal compounds shown in a formula 1,
in formula 1, M is a metal atom selected from group IVB, and may be a titanium atom, a zirconium atom or a hafnium atom. Preferably, in formula 1, M is a zirconium atom.
In formula 1, X1And X2The same or different, each independently a halogen atom. Preferably, in formula 1, X1And X2Are all chlorine atoms.
In formula 1, Rb is a divalent group of a group IVA element. In formula 1, Rb is preferably a divalent group containing silicon, more preferably a divalent group represented by formula 2,
in the formula 2, R1And R2Identical or different, each independently is C1-C10Alkyl group of (1). Said C is1-C10Alkyl of (2) includes C1-C10Straight chain alkyl of (1), C3-C10Branched alkyl of (2) and C3-C10Specific examples thereof may include, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl and its various isomers, hexyl and its various isomers, heptyl and its various isomers, octyl and its various isomers, nonyl and its various isomers, decyl and its various isomers, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
Preferably, in formula 2, R1And R2Are all methyl.
In the formula 1, L1And L2The same or different, each independently selected from the group represented by formula 3 to formula 6,
in formula 3, RA 1、RA 2、RA 3、RA 4And RA 5Are the same or different and are each independently a hydrogen atom or C1-C20Alkyl group of (1).
In the present invention, C1-C20Alkyl of (2) includes C1-C20Straight chain alkyl group of (1), C3-C20Branched alkyl and C3-C20Specific examples thereof may include, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl and its various isomers, hexyl and its various isomers, heptyl and its various isomers, octyl and its various isomers, nonyl and its various isomers, decyl and its various isomers, undecyl and its various isomers, dodecyl and its various isomers, tridecyl and its various isomers, tetradecyl and its various isomers, pentadecyl and its various isomers, hexadecyl and its various isomers, heptadecyl and its various isomers, octadecyl and its various isomers, nonadecyl and its various isomers, eicosyl and its various isomers, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
In one embodiment, in formula 3, RA 1、RA 2、RA 3、RA 4And RA 5And are simultaneously hydrogen atoms.
In another embodiment, in formula 3, RA 1、RA 2、RA 3、RA 4And RA 5Each independently is a hydrogen atom or C1-C20And R is alkyl ofA 1、RA 2、RA 3、RA 4And RA 5Not simultaneously hydrogen atoms. In this embodiment, RA 1、RA 2、RA 3、RA 4And RA 5At least one (preferably two) of (a) are preferably C1-C10More preferably C1-C6Further preferably C1-C3More preferably methyl, the remaining groups being hydrogen atoms.
In the formula 4, RB 1、RB 2、RB 3、RB 4And RB 5Are the same or different and are each independently a hydrogen atom or C1-C20Alkyl group of (1).
In one embodiment, in formula 4, RB 1、RB 2、RB 3、RB 4And RB 5And are simultaneously hydrogen atoms.
In another embodiment, in formula 4, RB 1、RB 2、RB 3、RB 4And RB 5Each independently is a hydrogen atom or C1-C20And R is alkyl ofB 1、RB 2、RB 3、RB 4And RB 5Not both being hydrogen atoms, in this embodiment RB 1、RB 2、RB 3、RB 4And RB 5At least one (preferably two, more preferably R)B 2And RB 4) Preferably C1-C10More preferably C1-C6Further preferably C1-C3More preferably methyl, the remaining groups being hydrogen atoms.
In the formula 5, RC 1、RC 2、RC 3And RC 4Are the same or different and are each independently a hydrogen atom or C1-C20Alkyl group of (1).
In a preferred embodiment, in formula 5, RC 1、RC 2、RC 3And RC 4At least one (preferably two, more preferably R)C 1And RC 3) Is C1-C20Is preferably C1-C6More preferably C1-C3The alkyl group of (3) is more preferably a methyl group, an ethyl group, an n-propyl group or an isopropyl group, and the remaining groups are hydrogen atoms. According to this preferred embodiment, in a more preferred example, RC 1Is methyl, RC 3Is ethyl or n-propyl, RC 2And RC 4Is a hydrogen atom.
In the formula 6, RD 1、RD 2、RD 3And RD 4Are the same or different and are each independently a hydrogen atom or C1-C20Alkyl group of (1).
In a preferred embodiment, in formula 6, RD 1、RD 2、RD 3And RD 4At least one (preferably two, more preferably R)D 1And RD 3) Is C1-C20Is preferably C1-C6More preferably C1-C3The alkyl group of (3) is more preferably a methyl group, an ethyl group, an n-propyl group or an isopropyl group, and the remaining groups are hydrogen atoms. According to this preferred embodiment, in a more preferred example, RD 1Is methyl, RD 3Is ethyl or n-propyl, RD 2And RD 4Is a hydrogen atom.
According to the production method of the present invention, the component a is preferably one or two or more selected from metal compounds represented by formulae 7 to 10:
in a more preferred embodiment, the component A is a metal compound selected from the group consisting of those represented by formula 7 and formula 8. According to this more preferred embodiment, the process according to the present invention can not only increase the content of the conjugated diene structural units derived from the conjugated diene and the structural units of the conjugated diene formed in a 1, 2-polymerization manner in the ethylene copolymer, but also obtain higher catalytic activity and produce an ethylene copolymer having a higher molecular weight.
In another more preferred embodiment, the component A is a metal compound selected from the group consisting of those represented by formula 9 and formula 10. According to this more preferred embodiment, the process according to the invention allows more conjugated diolefins to be polymerized in a 1, 2-polymerization mode under conditions such that a higher catalytic activity is obtained, thus obtaining ethylene copolymers having a higher content of 1, 2-polymerized structural units.
According to the production method of the present invention, the metal compound as the component a may be commercially available or may be produced by a conventional method.
According to the preparation method of the present invention, the component B contains aluminoxane, preferably contains organic aluminoxane, and more preferably contains methylaluminoxane. In a preferred embodiment, the component B is an aluminoxane, preferably an organoaluminoxane, more preferably methylaluminoxane.
According to the preparation method of the present invention, the molar ratio of the component a to the component B may be 1: 0.1 to 5000, preferably 1: 1-3000, more preferably 1: 1 to 1000, more preferably 1: 10-1000, more preferably 1: 100-800.
According to the production process of the present invention, the component A may be used in an amount of 0.1 to 100. mu. mol, preferably 1 to 80. mu. mol, more preferably 3 to 60. mu. mol, further preferably 5 to 30. mu. mol, relative to 1mol of the conjugated diene.
According to the production process of the present invention, the contact of ethylene with a conjugated diene may be carried out at a temperature of-50 ℃ to 150 ℃, preferably at a temperature of 10 ℃ to 120 ℃, more preferably at a temperature of 30 ℃ to 90 ℃, and further preferably at a temperature of 40 ℃ to 70 ℃. According to the production process of the present invention, when ethylene is contact-polymerized with a conjugated diene, the pressure of ethylene may be from 0 to 100MPa, preferably from 2 to 50MPa, more preferably from 3 to 30MPa, further preferably from 5 to 10MPa, in terms of gauge pressure (G).
According to the production method of the present invention, the contacting is carried out in the presence of a molecular weight modifier in an amount such that the weight average molecular weight of the produced olefin polymer is 20,000 to 300,000, preferably 25,000 to 250,000, more preferably 30,000 to 200,000, further preferably 40,000 to 150,000. The molecular weight regulator may be of conventional choice, preferably hydrogen.
According to the preparation method of the present invention, the solution polymerization can be performed. In solution polymerization, solvents that may be employed include C6-C12Of aromatic hydrocarbons, C6-C12Halogenated aromatic hydrocarbon of (1), C5-C10Linear alkane of (1) and C5-C10Cycloalkanes of (a), for example: one or more of toluene, chlorobenzene, dichlorobenzene, n-hexane and cyclohexane.
According to a third aspect of the present invention there is provided an ethylene copolymer produced by the process of the second aspect of the present invention.
The ethylene copolymer produced by the process according to the second aspect of the present invention has not only a high content of the conjugated diene structural unit but also a high content of the structural unit formed by 1, 2-polymerization of the conjugated diene, so that the ethylene copolymer according to the third aspect of the present invention has a low content of unsaturated double bonds in the molecular main chain and has good weather resistance, heat resistance and ozone resistance. More importantly, the ethylene copolymer according to the third aspect of the present invention has a higher content of 1, 2-polymerized vinyl structural units, and thus the ethylene copolymer according to the third aspect of the present invention has more excellent vulcanization properties, shows a faster vulcanization rate and a higher vulcanization degree.
The content of the conjugated diene structural unit is 20 to 45 mol%, for example, may be 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44 or 45 mol% based on the total amount of the ethylene copolymer according to the third aspect of the present invention. Preferably, the conjugated diene structural unit is contained in an amount of 25 to 40 mol% based on the total amount of the ethylene copolymer according to the third aspect of the present invention. More preferably, the content of the conjugated diene structural unit is 30 to 35 mol% based on the total amount of the ethylene copolymer according to the third aspect of the present invention.
According to the ethylene copolymer of the third aspect of the present invention, the conjugated diene structural unit is substantially a 1, 2-polymerized structural unit of a conjugated diene formed by 1, 2-polymerization. The total amount of the 1, 2-polymerized structural units is 95 mol% or more, preferably 98 mol% or more, and more preferably 100 mol% based on the total amount of conjugated diene units in the ethylene copolymer. The ethylene copolymer according to the third aspect of the present invention has a double bond content in the main chain of the ethylene copolymer of generally 5 mol% or less, preferably 2 mol% or less, more preferably 0 mol%.
According to the ethylene copolymer of the third aspect of the present invention, the 1, 2-polymerized structural unit includes a 1, 2-polymerized vinyl structural unit in which a conjugated diene is formed in a 1, 2-polymerization manner and which has a side chain double bond, a 1, 2-cyclopropane ring structural unit in which a conjugated diene is formed in a 1, 2-polymerization manner and which has a cyclopropane ring, and a 1, 5-cyclopentane ring structural unit in which a conjugated diene is formed in a 1, 2-polymerization manner and which has a cyclopentane ring. The content of 1, 2-polymerized vinyl structural units is from 18 to 40 mol%, based on the total amount of the ethylene copolymer according to the third aspect of the present invention, and may be, for example, 18, 18.5, 19, 19.5, 20, 20.5, 21, 21.5, 22, 22.5, 23, 23.5, 24, 24.5, 25, 25.5, 26, 26.5, 27, 27.5, 28, 28.5, 29, 29.5, 30, 30.5, 31, 31.5, 32, 32.5, 33, 33.5, 34, 34.5, 35, 35.5, 36, 36.5, 37, 37.5, 38, 38.5, 39, 39.5 or 40 mol%. Preferably, the 1, 2-polymerized vinyl structural units are present in an amount of from 20 to 35 mol%, based on the total amount of the ethylene copolymer according to the third aspect of the present invention. More preferably, the 1, 2-polymerized vinyl structural units are present in an amount of 21 to 30 mol%, based on the total amount of the ethylene copolymer according to the third aspect of the present invention.
The content of the 1, 2-polymerized vinyl structural units may be up to 55% or more, preferably 55 to 90%, based on the total amount of conjugated diene structural units in the ethylene copolymer according to the third aspect of the present invention, for example: 55. 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, or 90%. Preferably, the content of the 1, 2-polymerized vinyl structural unit is from 60 to 88% based on the total amount of conjugated diene structural units in the ethylene copolymer according to the third aspect of the present invention. More preferably, the content of the 1, 2-polymerized vinyl structural unit is from 63 to 85% based on the total amount of conjugated diene structural units in the ethylene copolymer according to the third aspect of the present invention.
The ethylene copolymer according to the third aspect of the present invention has a molar ratio of 1, 2-cyclopentane ring structural units to 1, 2-cyclopropane ring structural units in conjugated diene structural units of 0.1 to 3: 1, preferably 0.3 to 2.5: 1, more preferably 0.4 to 2: 1, more preferably 0.5 to 1.8: 1.
the weight average molecular weight (M) of the ethylene copolymer according to the third aspect of the present inventionw) May be 20,000 to 300,000, preferably 25,000 to 250,000, more preferably 30,000 to 200,000, and further preferably 40,000 to 150,000. The ethylene copolymer according to the third aspect of the present invention, which has a molecular weight distribution index (M)w/Mn) Is 3.5 or less, preferably 3.2 or less, more preferably 1.5 to 3.
An ethylene copolymer according to the third aspect of the present invention, which has a glass transition temperature (T)g) May be in the range of-50 ℃ to-15 ℃, preferably in the range of-40 ℃ to-20 ℃.
According to a fourth aspect of the present invention there is provided a composition comprising an ethylene copolymer and a cross-linking agent, wherein the ethylene copolymer is an ethylene copolymer according to the first or third aspect of the present invention.
The crosslinking agent may be a material sufficient to crosslink vinyl groups in the ethylene copolymer. Specifically, the crosslinking agent may be one or more of sulfur, sulfur monochloride, selenium, tellurium, and peroxide. In a preferred embodiment, the crosslinking agent is a peroxide, such as: dicumyl peroxide.
The composition according to the present invention may further contain a vulcanization accelerator to promote vulcanization, thereby shortening the vulcanization time, lowering the vulcanization temperature and reducing the amount of the vulcanizing agent used. The vulcanization accelerator may be a commonly used substance capable of achieving the above-described functions, such as: triallyl isocyanurate. The compositions according to the invention may also contain, depending on the specific requirements, other components, such as: one or two or more of an antioxidant and a filler, and preferred examples of the filler may include, but are not limited to, carbon black.
According to a fifth aspect of the present invention, there is provided a crosslinked polymer formed by crosslinking the ethylene copolymer according to the first aspect of the present invention or the third aspect of the present invention. The ethylene copolymer according to the first or third aspect of the present invention may be contacted with a crosslinking agent to carry out a crosslinking reaction, thereby obtaining a crosslinked polymer according to the fifth aspect of the present invention.
According to a sixth aspect of the present invention, there is provided a tire having at least one constituent element comprising the ethylene copolymer according to the first aspect of the present invention, the composition according to the fourth aspect of the present invention, or the crosslinked polymer according to the fifth aspect of the present invention.
The present invention is described in detail below with reference to examples, but the scope of the present invention is not limited thereby.
In the following examples and comparative examples, the molecular weight and molecular weight distribution index (M) of the polymerw/Mn) The measurement was carried out by 1260Infinity II high temperature gel permeation chromatograph manufactured by Agilent corporation using 2 columns (300X 7.5mm) of MIXD-B and 1 column (50X 7.5mm) of Guard. The mobile phase is trichlorobenzene, and the flow rate is 1 mL/min; the concentration of the sample solution is 1mg/mL, and the sample injection amount is 200 mu L; the test temperature is 150 ℃; monodispersed polystyrene was used as a standard.
In the following examples and comparative examples, the microstructure of the polymer was measured using a 400MHz NMR spectrometer commercially available from Bruker, using deuterated o-dichlorobenzene as a solvent and Tetramethylsilicon (TMS) as an internal standard. Wherein "conjugated diene structural unit" means a structural unit formed of conjugated diene, "1, 2-polymerization" means that conjugated diene is polymerized in a 1, 2-addition manner, "1, 4-polymerization" means that conjugated diene is polymerized in a 1, 4-addition manner, "1, 3-polymerization" means that conjugated diene is polymerized in a 1, 3-addition manner; "vinyl" refers to a structural unit of a conjugated diene that is formed by 1, 2-polymerization and has a pendant double bond (in the case of butadiene, vinyl is
) The term "cyclopropane ring" means a structural unit in which a conjugated diene is formed by 1, 2-polymerization and which has a cyclopropane ring (in the case of butadiene, the cyclopropane ring is
) "Cyclopentane ring" means a structural unit in which a conjugated diene is formed by 1, 2-polymerization and which has a cyclopentane ring (in the case of butadiene, the cyclopentane ring is
)。
The following examples and comparative examples relate to the following metal compounds and comparative metal compounds.
Preparation examples 1 to 4 were used for preparing metal compounds 1 to 4.
Preparation example 1
Synthesis of Metal Compound 1
0.94g (2mmol) of bis (2, 5-dimethylcyclopentylthiophene) -dimethylsilyl and 50mL of diethyl ether are placed in a reaction flask and 2.5mL (4mmol) of a 1.6M solution of butyllithium in hexane are added dropwise at-78 ℃. After stirring at room temperature (25 ℃ C.) for 6 hours, the temperature was lowered to-40 ℃ C, and 0.466g (2mmol) of zirconium tetrachloride was slowly added. Stir overnight. Filter and wash the solid with ether. The product was recrystallized from dichloromethane. Yield: 45% by weight.
H1-NMR(CDCl3,400MHz)：δppm 6.75(q,4H)，2.51(d,12H)，1.82(s,6H)。
Preparation example 2
Synthesis of Metal Compound 4
The same synthesis method as that of the metal compound 1 is adopted, except that the bis (2, 5-dimethylcyclopentylthiophene) -dimethyl silicon is replaced by 2mmol of bis (cyclopentylthiophene) -dimethyl silicon. Yield: 57% by weight.
H1-NMR(CDCl3,400MHz)：δppm 7.15(d,4H)，7.10(d,4H)，1.80(s,6H)。
Preparation example 3
Synthesis of Metal Compound 2.
Into a reaction flask were added 1.02g (2mmol) of bis (2-methyl-5-n-propyl-3- (9-phenanthryl) -6-hydro-cyclopenta [2,3-b ] thiophene-6) -dimethylsilyl ether and 50mL of diethyl ether, and 2.5mL (4mmol) of 1.6M butyllithium hexane solution was added dropwise at-78 ℃. After stirring at room temperature (25 ℃ C.) for 6 hours, 0.466g (2mmol) of zirconium tetrachloride was slowly added. Stir overnight. Filter and wash the solid with ether. And (4) pumping the filtrate to obtain a target product. Yield: 56% by weight.
H1-NMR(CDCl3,400MHz)：δppm 7.15-8.90(m,18H)，6.62(s,2H)，1.15-2.95(m,14H)，1.08(s,6H)，0.92(t,6H)。
Preparation example 4
Synthesis of Metal Compound 3
The same synthesis as for metal compound 5 was used, except that 2mmol of bis (2, 5-dimethyl-3-phenyl-6-hydro-cyclopenta [2,3-b ] thiophene-6) -dimethylsilyl was used instead of bis (2, 5-dimethyl-3-phenyl-6-hydro-cyclopenta [2,3-b ] thiophene-6) -dimethylsilyl. Yield: 61 wt%.
H1-NMR(CDCl3,400MHz)：δppm 7.10-8.85(m,18H)，6.60(s,2H)，1.85-2.80(m,10H)，1.10(s,6H)，0.85(s,6H)。
Examples 1-6 are intended to illustrate the ethylene polymers and the process for their preparation according to the invention.
Example 1
A500 mL stainless steel reactor was sufficiently purged with nitrogen and then purged with hydrogen, and 120g of toluene, 8mL of methylaluminoxane (10% by weight toluene solution), 25.0g of butadiene and 0.44kg/cm of butadiene were added2G hydrogen. At 60 ℃ with a volume of 7.8kg/cm2G ethylene saturates the liquid and gas phases. Thereafter, 5. mu. mol of the metal compound 1 dissolved in toluene in advance was added to start the polymerization. Ethylene gas was continuously supplied so that the total pressure was maintained at 7.8kg/cm2G. After 15 minutes of polymerization, the reaction was terminated by adding a small amount of methanol. The product was precipitated by pouring into a large amount of ethanol with hydrochloric acid (HCl concentration 2% by weight), the solid was separated by filtration, and the separated solid was washed with ethanol. The washed solid was dried in a vacuum oven until the weight was no longer reduced to give an ethylene copolymer according to the present invention. Specific experimental conditions are listed in table 1 and the results of the property parameter tests of the prepared ethylene copolymers are listed in table 2.
Comparative example 1
An ethylene copolymer was prepared in the same manner as in example 1, except that methylaluminoxane was not used, but 2.5mL of a triisobutylaluminum in n-hexane solution (concentration of triisobutylaluminum is 1M) was used, and 0.03mmol of trityl-tetrakis (pentafluorophenyl) borate was dissolved in toluene together with the metal compound 1 and added to the polymerization reaction vessel. Specific experimental conditions are listed in table 1 and the results of the property parameter tests of the prepared ethylene copolymers are listed in table 2.
Comparative example 2
An ethylene copolymer was prepared in the same manner as in comparative example 1, except that the metal compound 1 was replaced with the comparative metal compound 1. Specific experimental conditions are listed in table 1, and the results of the property parameter tests of the ethylene copolymers prepared are listed in table 2.
Comparative example 3
An ethylene copolymer was prepared in the same manner as in example 1, except that the metal compound 1 was replaced with the comparative metal compound 1. Specific experimental conditions are listed in table 1, and the results of the property parameter tests of the ethylene copolymers prepared are listed in table 2.
Example 2
An ethylene copolymer was prepared in the same manner as in example 1, except that: the metal compound 1 was replaced with the metal compound 2, and the properties of the ethylene copolymer obtained were as listed in Table 2.
Comparative example 4
An ethylene copolymer was prepared in the same manner as in example 2, except that methylaluminoxane was not used, but 2.5mL of a triisobutylaluminum in n-hexane solution (concentration of triisobutylaluminum is 1M) was used, and 0.03mmol of trityl-tetrakis (pentafluorophenyl) borate was dissolved in toluene together with the metal compound 2 and added to the polymerization reaction vessel. The specific experimental conditions are listed in table 1 and the results of the property parameter tests of the ethylene copolymers prepared are listed in table 2.
Comparative example 5
An ethylene copolymer was prepared in the same manner as in example 2, except that the metal compound 2 was replaced with the comparative metal compound 2. Specific experimental conditions are listed in table 1, and the results of the property parameter tests of the ethylene copolymers prepared are listed in table 2.
Example 3
A500 mL stainless steel autoclave was fully purged with nitrogen and then purged with hydrogen, and 120g of toluene, 7.5mL of MAO (10 wt% in toluene), 35g of butadiene were added to the autoclave, followed by addition of 0.44kg/cm2G hydrogen gas, 7.8kg/cm at 60 DEG C2G ethylene saturates the liquid and gas phases. Thereafter, 5. mu. mol of the metal compound 2 dissolved in toluene in advance was added to start the polymerization. Ethylene gas was continuously supplied so that the total pressure was maintained at 7.8kg/cm2G. After 15 minutes of polymerization, the reaction was terminated by adding a small amount of methanol. Will be provided withThe product is poured into a large amount of ethanol (2% by weight, hydrochloric acid in HCl) with hydrochloric acid, precipitated, filtered to separate the copolymer, and washed with ethanol. Drying in a vacuum oven until the weight is no longer reduced gives the ethylene copolymers according to the invention. Specific experimental conditions are listed in table 1, and the results of the property parameter tests of the ethylene copolymers prepared are listed in table 2.
Comparative example 6
An ethylene copolymer was prepared in the same manner as in example 4 except that the metal compound 2 was replaced with the comparative metal compound 2. Specific experimental conditions are listed in table 1, and the results of the property parameter tests of the ethylene copolymers prepared are listed in table 2.
Example 4
An ethylene copolymer was prepared in the same manner as in example 1, except that the metal compound 1 was replaced with the metal compound 3. Specific experimental conditions are listed in table 1, and the results of the property parameter tests of the ethylene copolymers prepared are listed in table 2.
Comparative example 7
An ethylene copolymer was prepared in the same manner as in example 4, except that methylaluminoxane was not used, but 2.5mL of a triisobutylaluminum in n-hexane solution (concentration of triisobutylaluminum is 1M) was used, and 0.03mmol of trityl-tetrakis (pentafluorophenyl) borate was dissolved in toluene together with the metal compound 3 and added to the polymerization reaction vessel. Specific experimental conditions are listed in table 1, and the results of the property parameter tests of the ethylene copolymers prepared are listed in table 2.
Comparative example 8
An ethylene copolymer was prepared in the same manner as in example 4 except that the metal compound 3 was replaced with the comparative metal compound 3. Specific experimental conditions are listed in table 1, and the results of the property parameter tests of the ethylene copolymers prepared are listed in table 2.
Comparative example 9
An ethylene copolymer was prepared in the same manner as in example 4 except that the metal compound 3 was replaced with the comparative metal compound 3. Specific experimental conditions are listed in table 1, and the results of the property parameter tests of the ethylene copolymers prepared are listed in table 2.
Example 5
An ethylene copolymer was prepared in the same manner as in example 1, except that the metal compound 1 was replaced with a metal compound 4. Specific experimental conditions are listed in table 1, and the results of the property parameter tests of the ethylene copolymers prepared are listed in table 2.
Comparative example 10
An ethylene copolymer was prepared in the same manner as in example 5, except that methylaluminoxane was not used, but 2.5mL of a triisobutylaluminum in n-hexane solution (concentration of triisobutylaluminum is 1M) was used, and 0.03mmol of trityl-tetrakis (pentafluorophenyl) borate was dissolved in toluene together with the metal compound 4 and added to the polymerization reaction vessel. Specific experimental conditions are listed in table 1, and the results of the property parameter tests of the ethylene copolymers prepared are listed in table 2.
Comparative example 11
An ethylene copolymer was prepared in the same manner as in example 5 except that the metal compound 4 was replaced with the comparative metal compound 4. The specific experimental conditions are listed in table 1 and the results of the property parameter tests of the ethylene copolymers prepared are listed in table 2.
Example 6
An ethylene copolymer was prepared in the same manner as in example 1, except that the metal compound 1 was replaced with a metal compound 4. Specific experimental conditions are listed in table 1, and the results of the property parameter tests of the ethylene copolymers prepared are listed in table 2.
Comparative example 12
An ethylene copolymer was produced in the same manner as in example 9 except that the metal compound 4 was replaced with the comparative metal compound 5. Specific experimental conditions are listed in table 1, and the results of the property parameter tests of the ethylene copolymers prepared are listed in table 2.
Comparative example 13
An ethylene copolymer was produced in the same manner as in example 9 except that the metal compound 4 was replaced with the comparative metal compound 6. Specific experimental conditions are listed in table 1, and the results of the property parameter tests of the ethylene copolymers prepared are listed in table 2.
TABLE 1
The results of Table 2 confirm that the ethylene copolymer according to the present invention has not only an increased molecular weight and a narrow molecular weight distribution index but also an increased content of conjugated diene structural units, while the main chain of the ethylene copolymer is substantially free from unsaturated groups. The results of table 2 also confirm that according to the olefin polymerization process of the present invention, not only the ethylene copolymer according to the present invention can be prepared, but also an improved catalyst activity can be obtained, thereby improving the production efficiency.
Test examples 1 to 2
The ethylene copolymers prepared in examples 2 and 4 were blended on a roll mill with carbon black, peroxide and a vulcanization aid according to the formulations shown in Table 3, respectively. The vulcanization characteristics of the blend were tested at 160 ℃ using an MDR vulcameter from alpha technologies for a 20 minute time period to evaluate the vulcanization rate. The test results are listed in table 4.
Testing of comparative examples 1-2
The ethylene copolymers prepared in comparative examples 5 and 9 were respectively tested for vulcanization characteristics in the same manner as in test examples 1-2, and the test results are shown in Table 4.
TABLE 3
TABLE 4
| Numbering | Test example 1 | Comparative test example 1 | Test example 2 | Comparative test example 2 |
| tc10(min) | 0.5 | 1.1 | 0.7 | 0.9 |
| tc90(min) | 8.5 | 13.2 | 8.6 | 12.1 |
| MH(dNm) | 92.3 | 45.1 | 90.5 | 56.8 |
| ML(dNm) | 0.5 | 0.6 | 0.5 | 0.7 |
As can be seen from the results of the vulcanization characteristics test in Table 4, the ethylene copolymer according to the present invention undergoes a faster rise in torque upon vulcanization, has a faster vulcanization rate and a higher degree of vulcanization.
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 various technical features being combined 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 (22)
1. An ethylene copolymer comprising an ethylene structural unit derived from ethylene and a conjugated diene structural unit derived from a conjugated diene, the content of the conjugated diene structural unit being 25 to 45 mol% based on the total amount of the ethylene copolymer, the content of a 1, 2-polymerized vinyl structural unit formed by 1, 2-polymerization of a conjugated diene and having a side chain double bond being 20 to 40 mol%, the total amount of the 1, 2-polymerized structural unit being 95 mol% or more based on the total amount of the conjugated diene structural unit in the ethylene copolymer, the ethylene copolymer having a weight average molecular weight of 20,000 to 300,000.
2. The ethylene copolymer according to claim 1, wherein the content of the 1, 2-polymerized vinyl structural units is from 20 to 35 mol%, preferably from 21 to 30 mol%, based on the total amount of the ethylene copolymer.
3. An ethylene copolymer as claimed in claim 1 or 2, wherein the content of said 1, 2-polymerized vinyl structural units is from 55 to 90%, preferably from 60 to 88%, more preferably from 63 to 85%, based on the content of said conjugated diene structural units.
4. The ethylene copolymer according to any one of claims 1 to 3, wherein the total amount of the 1, 2-polymerized structural units is 98 mol% or more, preferably 100 mol%, based on the total amount of conjugated diene structural units in the ethylene copolymer.
5. Ethylene copolymer according to any one of claims 1 to 4, wherein the conjugated diene structural units are present in an amount of from 25 to 40 mol%, preferably from 30 to 35 mol%, based on the total amount of the ethylene copolymer.
6. The ethylene copolymer according to any one of claims 1 to 5, wherein the molar ratio of the 1, 2-cyclopentane ring structure unit to the 1, 2-cyclopropane ring structure unit in the conjugated diene structure units of the copolymer is from 0.1 to 3: 1, preferably 0.3 to 2.5: 1, more preferably 0.4 to 2: 1, more preferably 0.5 to 1.8: 1.
7. ethylene copolymer according to any one of claims 1-6, wherein the ethylene copolymer has a weight average molecular weight of 25,000 to 250,000, preferably 30,000 to 200,000, more preferably 40,000 to 150,000;
preferably, the copolymer has a molecular weight distribution index of 3.5 or less, preferably 3.2 or less, more preferably 1.5 to 3.
8. Ethylene copolymer according to any one of claims 1 to 7, wherein the glass transition temperature of the ethylene copolymer is in the range of-50 ℃ to-15 ℃, preferably in the range of-40 ℃ to-20 ℃.
9. An ethylene copolymer as claimed in any one of claims 1 to 8 wherein the conjugated diene is butadiene.
10. A process for producing an ethylene copolymer, which comprises contacting ethylene with a conjugated diene in the presence of a polymerization catalyst comprising a component A and a component B,
the component A is selected from metal compounds shown in a formula 1,
in formula 1, M is a metal atom selected from group IVB,
X1and X2Identical or different, each independently a halogen atom,
rb is a divalent group containing a group IVA element,
L1and L2The same or different, each independently selected from the group represented by formula 3 to formula 6,
in the formula 3, RA 1、RA 2、RA 3、RA 4And RA 5Are the same or different and are each independently a hydrogen atom or C1-C20The alkyl group of (a) is,
in the formula 4, RB 1、RB 2、RB 3、RB 4And RB 5Are the same or different and are each independently a hydrogen atom or C1-C20The alkyl group of (a) is,
in the formula 5, RC 1、RC 2、RC 3And RC 4Are the same or different and are each independently a hydrogen atom or C1-C20The alkyl group of (a) is,
in the formula 6, RD 1、RD 2、RD 3And RD 4Are the same or different and are each independently a hydrogen atom or C1-C20Alkyl groups of (a);
the component B contains aluminoxane.
11. The method according to claim 10, wherein, in formula 1, M is a zirconium atom; and/or
In formula 1, X1And X2Each independently a chlorine atom.
12. The method according to claim 10 or 11, wherein Rb is a divalent group containing silicon in formula 1, preferably a divalent group represented by formula 2,
in the formula 2, R1And R2Identical or different, each independently is C1-C10Alkyl group of (1).
13. The method according to claim 10, wherein the component a is one or two or more selected from metal compounds represented by formulae 7 to 10:
14. the method of any one of claims 10-13, wherein the molar ratio of component a to component B is 1: 0.1-5000.
15. The process according to any one of claims 10 to 14, wherein said component a is used in an amount of 0.1 to 100 μmol with respect to 1mol of conjugated diene.
16. The process of any one of claims 10-15, wherein the conjugated diene is butadiene.
17. The process of any one of claims 10-16, wherein the contacting is carried out at a temperature of-50 ℃ to 150 ℃, the ethylene pressure being 0-100MPa, the pressure being in gauge.
18. The process according to any one of claims 10-17, wherein the contacting is carried out in the presence of a molecular weight regulator in an amount such that the weight average molecular weight of the ethylene copolymer produced is from 20,000 to 300,000, preferably from 25,000 to 250,000, more preferably from 30,000 to 200,000, further preferably from 40,000 to 150,000.
19. An ethylene copolymer prepared by the process of any one of claims 10-18.
20. A composition comprising an ethylene copolymer as claimed in any one of claims 1 to 9 and 19 and a crosslinking agent.
21. A crosslinked polymer formed by crosslinking the ethylene copolymer according to any one of claims 1 to 9 and 19.
22. A tire having at least one constituent element comprising the ethylene copolymer of any one of claims 1 to 9 and 19, the composition of claim 20, or the crosslinked polymer of claim 21.
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| PCT/CN2020/132147 WO2022104877A1 (en) | 2020-11-20 | 2020-11-27 | Ethylene copolymer and method for preparation thereof and composition and crosslinked polymer and tire |
| KR1020237020824A KR20230109729A (en) | 2020-11-20 | 2020-11-27 | Ethylene copolymers, methods for their preparation, compositions, cross-linked polymers and tires |
| JP2023530770A JP2023549958A (en) | 2020-11-20 | 2020-11-27 | Ethylene copolymer and its production method, composition, crosslinked polymer and tire |
| EP20962168.9A EP4242239A1 (en) | 2020-11-20 | 2020-11-27 | Ethylene copolymer and method for preparation thereof and composition and crosslinked polymer and tire |
| US18/253,626 US20240010768A1 (en) | 2020-11-20 | 2020-11-27 | Ethylene copolymer and method for preparation thereof and composition and crosslinked polymer and tire |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5191052A (en) * | 1985-06-21 | 1993-03-02 | Exxon Chemical Patents Inc. | Copolymers of ethylene and 1,3-butadiene |
| US20030036610A1 (en) * | 1999-12-28 | 2003-02-20 | Ofelia Fusco | Process for the preparation of ethylene polymers |
| CN102356100A (en) * | 2009-03-30 | 2012-02-15 | 三井化学株式会社 | Copolymer of olefin and conjugated diene, and process for producing same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5191052A (en) * | 1985-06-21 | 1993-03-02 | Exxon Chemical Patents Inc. | Copolymers of ethylene and 1,3-butadiene |
| US20030036610A1 (en) * | 1999-12-28 | 2003-02-20 | Ofelia Fusco | Process for the preparation of ethylene polymers |
| CN102356100A (en) * | 2009-03-30 | 2012-02-15 | 三井化学株式会社 | Copolymer of olefin and conjugated diene, and process for producing same |
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