CN114516929B - Ethylene copolymer, process for producing the same, composition and crosslinked polymer, and tire - Google Patents

Ethylene copolymer, process for producing the same, composition and crosslinked polymer, and tire Download PDF

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CN114516929B
CN114516929B CN202011311765.9A CN202011311765A CN114516929B CN 114516929 B CN114516929 B CN 114516929B CN 202011311765 A CN202011311765 A CN 202011311765A CN 114516929 B CN114516929 B CN 114516929B
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ethylene copolymer
structural units
conjugated diene
ethylene
molecular weight
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CN114516929A (en
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高念
陈建军
李洪泊
徐林
吴宁
郝建国
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Priority to CN202011311765.9A priority Critical patent/CN114516929B/en
Priority to PCT/CN2020/132147 priority patent/WO2022104877A1/en
Priority to KR1020237020824A priority patent/KR20230109729A/en
Priority to JP2023530770A priority patent/JP2023549958A/en
Priority to EP20962168.9A priority patent/EP4242239A1/en
Priority to US18/253,626 priority patent/US20240010768A1/en
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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
    • 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
    • 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
    • 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
    • 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

Disclosed are an ethylene copolymer comprising ethylene structural units derived from ethylene and conjugated diene structural units derived from a conjugated diene, the content of the conjugated diene structural units being 25 to 45 mol% based on the total amount of the ethylene copolymer, the content of 1, 2-polymerized vinyl structural units formed in a 1, 2-polymerization manner and having a side chain double bond being 20 to 40 mol%, the total amount of the 1, 2-polymerized structural units being 95 mol% or more based on the total amount of the conjugated diene structural units in the ethylene copolymer, and a weight average molecular weight of the ethylene copolymer being 20,000 to 300,000, a method for producing the same, a crosslinked polymer and a tire containing the same. The ethylene copolymers according to the invention have good crosslinking properties.

Description

Ethylene copolymer, process for producing the same, composition and crosslinked polymer, and tire
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 structural units derived from ethylene and containing structural units derived from 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 widely used and readily available monomer. Conjugated dienes, particularly butadiene and isoprene, are the most important monomers for synthetic rubbers. Butadiene, a by-product of the process of preparing ethylene by petroleum route, has been similar to ethylene in price. Recently, the production of butadiene has been reduced due to the change of the production route of ethylene, and the price has been greatly increased. In contrast, the price of ethylene is reduced. Therefore, the use of ethylene as a raw material for producing rubber for tires is attractive and can greatly save raw material costs.
However, it is difficult to copolymerize due to the different polymerization mechanisms of conjugated dienes and α -olefins. Thus, the use of the same catalytic system to catalyze the copolymerization of ethylene and a conjugated diene is a very challenging task, and the realization of the copolymerization of both has been the direction of academia and industry efforts.
The existing method for copolymerizing ethylene and conjugated diene has the main 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, which results in improving the physical properties of the copolymer such as weatherability, heat resistance, ozone resistance and the like.
Accordingly, there is a need to develop polymerization processes suitable for copolymerizing ethylene with conjugated dienes to increase the catalytic activity, the molecular weight of the polymer, and the content of conjugated diene building blocks in the polymer.
Disclosure of Invention
The object of the present invention is to provide an ethylene copolymer containing conjugated diene structural units derived from conjugated dienes, which has not only a higher content of conjugated diene structural units but also a higher content of 1, 2-polymerized vinyl structural units of conjugated dienes formed in a 1, 2-polymerization manner and having side chain double bonds, while the unsaturated bond content in the copolymer main chain is low.
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, the content of the conjugated diene structural units being 25 to 45 mol% based on the total amount of the ethylene copolymer, the content of 1, 2-polymerized vinyl structural units having side chain double bonds formed in a 1, 2-polymerization manner being 20 to 40 mol% based on the total amount of the conjugated diene structural units in the ethylene copolymer, the total amount of the 1, 2-polymerized structural units being 95 mol% or more based on the total amount of the conjugated diene structural units, and 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 the preparation of an ethylene copolymer, the process comprising contacting ethylene with a conjugated diene in the presence of a polymerisation 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,
X 1 and X 2 Identical or different, are each independently a halogen atom,
rb is a divalent group containing an element of group IVA,
L 1 and L 2 Identical or different, are each independently selected from the groups represented by formulae 3 to 6,
in formula 3, R A 1 、R A 2 、R A 3 、R A 4 And R is A 5 Identical or different, each independently of the other is a hydrogen atom or C 1 -C 20 Is a group comprising an alkyl group,
in formula 4, R B 1 、R B 2 、R B 3 、R B 4 And R is B 5 Identical or different, each independently of the other is a hydrogen atom or C 1 -C 20 Is a group comprising an alkyl group,
in formula 5, R C 1 、R C 2 、R C 3 And R is C 4 Identical or different, each independently of the other is a hydrogen atom or C 1 -C 20 Is a group comprising an alkyl group,
in formula 6, R D 1 、R D 2 、R D 3 And R is D 4 Identical or different, each independently of the other is a hydrogen atom or C 1 -C 20 Alkyl of (a);
the component B is aluminoxane.
According to a third aspect of the present invention there is provided an ethylene copolymer prepared 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 as described in the first or third aspect 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 of the first or third aspect of the present invention.
According to a sixth aspect of the present invention, there is provided a tyre comprising at least one constituent element of the tyre 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 copolymers according to the invention have not only a higher content of conjugated diene building blocks but also a higher content of 1, 2-polymerized vinyl building blocks, while the unsaturated double bonds in the copolymer backbone are low. The ethylene copolymer has good crosslinking performance, and the crosslinked product has good weatherability, heat resistance and ozone resistance. The ethylene copolymer has wide application prospect in the rubber field, particularly the field of automobile tire rubber.
According to the method for preparing the ethylene copolymer, not only can the ethylene copolymer according to the invention be prepared, but also the catalytic activity can be improved, so that the production efficiency can be improved, and the method is suitable for industrial scale application.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to 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, the term "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 except that the electronic structure of the structural unit is changed as compared with ethylene; "structural unit derived from conjugated diene" means that the structural unit is formed of conjugated diene, and the atomic species and the number of each atom are the same except that the electronic structure is changed as compared with the conjugated diene.
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 two or more selected from the compounds represented by formula 11,
in formula 11, R 3 、R 4 And R is 5 Identical or different, each selected from hydrogen and C 1 -C 5 Straight or branched alkyl of (a).
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 has a content of the conjugated diene structural units 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 conjugated diene structural units are present in an amount of 25 to 40 mole%, based on the total amount of ethylene copolymer. More preferably, the conjugated diene structural units are present in an amount of 30 to 35 mole%, based on the total amount of ethylene copolymer.
The ethylene copolymer according to the present invention has a 1, 2-polymerized structural unit formed by 1, 2-polymerizing a conjugated diene as a main chain, and thus has a high content of 1, 2-polymerized structural units 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 1, 2-polymerized structural units of 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 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 bonds in the main chain of the ethylene copolymer may be derived, for example, from structural units formed by 1, 4-polymerization or 1, 3-polymerization of conjugated diolefins.
In the present invention, 1, 2-polymerized structural units refer to structural units formed by 1, 2-polymerization of conjugated dienes (i.e., 1, 2-addition), 1, 4-polymerized structural units refer to structural units formed by 1, 4-polymerization of conjugated dienes (i.e., 1, 4-addition), and 1, 3-polymerized structural units refer to structural units formed by 1, 3-polymerization of conjugated dienes (i.e., 1, 3-addition).
The ethylene copolymer according to the present invention, the 1, 2-polymeric structural unit includes a 1, 2-polymeric vinyl structural unit in which a conjugated diene is formed in a 1, 2-polymerization manner and 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 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 has a cyclopentane ring.
Taking butadiene as an example, the 1, 2-polymerized vinyl structural unit is shown as formula 14, the 1, 2-cyclopropane ring structural unit is shown as formula 15, and the 1, 5-cyclopentane ring structural unit is shown as formula 16:
according to the ethylene copolymer of the present invention, the conjugated diene is formed in a 1, 2-polymerization manner and has a high 1, 2-polymerized vinyl structural unit having a side chain double bond. The content of 1, 2-polymerized vinyl structural units (i.e. vinyl content) may be 20 to 40 mol%, 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%, based on the total amount of the ethylene copolymer according to the invention. Preferably, the content of 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 1, 2-polymerized vinyl structural units is 21 to 30 mol% based on the total amount of the ethylene copolymer according to the present 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 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 1, 2-polymeric vinyl structural units are present in an amount of 60 to 88% based on the total amount of conjugated diene structural units in the ethylene copolymer. More preferably, the 1, 2-polymerized vinyl structural units are present in an amount of 63 to 85% based on the total amount of 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 of 0.1 to 3 in conjugated diene structural units: 1, preferably 0.3-2.5:1, more preferably 0.4-2:1, further preferably 0.5 to 1.8:1.
in the present invention, the microstructure composition of the ethylene copolymer is determined by nuclear magnetic resonance spectroscopy.
The ethylene copolymers according to the invention not only have a higher content of 1, 2-polymerized vinyl building blocks, but also have a higher molecular weight. Weight average molecular weight (M) of ethylene copolymer according to the present invention w ) From 20,000 to 300,000, preferably from 25,000 to 250,000, more preferably from 30,000 to 200,000, still more preferably from 40,000 to 150,000. According to the ethylene copolymer of the present invention, the ethylene copolymer has a molecular weight distribution index (M w /M n ) Is 3.5 or less, preferably 3.2 or less, more preferably 1.5 to 3.
In the present invention, the molecular weight (unit is g/mol) and the molecular weight distribution index are measured by Gel Permeation Chromatography (GPC) using monodisperse polystyrene as a standard.
According to the ethylene copolymer of the present invention, the ethylene copolymer has a glass transition temperature (T g ) May be in the range of-50℃to-15℃and 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 the preparation of an ethylene copolymer, the process comprising contacting ethylene with a conjugated diene in the presence of a polymerisation catalyst.
According to the preparation method of the invention, the conjugated diene refers to a compound containing conjugated double bonds in a molecular structure. The conjugated diene may be one or two or more selected from the compounds represented by formula 11,
In formula 11, R 3 、R 4 And R is 5 Identical or different, each selected from hydrogen and C 1 -C 5 Straight or branched alkyl of (a).
Specific examples of the conjugated diene according to the production 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 preparation method of the invention, the polymerization catalyst contains 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, 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, X 1 And X 2 The same or different are each independently a halogen atom. Preferably, in formula 1, X 1 And X 2 All are chlorine atoms.
In formula 1, rb is a divalent group of a group IVA element. In formula 1, rb is preferably a silicon-containing divalent group, more preferably a divalent group represented by formula 2,
in formula 2, R 1 And R is 2 Identical or different, each independently C 1 -C 10 Is a hydrocarbon group. The C is 1 -C 10 The alkyl group of (C) includes C 1 -C 10 Straight chain alkyl, C 3 -C 10 Branched alkyl and C of (2) 3 -C 10 Specific examples of which 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, R 1 And R is 2 Are all methyl groups.
In formula 1, L 1 And L 2 Identical or different, are each independently selected from the groups represented by formulae 3 to 6,
in formula 3, R A 1 、R A 2 、R A 3 、R A 4 And R is A 5 Identical or different, each independently of the other is a hydrogen atom or C 1 -C 20 Is a hydrocarbon group.
In the invention, C 1 -C 20 The alkyl group of (C) includes C 1 -C 20 Straight chain alkyl, C 3 -C 20 Branched alkyl of (C) 3 -C 20 Specific examples of which 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, R A 1 、R A 2 、R A 3 、R A 4 And R is A 5 And is also a hydrogen atom.
In another embodiment, in formula 3, R A 1 、R A 2 、R A 3 、R A 4 And R is A 5 Each independently is a hydrogen atom or C 1 -C 20 And R is an alkyl group of A 1 、R A 2 、R A 3 、R A 4 And R is A 5 Not both hydrogen atoms. In this embodiment, R A 1 、R A 2 、R A 3 、R A 4 And R is A 5 At least one (preferably both) of which is preferably C 1 -C 10 More preferably C 1 -C 6 More preferably C 1 -C 3 More preferably methyl, the remainder being hydrogen atoms.
In formula 4, R B 1 、R B 2 、R B 3 、R B 4 And R is B 5 Identical or different, each independently of the other is a hydrogen atom or C 1 -C 20 Is a hydrocarbon group.
In one embodiment, in formula 4, R B 1 、R B 2 、R B 3 、R B 4 And R is B 5 And is also a hydrogen atom.
In another embodiment, in formula 4, R B 1 、R B 2 、R B 3 、R B 4 And R is B 5 Each independently is a hydrogen atom or C 1 -C 20 And R is an alkyl group of B 1 、R B 2 、R B 3 、R B 4 And R is B 5 Not both hydrogen atoms, in this embodiment R B 1 、R B 2 、R B 3 、R B 4 And R is B 5 At least one (preferably two, more preferably R B 2 And R is B 4 ) Preferably C 1 -C 10 More preferably C 1 -C 6 More preferably C 1 -C 3 More preferably methyl, the remainder being hydrogen atoms.
In formula 5, R C 1 、R C 2 、R C 3 And R is C 4 Identical or different, each independently of the other is a hydrogen atom or C 1 -C 20 Is a hydrocarbon group.
In a preferred embodiment, in formula 5, R C 1 、R C 2 、R C 3 And R is C 4 At least one (preferably two, more preferably R C 1 And R is C 3 ) Is C 1 -C 20 Alkyl of (C) is preferred 1 -C 6 More preferably C 1 -C 3 More preferably methyl, ethyl, n-propyl or isopropyl, and the remaining groups are hydrogen atoms. According to this preferred embodiment, in a more preferred embodiment, R C 1 Is methyl, R C 3 Is ethyl or n-propyl, R C 2 And R is C 4 Is a hydrogen atom.
In formula 6, R D 1 、R D 2 、R D 3 And R is D 4 Identical or different, each independently of the other is a hydrogen atom or C 1 -C 20 Is a hydrocarbon group.
In a preferred embodiment, in formula 6, R D 1 、R D 2 、R D 3 And R is D 4 At least one (preferably two, more preferably R D 1 And R is D 3 ) Is C 1 -C 20 Alkyl of (C) is preferred 1 -C 6 More preferably C 1 -C 3 More preferably methyl, ethyl, n-propyl or isopropyl, and the remaining groups are hydrogen atoms. According to this preferred embodiment, in a more preferred embodiment, R D 1 Is methyl, R D 3 Is ethyl or n-propyl, R D 2 And R is D 4 Is a hydrogen atom.
According to the production method of the present invention, the component a is preferably one or two or more selected from the group consisting of metal compounds represented by formulas 7 to 10:
in a more preferred example, the component a is a metal compound selected from the group consisting of those represented by formulas 7 and 8. According to this more preferred example, the process according to the present invention can not only increase the content of conjugated diene structural units derived from conjugated diene and structural units formed by 1, 2-polymerization of conjugated diene in the ethylene copolymer, but also obtain higher catalytic activity, producing an ethylene copolymer having a higher molecular weight.
In another more preferred example, the component a is a metal compound selected from the group consisting of those represented by formulas 9 and 10. According to this more preferred example, the process according to the invention allows more conjugated diolefins to be polymerized in a 1, 2-polymerization manner, under conditions such that a higher catalytic activity is obtained, thus obtaining ethylene copolymers with a higher content of 1, 2-polymerized structural units.
According to the preparation method of the present invention, the metal compound as the component A is commercially available or can be prepared by a conventional method.
According to the preparation process of the present invention, the component B contains an aluminoxane, preferably an organoaluminoxane, more preferably a methylaluminoxane. In a preferred embodiment, the component B is an aluminoxane, preferably an organoaluminum oxy-alkane, 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 1:1-1000, further 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, still more preferably 5 to 30. Mu. Mol, relative to 1mol of the conjugated diene.
According to the preparation process of the present invention, the contacting of ethylene with conjugated diene may be carried out at a temperature of from-50℃to 150℃and preferably at a temperature of from 10 to 120℃and more preferably at a temperature of from 30 to 90℃and even more preferably at a temperature of from 40 to 70 ℃. According to the production process of the present invention, when ethylene and conjugated diene are polymerized in contact, the pressure of ethylene may be 0 to 100MPa, preferably 2 to 50MPa, more preferably 3 to 30MPa, still more preferably 5 to 10MPa, in terms of gauge pressure (G).
According to the production method of the present invention, the contacting is performed in the presence of a molecular weight regulator 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, still more preferably 40,000 to 150,000. The molecular weight regulator may be a conventional choice, preferably hydrogen.
According to the preparation method of the invention, the preparation method can be carried out in a solution polymerization mode. In solution polymerization, a solvent may be usedThe agent comprises C 6 -C 12 Aromatic hydrocarbons, C 6 -C 12 Halogenated aromatic hydrocarbon, C 5 -C 10 Straight-chain alkane and C 5 -C 10 For example: toluene, chlorobenzene, dichlorobenzene, n-hexane and cyclohexane.
According to a third aspect of the present invention there is provided an ethylene copolymer prepared by the process of the second aspect of the present invention.
The ethylene copolymer prepared by the method according to the second aspect of the present invention has not only a relatively high content of conjugated diene structural units, but also a high content of structural units formed by 1, 2-polymerization of conjugated diene, and thus 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 weatherability, heat resistance and ozone resistance. More importantly, the ethylene copolymers according to the third aspect of the present invention have a higher content of 1, 2-polymerized vinyl structural units, and thus have more excellent vulcanization properties, exhibiting a faster vulcanization rate and a higher degree of vulcanization.
The conjugated diene building blocks may be present in an amount of from 20 to 45 mole%, based on the total amount of ethylene copolymer according to the third aspect of the present invention, for example 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 mole%. Preferably, the conjugated diene structural units are present in an amount of 25 to 40 mole%, based on the total amount of the ethylene copolymer according to the third aspect of the present invention. More preferably, the conjugated diene structural units are present in an amount of from 30 to 35 mole%, 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 in a 1, 2-polymerization manner. 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 the 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-polymeric structural unit includes a 1, 2-polymeric vinyl structural unit formed by 1, 2-polymerization of a conjugated diene and having a side chain double bond, a 1, 2-cyclopropane ring structural unit formed by 1, 2-polymerization of a conjugated diene and having a cyclopropane ring, and a 1, 5-cyclopentane ring structural unit formed by 1, 2-polymerization of a conjugated diene and having a cyclopentane ring. The content of 1, 2-polymerized vinyl structural units may be 18 to 40 mol%, 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%, based on the total amount of the ethylene copolymer according to the third aspect of the present invention. Preferably, the 1, 2-polymeric vinyl structural unit is present in an amount of 20 to 35 mole% 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 unit is contained 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 1, 2-polymeric vinyl structural units are present in an amount of 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 1, 2-polymerized vinyl structural unit is present in an amount of 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.
According to the ethylene copolymer of the third aspect of the present invention, the molar ratio of the 1, 2-cyclopentane ring structural unit to the 1, 2-cyclopropane ring structural unit in the conjugated diene structural unit of the copolymer is 0.1 to 3:1, preferably 0.3-2.5:1, more preferably 0.4-2:1, further preferably 0.5 to 1.8:1.
Weight average molecular weight (M) of ethylene copolymer according to the third aspect of the present invention w ) May be 20,000 to 300,000, preferably 25,000 to 250,000, more preferably 30,000 to 200,000, still more preferably 40,000 to 150,000. According to the ethylene copolymer of the third aspect of the present invention, the ethylene copolymer has a molecular weight distribution index (M w /M n ) Is 3.5 or less, preferably 3.2 or less, more preferably 1.5 to 3.
According to the third aspect of the present invention, the ethylene copolymer has a glass transition temperature (T g ) May be in the range of-50℃to-15℃and 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 the vinyl groups in the ethylene copolymer. Specifically, the cross-linking agent can be one or more than two of sulfur, sulfur monochloride, selenium, tellurium and peroxide. In a preferred embodiment, the crosslinking agent is a peroxide, for example: dicumyl peroxide.
The composition according to the invention may also contain a vulcanization accelerator to promote vulcanization, thereby shortening the vulcanization time, lowering the vulcanization temperature and reducing the amount of vulcanizing agent used. The vulcanization accelerator may be a commonly used one capable of achieving the above functions, for example: triallyl isocyanurate. The composition according to the invention may also contain other components according to specific requirements, such as: one or more of antioxidants and fillers, preferred examples of which 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 an ethylene copolymer according to the first aspect of the present invention or according to 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 effect 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 tyre comprising at least one constituent element of the tyre 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 will be described in detail with reference to examples, but it is not limited thereto.
In the following examples and comparative examples, the molecular weight and molecular weight distribution index (M w /M n ) The measurement was carried out by using 1260Infinity II high temperature gel permeation chromatograph (Agilent) and using 2 MIXD-B columns (300X 7.5 mm) and 1 Guard column (50X 7.5 mm). The mobile phase is trichlorobenzene, and the flow rate is 1mL/min; the concentration of the sample solution is 1mg/mL, and the sample injection amount is 200 mu L; the test temperature was 150 ℃; as a standard sample, a single-distributed polystyrene was used.
In the following examples and comparative examples, nuclear magnetic resonance spectroscopy was performed using 400MHz nuclear magnetic resonance apparatus commercially available from Bruker, inc., to test the microstructure of the polymer using deuterated o-dichlorobenzene as a solvent and tetramethyl silicon (TMS) as an internal standard. Wherein "conjugated diene structural unit" means a structural unit formed from a conjugated diene, "1, 2-polymerization" means that a conjugated diene is polymerized in a 1, 2-addition manner, "1, 4-polymerization" means that a conjugated diene is polymerized in a 1, 4-addition manner, "1, 3-polymerization"Refers to the polymerization of conjugated diolefins in the form of 1, 3-addition; "vinyl" refers to a structural unit of conjugated diolefin formed by 1, 2-polymerization and having a pendant double bond (in the case of butadiene, vinyl ) "cyclopropane ring" means a structural unit of a conjugated diene formed by 1, 2-polymerization and having a cyclopropane ring (in the case of butadiene, cyclopropane ring +.>) "cyclopentane ring" means a structural unit of a conjugated diene formed by 1, 2-polymerization and having a cyclopentane ring (in the case of butadiene, cyclopentane ring is +.>)。
The following examples and comparative examples relate to the following metal compounds and comparative metal compounds.
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Preparation examples 1-4 were used to prepare metal compounds 1-4.
Preparation example 1
Synthesis of Metal Compound 1
Into the reaction flask were charged 0.94g (2 mmol) of bis (2, 5-dimethylcyclopentabithiophene) -dimethylsilicon and 50mL of diethyl ether, and 2.5mL (4 mmol) of 1.6M butyllithium hexane solution was added dropwise at-78 ℃. After stirring at room temperature (25 ℃) for 6 hours, the temperature was reduced to-40℃and 0.466g (2 mmol) of zirconium tetrachloride was slowly added. Stir overnight. The mixture was filtered and the solid was washed with diethyl ether. The product was recrystallized from methylene chloride. Yield: 45% by weight.
H 1 -NMR(CDCl 3 ,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 as for metal compound 1 was used, except that bis (2, 5-dimethylcyclopentabithiophene) -dimethylsilicon was replaced with 2mmol of bis (cyclopentabithiophene) -dimethylsilicon. Yield: 57 wt%.
H 1 -NMR(CDCl 3 ,400MHz)：δppm 7.15(d,4H)，7.10(d,4H)，1.80(s,6H)。
Preparation example 3
Synthesis of metal compound 2.
1.02g (2 mmol) of bis (2-methyl-5-n-propyl-3- (9-phenanthryl) -6-hydro-cyclopenta [2,3-b ] thiophene-6) -dimethylsilicon and 50mL of diethyl ether were added to the reaction flask, and 2.5mL (4 mmol) of a 1.6M solution of butyllithium in hexane was added dropwise at-78 ℃. After stirring at room temperature (25 ℃ C.) for 6 hours, 0.466g (2 mmol) of zirconium tetrachloride was slowly added. Stir overnight. The mixture was filtered and the solid was washed with diethyl ether. And (5) pumping out the filtrate to obtain a target product. Yield: 56% by weight.
H 1 -NMR(CDCl 3 ,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 that of metal compound 5 was employed, except that 2mmol of bis (2-methyl-5-ethyl-3- (9-phenanthryl) -6-hydro-cyclopenta [2,3-b ] thiophene-6) -dimethylsilicon was used instead of bis (2, 5-dimethyl-3-phenyl-6-hydro-cyclopenta [2,3-b ] thiophene-6) -dimethylsilicon. Yield: 61% by weight.
H 1 -NMR(CDCl 3 ,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 provided to illustrate ethylene polymers and methods of making the same according to the present invention.
Example 1
A500 mL stainless steel reaction vessel was thoroughly replaced with nitrogen, then with hydrogen, 120g of toluene, 8mL of methylaluminoxane (10 wt% toluene solution), 25.0g of butadiene, and further 0.44kg/cm were added 2 G hydrogen. At 60℃with 7.8kg/cm 2 G ethylene saturates the liquid and gaseous phases. Then, 5. Mu. Mol of metal compound 1 dissolved in toluene in advance was added to start polymerization. Continuously supplying ethylene gas to maintain the total pressure at 7.8kg/cm 2 G. After 15 minutes of polymerization, the reaction was terminated by adding a small amount of methanol. The product was precipitated by pouring it into a large amount of ethanol with hydrochloric acid (HCl concentration: 2 wt.%) added thereto, and the solid was separated by filtration and washed with ethanol. The washed solid was dried with a vacuum oven until the weight was no longer reduced, giving an ethylene copolymer according to the invention. Specific experimental conditions are listed in table 1, and the results of the property parameter test of the prepared ethylene copolymer are listed in table 2.
Comparative example 1
An ethylene copolymer was produced in the same manner as in example 1 except that not methylaluminoxane was used, but 2.5mL of a triisobutylaluminum in n-hexane (triisobutylaluminum concentration was 1M) was used, and 0.03mmol of trityl-tetrakis (pentafluorophenyl) borate was dissolved in toluene together with the metal compound 1 and added to a polymerization reactor. Specific experimental conditions are listed in table 1, and the results of the property parameter test of the prepared ethylene copolymer 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 test of the prepared ethylene copolymer 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 test of the prepared ethylene copolymer are listed in table 2.
Example 2
An ethylene copolymer was produced in the same manner as in example 1, except that: metal compound 1 was replaced with metal compound 2, and the property parameters of the prepared ethylene copolymer are listed in table 2.
Comparative example 4
An ethylene copolymer was produced in the same manner as in example 2 except that not methylaluminoxane was used, but 2.5mL of a triisobutylaluminum in n-hexane (triisobutylaluminum concentration was 1M) was used, and 0.03mmol of trityl-tetrakis (pentafluorophenyl) borate was dissolved in toluene together with the metal compound 2 and added to a polymerization reactor. Specific experimental conditions are listed in table 1, and the results of the property parameter test of the prepared ethylene copolymer 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 test of the prepared ethylene copolymer are listed in table 2.
Example 3
A500 mL stainless steel reactor was thoroughly replaced with nitrogen, then with hydrogen, 120g of toluene, 7.5mL of MAO (10 wt% toluene solution), 35g of butadiene, and then 0.44kg/cm were added 2 G hydrogen gas at 60℃with 7.8kg/cm 2 G ethylene saturates the liquid and gaseous phases. Then, 5. Mu. Mol of metal compound 2 dissolved in toluene in advance was added to start polymerization. Continuously supplying ethylene gas to maintain the total pressure at 7.8kg/cm 2 G. After 15 minutes of polymerization, the reaction was terminated by adding a small amount of methanol. The product was poured into a large amount of ethanol (2 wt% hydrochloric acid in HCl), precipitated, and the copolymer was isolated by filtration and washed with ethanol. Drying with a vacuum oven until the weight is no longer reduced gives the ethylene copolymer according to the invention. Specific experimental conditions are listed in table 1, and the results of the property parameter test of the prepared ethylene copolymer 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 test of the prepared ethylene copolymer are listed in table 2.
Example 4
An ethylene copolymer was produced 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 test of the prepared ethylene copolymer are listed in table 2.
Comparative example 7
An ethylene copolymer was produced in the same manner as in example 4 except that not methylaluminoxane was used, but 2.5mL of a triisobutylaluminum in n-hexane (triisobutylaluminum concentration was 1M) was used, and 0.03mmol of trityl-tetrakis (pentafluorophenyl) borate was dissolved in toluene together with the metal compound 3 and added to a polymerization reactor. Specific experimental conditions are listed in table 1, and the results of the property parameter test of the prepared ethylene copolymer 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 test of the prepared ethylene copolymer 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 test of the prepared ethylene copolymer are listed in table 2.
Example 5
An ethylene copolymer was produced in the same manner as in example 1, except that the metal compound 1 was replaced with the metal compound 4. Specific experimental conditions are listed in table 1, and the results of the property parameter test of the prepared ethylene copolymer are listed in table 2.
Comparative example 10
An ethylene copolymer was produced in the same manner as in example 5 except that not methylaluminoxane was used, but 2.5mL of a triisobutylaluminum in n-hexane (triisobutylaluminum concentration was 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 reactor. Specific experimental conditions are listed in table 1, and the results of the property parameter test of the prepared ethylene copolymer 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. Specific experimental conditions are listed in table 1, and the results of the property parameter test of the prepared ethylene copolymer are listed in table 2.
Example 6
An ethylene copolymer was produced in the same manner as in example 1, except that the metal compound 1 was replaced with the metal compound 4. Specific experimental conditions are listed in table 1, and the results of the property parameter test of the prepared ethylene copolymer are listed in table 2.
Comparative example 12
An ethylene copolymer was prepared 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 test of the prepared ethylene copolymer are listed in table 2.
Comparative example 13
An ethylene copolymer was prepared 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 test of the prepared ethylene copolymer are listed in table 2.
TABLE 1
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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 of unsaturated groups. The results of table 2 also confirm that not only the ethylene copolymer according to the present invention can be produced according to the olefin polymerization method of the present invention, but also an improved catalyst activity can be obtained, thereby improving production efficiency.
Test examples 1 to 2
The ethylene copolymers prepared in examples 2 and 4 were blended with carbon black, peroxide and vulcanization aid on an open mill according to the formulations shown in Table 3. The vulcanization characteristics of the blends were evaluated using an MDR vulcanizer available from alpha technologies at 160℃for 20 minutes. The test results are listed in table 4.
Test comparative examples 1 to 2
The ethylene copolymers prepared in comparative examples 5 and 9 were each tested for vulcanization characteristics by the same method as in test examples 1-2, and the test results are shown in Table 4.
TABLE 3 Table 3
TABLE 4 Table 4
Numbering device Test example 1 Comparative test example 1 Test example 2 Comparative test example 2
t c 10(min) 0.5 1.1 0.7 0.9
t c 90(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
From the results of the vulcanization characteristics test in Table 4, it can be seen that the ethylene copolymer according to the present invention has a faster torque rise when subjected to vulcanization, a faster vulcanization rate and a higher degree of vulcanization.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims (39)

1. An ethylene copolymer comprising ethylene structural units derived from ethylene and conjugated diene structural units derived from a conjugated diene, wherein the content of the conjugated diene structural units is 25 to 45 mol% based on the total amount of the ethylene copolymer, the content of 1, 2-polymerized vinyl structural units having side chain double bonds formed by 1, 2-polymerization of the conjugated diene is 20 to 40 mol%, the total amount of the 1, 2-polymerized structural units is 95 mol% or more based on the total amount of the conjugated diene structural units in the ethylene copolymer, and the weight average molecular weight of the ethylene copolymer is 20,000 to 300,000.
2. The ethylene copolymer according to claim 1, wherein the content of the 1, 2-polymerized vinyl structural unit is 20 to 35 mol% based on the total amount of the ethylene copolymer.
3. The ethylene copolymer according to claim 1, wherein the content of the 1, 2-polymerized vinyl structural unit is 21 to 30 mol% based on the total amount of the ethylene copolymer.
4. The ethylene copolymer according to any one of claims 1 to 3, wherein the content of the 1, 2-polymerized vinyl structural unit is 55 to 90% based on the content of the conjugated diene structural unit.
5. The ethylene copolymer according to any one of claims 1 to 3, wherein the content of the 1, 2-polymerized vinyl structural unit is 60 to 88% based on the content of the conjugated diene structural unit.
6. The ethylene copolymer according to any one of claims 1 to 3, wherein the content of the 1, 2-polymerized vinyl structural unit is 63 to 85% based on the content of the conjugated diene structural unit.
7. 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 based on the total amount of the conjugated diene structural units in the ethylene copolymer.
8. The ethylene copolymer according to any one of claims 1 to 3, wherein the total amount of 1, 2-polymeric structural units is 100 mol% based on the total amount of conjugated diene structural units in the ethylene copolymer.
9. The ethylene copolymer according to claim 1, wherein the content of the conjugated diene structural units is 25 to 40 mol% based on the total amount of the ethylene copolymer.
10. The ethylene copolymer according to claim 1, wherein the content of the conjugated diene structural units is 30 to 35 mol% based on the total amount of the ethylene copolymer.
11. The ethylene copolymer according to any one of claims 1, 9 and 10, wherein the molar ratio of 1, 2-cyclopentane ring structural units to 1, 2-cyclopropane ring structural units in conjugated diene structural units of the copolymer is from 0.1 to 3:1.
12. the ethylene copolymer according to any one of claims 1, 9 and 10, wherein the molar ratio of 1, 2-cyclopentane ring structural units to 1, 2-cyclopropane ring structural units in conjugated diene structural units of the copolymer is 0.3 to 2.5:1.
13. the ethylene copolymer according to any one of claims 1, 9 and 10, wherein the molar ratio of 1, 2-cyclopentane ring structural units to 1, 2-cyclopropane ring structural units in conjugated diene structural units of the copolymer is from 0.4 to 2:1.
14. The ethylene copolymer according to any one of claims 1, 9 and 10, wherein the molar ratio of 1, 2-cyclopentane ring structural units to 1, 2-cyclopropane ring structural units in conjugated diene structural units of the copolymer is from 0.5 to 1.8:1.
15. the ethylene copolymer according to claim 1, wherein the weight average molecular weight of the ethylene copolymer is 25,000 to 250,000.
16. The ethylene copolymer according to claim 1, wherein the weight average molecular weight of the ethylene copolymer is 30,000 to 200,000.
17. The ethylene copolymer according to claim 1, wherein the weight average molecular weight of the ethylene copolymer is 40,000 to 150,000.
18. The ethylene copolymer according to any one of claims 1 and 15 to 17, wherein the copolymer has a molecular weight distribution index of 3.5 or less.
19. The ethylene copolymer according to any one of claims 1 and 15 to 17, wherein the copolymer has a molecular weight distribution index of 3.2 or less.
20. The ethylene copolymer of any one of claims 1 and 15-17, wherein the copolymer has a molecular weight distribution index of 1.5-3.
21. The ethylene copolymer according to claim 1, wherein the glass transition temperature of the ethylene copolymer is in the range of-50 ℃ to-15 ℃.
22. The ethylene copolymer according to claim 1, wherein the glass transition temperature of the ethylene copolymer is in the range of-40 ℃ to-20 ℃.
23. The ethylene copolymer of any one of claims 1-3, 9, 10, 15-17, 21, and 22, wherein the conjugated diene is butadiene.
24. A process for the preparation of an ethylene copolymer according to claim 1, 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,
X 1 and X 2 Identical or different, are each independently a halogen atom,
rb is a divalent group containing an element of group IVA,
L 1 and L 2 Identical or different, are each independently selected from the groups represented by formulae 3 to 6,
in formula 3, R A 1 、R A 2 、R A 3 、R A 4 And R is A 5 Identical or different, each independently of the other is a hydrogen atom or C 1 -C 20 Is a group comprising an alkyl group,
in formula 4, R B 1 、R B 2 、R B 3 、R B 4 And R is B 5 The same or a different one of the above,each independently is a hydrogen atom or C 1 -C 20 Is a group comprising an alkyl group,
in formula 5, R C 1 、R C 2 、R C 3 And R is C 4 Identical or different, each independently of the other is a hydrogen atom or C 1 -C 20 Is a group comprising an alkyl group,
in formula 6, R D 1 、R D 2 、R D 3 And R is D 4 Identical or different, each independently of the other is a hydrogen atom or C 1 -C 20 Alkyl of (a);
the component B is aluminoxane.
25. The method of claim 24, wherein in formula 1, M is a zirconium atom; and/or
In formula 1, X 1 And X 2 Each independently is a chlorine atom.
26. The method of claim 24 or 25, wherein in formula 1 Rb is a silicon-containing divalent group.
27. The method according to claim 26, wherein in formula 1, rb is a divalent group represented by formula 2,
in formula 2, R 1 And R is 2 Identical or different, each independently C 1 -C 10 Is a hydrocarbon group.
28. The method according to claim 24, wherein the component a is one or two or more selected from the group consisting of metal compounds represented by formulas 7 to 10:
29. the method of claim 24, wherein the molar ratio of component a to component B is 1:0.1-5000.
30. The process according to claim 24 or 29, wherein component a is used in an amount of 0.1 to 100 μmol relative to 1mol of conjugated diene.
31. The method of any one of claims 24, 25, 28 and 29, wherein the conjugated diene is butadiene.
32. The process of any one of claims 24, 25, 28 and 29, wherein the contacting is performed at a temperature of-50 ℃ to 150 ℃, the ethylene pressure being 0-100MPa, the pressure being in gauge pressure.
33. The process of any one of claims 24, 25, 28 and 29, wherein the contacting is performed 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.
34. The process of any one of claims 24, 25, 28 and 29, wherein the contacting is performed 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 25,000 to 250,000.
35. The process of any one of claims 24, 25, 28 and 29, wherein the contacting is performed 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 30,000 to 200,000.
36. The process of any one of claims 24, 25, 28 and 29, wherein the contacting is performed 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 40,000 to 150,000.
37. A composition comprising an ethylene copolymer as claimed in any one of claims 1 to 23 and a cross-linking agent.
38. A crosslinked polymer formed by crosslinking the ethylene copolymer of any one of claims 1-23.
39. A tire, at least one of the constituent elements of which comprises the ethylene copolymer of any one of claims 1-23, the composition of claim 37, or the crosslinked polymer of claim 38.
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