An ethylene copolymer with a method for its preparation, a composition, a cross-linked polymer and a tire
Patent Information
- Application Number
- BR112023009697
- Authority / Receiving Office
- BR · BR
- Patent Type
- Patents
- Current Assignee / Owner
- Publication Date
- 2026-08-11
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Abstract
Description
An ethylene copolymer with a method for its preparation, a composition, a crosslinked polymer, and a tire.
[001] Cross-reference to related requests
[002] This application claims the benefits of Chinese patent applications 202011311765.9 and 202011314968.3, filed on November 20, 2020, the content of which is incorporated herein by reference.
[003] Field of invention
[004] This disclosure relates to an ethylene copolymer and a method of preparing it, more particularly, this disclosure relates to an ethylene copolymer comprising an ethylene-derived structural unit and a structural unit derived from a conjugated diene, as well as a related method of preparation; this disclosure also relates to a composition comprising the ethylene copolymer and a crosslinked polymer comprising an ethylene copolymer-derived unit; and this disclosure further relates to a tire having at least one constituent element including the ethylene copolymer, the composition or the crosslinked polymer.
[005] Background of the invention
[006] Ethylene, as a widely used and readily available monomer, is extensively used in the plastics industry. Conjugated dienes, particularly butadiene and isoprene, are the most important monomers for rubber synthesis. Butadiene, as a byproduct of the ethylene preparation process via the petroleum route, had a similar price to ethylene. Recently, due to a change in the ethylene preparation route, the yield of butadiene has decreased and its price has increased significantly. Conversely, the price of ethylene is reduced. Therefore, the use of ethylene as a raw material for the preparation of tire rubber is quite attractive, which can save considerably on raw material costs.
[007] However, copolymerization is difficult due to different polymerization mechanisms of conjugated dienes and alpha-olefins. Thus, catalyzing the copolymerization of Petition 870230061875, dated 07 / 14 / 2023, page 5 / 42 2 / 34 ethylene and conjugated dienes using the same catalytic system is a highly challenging topic, and achieving copolymerization of ethylene and conjugated dienes has always been a focus of academic and industrial efforts.
[008] Existing methods for copolymerizing ethylene and conjugated dienes have the main problems that the content of a conjugated diene structural unit in the prepared polymer is not high and the content of an unsaturated bond in a backbone of the prepared polymer is high, which makes it difficult to improve physical properties such as weather resistance, thermal resistance and ozone resistance of the copolymer.
[009] Therefore, it is urgent to develop a suitable polymerization process for the copolymerization of ethylene and conjugated dienes in order to increase the catalytic activity, the molecular weight of a polymer and the content of the conjugated diene structural unit in the polymer.
[0010] Summary of the invention
[0011] The present disclosure aims to provide an ethylene copolymer comprising a conjugated diene structural unit derived from a conjugated diene, the ethylene copolymer not only having a higher content of conjugated diene structural unit, but also a higher content of 1,2-polymerized vinyl structural unit formed by 1,2-polymerization of the conjugated diene, in addition to possessing side chain double bonds while having a low content of unsaturated bonds in a copolymer backbone.
[0012] According to a first aspect of the present disclosure, the present disclosure provides an ethylene copolymer, wherein the ethylene copolymer comprises an ethylene structural unit derived from ethylene and a conjugated diene structural unit derived from a conjugated diene; based on the total amount of ethylene copolymer, the content of the conjugated diene structural unit is 25-45 mol% and the content of a 1,2-polymerized vinyl structural unit formed by 1,2-polymerization of the conjugated diene and having side-chain double bonds is 20-40 mol%; the total amount of a 1,2-polymerized structural unit is 95 mol% or more based on the total amount of the conjugated diene structural unit in the ethylene copolymer, and the ethylene copolymer having an average molecular weight of 20,000 to 300,000. Petition 870230061875, dated 07 / 14 / 2023, page 6 / 42 3 / 34
[0013] According to a second aspect of the present disclosure, the present disclosure provides a method for the preparation of an ethylene copolymer, comprising contacting ethylene with a conjugated diene in the presence of a polymerization catalyst, wherein the polymerization catalyst comprises a component A and a component B,
[0014] component A is selected from metallic compounds represented by a formula 1, / L1\ / X1
[0015] LiX2 (Formula 1)
[0016] in formula 1, M is a metal atom selected from a Group IVB,
[0017] Xi and X2 are the same or different, and each is independently a halogen atom,
[0018] Rb is a divalent group containing an element from Group IVA,
[0019] Li and L2 are equal or different, and each is selected independently from the groups represented by formulas 3 to 6, Ra3RA\ Λ' .wx. RA Ra5 SSA Formula 3 Rb3Rb Rb4 Rb1 Rb5 Formula 4 Petition 870230061875, dated 07 / 14 / 2023, p. 7 / 42 4 / 34
[0020] in formula 3, Ra1, Ra2, Ra3, Ra4 and Ra5 are the same or different and are each independently a hydrogen atom or C1-C20 alkyl,
[0021] in formula 4, Rb1, Rb2, Rb3, Rb4 and Rb5 are the same or different, and are each independently a hydrogen atom or a C1-C20 alkyl atom,
[0022] in formula 5, Rc1, Rc2, Rc3 and Rc4 are the same or different and are each independently a hydrogen atom or C1-C20 alkyl, and
[0023] in formula 6, Rd1, Rd2, Rd3 and Rd4 are the same or different, and are each independently a hydrogen atom or a C1-C20 alkyl atom; and
[0024] component B is an aluminoxane.
[0025] According to a third aspect of this disclosure, this disclosure provides an ethylene copolymer prepared by the method in the second aspect of this disclosure.
[0026] According to a fourth aspect of this disclosure, this disclosure provides a composition comprising an ethylene copolymer and a crosslinking agent, wherein the ethylene copolymer is the ethylene copolymer according to the first or third aspect of this disclosure.
[0027] According to a fifth aspect of this disclosure, this disclosure provides a crosslinked polymer comprising a unit derived from the ethylene copolymer according to the first or third aspect of this disclosure. Petition 870230061875, dated 07 / 14 / 2023, p. 8 / 42 5 / 34
[0028] According to a sixth aspect of this disclosure, this disclosure provides a tire having at least one constituent element comprising ethylene copolymer according to the first or third aspect of this disclosure, the composition according to the fourth aspect of this disclosure, or the cross-linked polymer according to the fifth aspect of this disclosure.
[0029] The ethylene copolymer according to the present disclosure not only has a higher content of conjugated diene structural units, but also has a higher content of 1,2-polymerized vinyl structural units while having a low content of unsaturated double bonds in the copolymer backbone. The ethylene copolymer according to the present disclosure has good crosslinking properties and a crosslinked product has good weather resistance, thermal resistance and ozone resistance. The ethylene copolymer according to the present disclosure has broad application prospects in the field of rubber, especially in the field of rubber tires for vehicles.
[0030] The method for preparing ethylene copolymer according to the present disclosure not only allows the preparation of ethylene copolymer according to the present disclosure, but also achieves improved catalytic activity, thereby improving production efficiency and being suitable for industrial-scale applications.
[0031] Detailed description of the modalities
[0032] The endpoints and any range values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood as including values close to such ranges or values. For numerical ranges, the endpoint values of each range, the endpoint values of each range and individual point values, as well as the individual point values, may be combined with each other to obtain one or more new numerical ranges, and such numerical ranges should be considered as specifically disclosed herein.
[0033] According to a first aspect of the present disclosure, the present disclosure provides an ethylene copolymer, wherein the ethylene copolymer comprises an ethylene-derived structural unit and a conjugated diene-derived structural unit. Petition 870230061875, dated 07 / 14 / 2023, page 9 / 42 6 / 34
[0034] In the present disclosure, the term “ethylene-derived structural unit” means that the structural unit is formed from ethylene and the structural unit has the same type of atoms and the same number of atoms respectively, except for a change in the electronic structure compared with ethylene; and the term “conjugated diene-derived structural unit” means that the structural unit is formed from the conjugated diene, and that the structural unit has the same type of atoms and the same number of atoms respectively, except for a change in the electronic structure compared with the conjugated diene.
[0035] The ethylene copolymer according to the present disclosure, the conjugated diene means a compound containing a conjugated double bond in a molecular structure. The conjugated diene may be one or two or more selected from the compounds represented by a formula 11,H c=R3 R'H
[0036] H2C CCC R5 (Formula 11)
[0037] In formula 11, R3, R4, and R5 are either the same or different, and each is selected from the group consisting of hydrogen and linear or branched C1-C5 alkyl.
[0038] The ethylene copolymer according to the present disclosure, wherein specific examples of the conjugated diene may include, but are not limited to, butadiene and / or isoprene. Preferably, the conjugated diene is butadiene.
[0039] The ethylene copolymer according to the present disclosure, the content of the conjugated diene structural unit being 25-45 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 ethylene copolymer. Preferably, the content of the conjugated diene structural unit is 25-40 mol% based on the total amount of ethylene copolymer. More preferably, the content of the conjugated diene structural unit is 30-35 mol% based on the total amount of ethylene copolymer.
[0040] The ethylene copolymer according to the present disclosure, wherein the conjugated diene structural unit is essentially a 1,2-polymerized structural unit formed by 1,2-polymerization of the conjugated diene and, therefore, the ethylene copolymer according to the present disclosure, wherein the content of the 1,2-polymerized structural unit is high and the content of unsaturated double bonds in a copolymer backbone is low. Petition 870230061875, dated 07 / 14 / 2023, page 10 / 42 7 / 34 Ethylene copolymer according to the present disclosure, wherein the total amount of the 1,2-polymerized structural unit is 95 mol% or more, preferably 98 mol% or more, more preferably 100 mol% based on the total amount of the conjugated diene structural unit in the ethylene copolymer. The ethylene copolymer according to the present disclosure, wherein the double bond content in a backbone of the ethylene copolymer is generally 5 mol% or less, preferably 2 mol% or less, more preferably 0 mol%. The double bonds in the backbone of the ethylene copolymer may be derived, for example, from structural units formed by 1,4-polymerization and 1,3-polymerization of conjugated dienes.
[0041] In the present disclosure, a 1,2-polymerized structural unit refers to a structural unit formed by 1,2-polymerization (i.e., 1,2-addition) of conjugated dienes, a 1,4-polymerized structural unit refers to a structural unit formed by 1,4-polymerization (i.e., 1,4-addition) of conjugated dienes, and a 1,3-polymerized structural unit refers to a structural unit formed by 1,3-polymerization (i.e., 1,3-addition) of conjugated dienes.
[0042] The ethylene copolymer according to the present disclosure, the 1,2-polymerized structural unit includes a 1,2-polymerized vinyl structural unit formed by 1,2-polymerization of the conjugated diene and having side chain double bonds, a 1,2-cyclopropane ring structural unit formed by 1,2-polymerization of the conjugated diene and having a cyclopropane ring, and a 1,2-cyclopentane ring structural unit formed by 1,2-polymerization of the conjugated diene and having a cyclopentane ring.
[0043] Taking butadiene as an example, the 1,2-vinyl polymerized structural unit is represented by formula 14, the 1,2-cyclopropane ring structural unit is represented by formula 15, and the 1,2-cyclopentane ring structural unit is represented by formula 16: HH II —c—c— II H CH II CH2 Formula 14 Formula 15 Petition 870230061875, dated 07 / 14 / 2023, p. 11 / 42 8 / 34
[0044] The ethylene copolymer according to the present disclosure, wherein the content of the 1,2-polymerized vinyl structural unit formed by 1,2-polymerization of the conjugated diene and having side chain double bonds is high. The content of the 1,2-polymerized vinyl structural unit (i.e., the vinyl content) is 20-40 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% with Based on the total amount of ethylene copolymer according to this disclosure. Preferably, the content of the 1,2-polymerized vinyl structural unit is 20-35 mol% based on the total amount of ethylene copolymer according to this disclosure.More preferably, the content of the 1,2-polymerized vinyl structural unit is 21-30 mol% based on the total amount of ethylene copolymer according to this disclosure.
[0045] The ethylene copolymer according to the present disclosure, wherein the content of the 1,2-polymerized vinyl structural unit may be up to 55% or more, preferably 55-90%, 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% based on the total amount of the conjugated diene structural unit in the ethylene copolymer. Preferably, the content of the 1,2-polymerized vinyl structural unit is 60-88% based on the total amount of the conjugated diene structural unit in the ethylene copolymer. More preferably, the content of the 1,2-polymerized vinyl structural unit is 63-85% based on the total amount of the conjugated diene structural unit in the ethylene copolymer.
[0046] The ethylene copolymer according to the present disclosure, in the conjugated diene structural unit of the copolymer, wherein the molar ratio of the 1,2-cyclopentane ring structural unit to the 1,2-cyclopropane ring structural unit is 0.1-3:1, preferably 0.3-2.5:1, more preferably 0.4-2:1, even more preferably 0.5-1.8:1.
[0047] In this disclosure, the microstructure composition of the ethylene copolymer is determined by nuclear magnetic resonance spectroscopy.
[0048] The ethylene copolymer according to the present disclosure not only has a higher content of polymerized vinyl 1,2 structural unit, but also has a molecular weight Petition 870230061875, dated 07 / 14 / 2023, page 12 / 42 9 / 34 higher. The ethylene copolymer according to the present disclosure has an average molecular weight (Mw) of 20,000 to 300,000, preferably 25,000 to 250,000, more preferably 30,000 to 200,000, even more preferably 40,000 to 150,000. The ethylene copolymer according to the present disclosure, wherein the ethylene copolymer has a molecular weight distribution index (Mw / Mn) of 3.5 or less, preferably 3.2 or less, more preferably 1.5-3.
[0049] In this disclosure, molecular weight (g / mol) and molecular weight distribution index are determined by gel permeation chromatography (GPC) with monodisperse polystyrene as a standard.
[0050] The ethylene copolymer according to the present disclosure, wherein the glass transition temperature (Tg) of the ethylene copolymer may be in the range of -50°C to -15°C, preferably in the range of -40°C to -20°C.
[0051] In this disclosure, the glass transition temperature is determined by differential scanning calorimetry (DSC).
[0052] According to a second aspect of the present disclosure, the present disclosure provides a method for the preparation of an ethylene copolymer, comprising contacting ethylene with a conjugated diene in the presence of a polymerization catalyst.
[0053] According to the method of preparation of the present disclosure, a conjugated diene means a compound containing a conjugated double bond in a molecular structure. The conjugated diene may be one or two or more selected from the compounds represented by a formula 11,H c=R3 R'H
[0054] H2C CCC R5 (Formula 11)
[0055] in formula 11, R3, R4 and R5 are the same or different, and each is selected from the group consisting of hydrogen and linear or branched C1-C5 alkyl.
[0056] According to the method of preparation of this disclosure, specific examples of the conjugated diene may include, but are not limited to, butadiene and / or isoprene. Preferably, the conjugated diene is butadiene.
[0057] According to the preparation method of the present disclosure, the polymerization catalyst includes a component A and a component B. Petition 870230061875, dated 07 / 14 / 2023, p. 13 / 42 10 / 34
[0058] Component A is selected from metallic compounds represented by formula 1, / L1\ / X1
[0059] L^X2 (Formula 1)
[0060] In formula 1, M is a metal atom selected from a Group IVB, which may be a titanium atom, a zirconium atom or a hafnium atom. Preferably, in formula 1, M is a zirconium atom.
[0061] In formula 1, X1 and X2 are either the same or different and are each independently a halogen atom. Preferably, in formula 1, X1 and X2 are both chlorine atoms.
[0062] In formula 1, Rb is a divalent group containing an element from Group IVA. In formula 1, Rb is preferably a divalent group containing silicon, more preferably a divalent group represented by formula 2, R1 -----S'----
[0063] R2(Formula 2)
[0064] In formula 2, R1 and R2 are the same or different, and each is independently C1-C10 alkyl. C1-C10 alkyl includes linear C1-C10 alkyl, branched C3-C10 alkyl and C3-C10 cycloalkyl, and specific examples of C1-C10 alkyl 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.
[0065] Preferably, in formula 2, R1 and R2 are both methyl.
[0066] In formula 1, L1 and L2 are either the same or different, and each is selected independently from groups represented by formulas 3 to 6, Petition 870230061875, dated 07 / 14 / 2023, page 14 / 42 11 / 34 Ra3 Ra1 Ra4 Ra5 Formula 3 Formula 5 Formula 6
[0067] in formula 3, Ra1, Ra2, Ra3, Ra4 and Ra5 are either the same or different, and each is independently a hydrogen atom or a C1-C20 alkyl atom.
[0068] In the present disclosure, C1-C20 alkyl includes linear C1-C20 alkyl, branched C3-C20 alkyl and C3-C20 cycloalkyl, and specific examples of C1-C20 alkyl may include, but are not limited to, 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. Petition 870230061875, dated 07 / 14 / 2023, page 15 / 42 12 / 34
[0069] In one embodiment, in formula 3, Ra1, Ra2, Ra3, Ra4 and Ra5 are simultaneously hydrogen atoms.
[0070] In another embodiment, in formula 3, Ra1, Ra2, Ra3, Ra4 and Ra5 are each independently a hydrogen atom or C1-C20 alkyl, and Ra1, Ra2, Ra3, Ra4 and Ra5 are not simultaneously a hydrogen atom. In this embodiment, at least one (preferably two) of Ra1, Ra2, Ra3, Ra4 and Ra5 is preferably C1-C10 alkyl, preferably C1-C20 alkyl, preferably C1-C3 alkyl, more preferably methyl, and the remaining groups are hydrogen atoms.
[0071] In formula 4, Rb1, Rb2, Rb3, Rb4 and Rb5 are either the same or different, and each is independently a hydrogen atom or a C1-C20 alkyl atom.
[0072] In one embodiment, in formula 4, Rb1, Rb2, Rb3, Rb4 and Rb5 are simultaneously hydrogen atoms.
[0073] In another embodiment, in formula 4, Rb1, Rb2, Rb3, Rb4 and Rb5 are each independently a hydrogen atom or C1-C20 alkyl and Rb1, Rb2, Rb3, Rb4 and Rb5 are not simultaneously a hydrogen atom, and in this embodiment, at least one (preferably two, more preferably Rb2 and Rb4) of Rb1, Rb2, Rb3, Rb4 and Rb5 is preferably C1-C10 alkyl, preferably C1-C20 alkyl, more preferably C1-C3 alkyl, even more preferably methyl, and the other groups are hydrogen atoms.
[0074] In formula 5, Rc1, Rc2, Rc3 and Rc4 are either the same or different, and each is independently a hydrogen atom or a C1-C20 alkyl atom.
[0075] In a preferred embodiment, in formula 5, at least one (preferably two, more preferably Rc1 and Rc3) of Rc1, Rc2, Rc3 and Rc4 is C1-C20 alkyl, preferably C1-C20 alkyl, more preferably C1-C3 alkyl, even more preferably methyl, ethyl, n-propyl or isopropyl, and the remaining groups are hydrogen atoms. According to this preferred embodiment, in a further preferred example, Rc1 is methyl, Rc3 is ethyl or n-propyl and Rc2 and Rc4 are hydrogen atoms.
[0076] In formula 6, Rd1, Rd2, Rd3 and Rd4 are either the same or different, and each is independently a hydrogen atom or a C1-C20 alkyl atom.
[0077] In a preferred embodiment, in formula 6, at least one (preferably two, more preferably Rd1 and Rd3) of Rd1, Rd2, Rd3 and Rd4 are C1-C20 alkyl, preferably Petition 870230061875, dated 07 / 14 / 2023, page 16 / 42 13 / 34 C1-C6 alkyl, preferably C1-C3 alkyl, more preferably methyl, ethyl, n-propyl or isopropyl, and the remaining groups are hydrogen atoms. According to this preferred embodiment, in yet another preferred example, Rd1 is methyl, Rd3 is ethyl or n-propyl, and Rd2 and Rd4 are hydrogen atoms.
[0078] According to the method of preparation of this disclosure, component A is preferably one or two or more metallic compounds represented by formulas 7 to Formula 8 Petition 870230061875, dated 07 / 14 / 2023, p. 17 / 42 14 / 34
[0079] In a more preferred example, component A is selected from metal compounds represented by formula 7 and formula 8. According to this more preferred example, the method according to the present disclosure not only increases the content of the conjugated diene structural unit derived from the conjugated diene and the content of a structural unit formed by 1,2-polymerization of the conjugated diene in the ethylene copolymer, but also achieves greater catalytic activity, preparing the ethylene copolymer with higher molecular weight.
[0080] In another more preferred example, component A is selected from metal compounds represented by formula 9 and formula 10. According to this more preferred example, the method according to the present disclosure allows more conjugated dienes to be polymerized in a 1,2-polymerization manner under the condition of obtaining a higher catalytic activity, thus obtaining the ethylene copolymer with a higher content of 1,2-polymerized structural unit.
[0081] According to the method of preparation of the present disclosure, the metallic compound Petition 870230061875, dated 07 / 14 / 2023, page 18 / 42 15 / 34 as component A can be obtained commercially or can be prepared by a conventional method.
[0082] According to the method of preparation of the present disclosure, component B comprises an aluminoxane, preferably an organoaluminoxane, more preferably a methylaluminoxane. In a preferred embodiment, component B is an aluminoxane, preferably an organoaluminoxane, more preferably a methylaluminoxane.
[0083] According to the preparation method of the present disclosure, a molar ratio of component A to component B can be 1:0.1-5000, preferably 1:1-3000, more preferably 1:1-1000, even more preferably 1:10-1000, even more preferably 1:100-800.
[0084] According to the preparation method of the present disclosure, component A can be used in an amount of 0.1-100 μmol, preferably 1-80 μmol, more preferably 3-60 μmol, still preferably 5-30 μmol in relation to 1 mol of the conjugated diene.
[0085] According to the preparation method of the present disclosure, the contact of ethylene with the conjugated diene can be carried out at a temperature of -50°C to 150°C, preferably 10-120°C, more preferably 30-90°C, even more preferably 40-70°C. According to the preparation method of the present disclosure, when ethylene is in contact with the conjugated diene for polymerization, the ethylene pressure can be 0-100 MPa, preferably 2-50 MPa, more preferably 3-30 MPa, even more preferably 5-10 MPa, the pressure being in terms of gauge pressure (G).
[0086] According to the preparation method of the present disclosure, the contact is carried out in the presence of a molecular weight regulator and the molecular weight regulator is used in an amount such that the prepared olefin polymer has an average molecular weight of 20,000 to 300,000, preferably 25,000 to 250,000, more preferably 30,000 to 200,000, even more preferably 40,000 to 150,000. The molecular weight regulator may be conventionally selected, preferably hydrogen.
[0087] The method of preparation of the present disclosure can be carried out by solution polymerization. Solvents that can be used in solution polymerization include Petition 870230061875, dated 07 / 14 / 2023, page 19 / 42 16 / 34 C6-C12 aromatic hydrocarbons, C6-C12 halogenated aromatic hydrocarbons, C5-C10 linear alkanes and C5-C10 cycloalkanes, for example, one or two or more of toluene, chlorobenzene, dichlorobenzene, n-hexane and cyclohexane.
[0088] According to a third aspect of this disclosure, this disclosure provides an ethylene copolymer prepared by the method in the second aspect of this disclosure.
[0089] The ethylene copolymer prepared by the method according to the second aspect of this disclosure not only has a higher content of conjugated diene structural units, but also has a high content of structural units formed by 1,2-polymerization of the conjugated diene, and thus, the ethylene copolymer according to the third aspect of this disclosure has a low content of unsaturated double bonds in a molecular structure and has good weather resistance, thermal resistance and ozone resistance. More importantly, the ethylene copolymer according to the third aspect of this disclosure has a higher content of 1,2-polymerized vinyl structural units and, therefore, the ethylene copolymer according to the third aspect of this disclosure has more excellent vulcanization properties, showing a faster vulcanization rate and a higher degree of vulcanization.
[0090] The content of the conjugated diene structural unit is 20-45 mol%, 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 mol% based on the total amount of ethylene copolymer according to the third aspect of this disclosure. Preferably, the content of the conjugated diene structural unit is 25-40 mol% based on the total amount of ethylene copolymer according to the third aspect of this disclosure. More preferably, the content of the conjugated diene structural unit is 30-35 mol% based on the total amount of ethylene copolymer according to the third aspect of this disclosure.
[0091] The ethylene copolymer according to the third aspect of this disclosure, the conjugated diene structural unit is substantially a 1,2-polymerized structural unit formed by 1,2-polymerization of the conjugated diene. The total amount of the 1,2-polymerized structural unit is 95 mol% or more, preferably 98 mol% or more, more preferably 100 mol% based on the total amount of the unit. Petition 870230061875, dated 07 / 14 / 2023, page 20 / 42 17 / 34 structural conjugated diene in ethylene copolymer. The ethylene copolymer according to the third aspect of the present disclosure, the content of double bonds in a backbone of the ethylene copolymer is generally 5 mol% or less, preferably 2 mol% or less, more preferably 0 mol%.
[0092] The ethylene copolymer according to the third aspect of the present disclosure, the 1,2-polymerized structural unit includes a 1,2-polymerized vinyl structural unit formed by 1,2-polymerization of the conjugated diene and having side chain double bonds, a 1,2-cyclopropane ring structural unit formed by 1,2-polymerization of the conjugated diene and having a cyclopropane ring, as well as a 1,2-cyclopentane ring structural unit formed by 1,2-polymerization of the conjugated diene and having a cyclopentane ring. The content of the 1,2-polymerized vinyl structural unit is 18-40 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 ethylene copolymer, according to the third aspect of this disclosure.Preferably, the content of the 1,2-polymerized vinyl structural unit is 20-35 mol% based on the total amount of ethylene copolymer according to the third aspect of this disclosure. More preferably, the content of the 1,2-polymerized vinyl structural unit is 21-30 mol% based on the total amount of ethylene copolymer according to the third aspect of this disclosure.
[0093] The content of the 1,2-polymerized vinyl structural unit may be up to 55% or more, preferably 55-90%, 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% based on the total amount of the conjugated diene structural unit in the ethylene copolymer according to the third aspect of this disclosure. Preferably, the content of the 1,2-polymerized vinyl structural unit is 60-88% based on the total amount of the conjugated diene structural unit in the ethylene copolymer according to the third aspect of this disclosure. More preferably, the content of the 1,2-polymerized vinyl structural unit is 63-85% based on the total amount of the conjugated diene structural unit in the ethylene copolymer according to the third aspect of this disclosure. Petition 870230061875, dated 07 / 14 / 2023, page 21 / 42 18 / 34
[0094] The ethylene copolymer according to the third aspect of the present disclosure, in the conjugated diene structural unit of the copolymer, wherein the molar ratio of the 1,2-cyclopentane ring structural unit to the 1,2-cyclopropane ring structural unit is 0.1-3:1, preferably 0.3-2.5:1, more preferably 0.4-2:1, and still more preferably 0.5-1.8:1.
[0095] The ethylene copolymer according to the third aspect of this disclosure may have an average molecular weight (Mw) of 20,000 to 300,000, preferably 25,000 to 250,000, more preferably 30,000 to 200,000, even more preferably 40,000 to 150,000. The ethylene copolymer according to the third aspect of this disclosure, wherein the ethylene copolymer has a molecular weight distribution index (Mw / Mn) of 3.5 or less, preferably 3.2 or less, more preferably 1.5-3.
[0096] The ethylene copolymer according to the third aspect of this disclosure, the glass transition temperature (Tg) of the ethylene copolymer may be in the range of -50°C to -15°C, preferably in the range of -40°C to -20°C.
[0097] According to a fourth aspect of this disclosure, this disclosure provides a composition comprising an ethylene copolymer and a crosslinking agent, wherein the ethylene copolymer is the ethylene copolymer according to the first or third aspect of this disclosure.
[0098] The crosslinking agent may be a substance sufficient to crosslink vinyl in the ethylene copolymer. In particular, the crosslinking agent may be one or two or more selected from the group consisting of sulfur, sulfur monochloride, selenium, tellurium and peroxide. In a preferred embodiment, the crosslinking agent is a peroxide, such as dicumyl peroxide.
[0099] The composition according to the present disclosure may also comprise a vulcanization accelerator to speed up vulcanization, thereby shortening the vulcanization time, lowering the vulcanization temperature and reducing the amount of vulcanizing agent used. The vulcanization accelerator may be a conventional substance capable of fulfilling the above function, for example triallyl isocyanurate. The composition according to the present disclosure may also comprise other Petition 870230061875, dated 07 / 14 / 2023, page 22 / 42 19 / 34 components according to specific requirements, such as one or two or more antioxidants and fillers, and a preferred example of a filler may include, but is not limited to, carbon black.
[00100] According to a fifth aspect of this disclosure, this disclosure provides a crosslinked polymer formed by crosslinking the ethylene copolymer according to the first aspect of this disclosure or the third aspect of this disclosure. The ethylene copolymer according to the first or third aspect of this disclosure may be in contact with a crosslinking agent for a crosslinking reaction to obtain the crosslinked polymer according to the fifth aspect of this disclosure.
[00101] According to a sixth aspect of this disclosure, this disclosure provides a tire having at least one constituent element comprising ethylene copolymer according to the first aspect of this disclosure, the composition according to the fourth aspect of this disclosure or the cross-linked polymer according to the fifth aspect of this disclosure.
[00102] This disclosure is described in detail below with reference to examples, but the scope of this disclosure is not limited to this.
[00103] In the following examples and comparative examples, the molecular weight and molecular weight distribution index (Mw / Mn) of a polymer were determined using an Agilent Corporation 1260 Infinity II high-temperature gel permeation chromatograph using two MIXD-B chromatographic columns (300 x 7.5 mm) and one Guard chromatographic column (50 x 7.5 mm). The mobile phase was trichlorobenzene and the flow rate was 1 mL / min; the sample solution had a concentration of 1 mg / mL and an injection volume of 200 μE; the test temperature was 150°C; and monodisperse polystyrene was used as the standard sample.
[00104] In the following examples and comparative examples, NMR spectroscopy was performed using a commercially available 400 MHz NMR spectrometer from Bruker Corporation, deuterated o-dichlorobenzene was used as solvent, and tetramethylsilicon (TMS) was used as an internal standard when the microstructure of a polymer was tested. Where the term conjugated diene structural unit refers to a structural unit formed from a conjugated diene, the term 1,2-polymerization Petition 870230061875, dated 07 / 14 / 2023, page 23 / 42 20 / 34 refers to the polymerization of conjugated dienes in a 1,2-addition manner, the term 1,4-polymerization refers to the polymerization of conjugated dienes in a 1,4-addition manner, and the term 1,3-polymerization refers to the polymerization of conjugated dienes in a 1,3-addition manner; and the term “vinyl” refers to a structural unit formed by the 1,2-polymerization of conjugated dienes possessing side-chain double bonds (taking butadiene as an example, vinyl is The term "cyclopropane ring" refers to a structural unit formed by the 1,2-polymerization of conjugated dienes and possessing a cyclopropane ring, taking butadiene as an example. The term "cyclopentane ring" refers to a structural unit formed by 1,2-polymerization of conjugated dienes and having a cyclopentane ring (taking butadiene as an example, the cyclopentane ring is...).
[00105] The following examples and comparative examples refer to the following metallic compounds and comparative metallic compounds. Metallic compound 1 Petition 870230061875, dated 07 / 14 / 2023, page 24 / 42 21 / 34 Metallic compound 2 Metallic compound 3 Comparative metallic compound 1 Comparative metallic compound 4 Petition 870230061875, dated 07 / 14 / 2023, page 25 / 42 22 / 34 Comparative metallic compound 2 Comparative metallic compound 3 Comparative metallic compound 5 Comparative metallic compound 6
[00106] Preparatory examples 1-4 were used to prepare metal compounds 1-4.
[00107] Preparatory Example 1
[00108] Synthesis of metallic compound 1
[00109] 0.94 g (2 mmol) of bis(2,5-dimethylcyclopentadithiophene)-dimethylsilicon and 50 mL of diethyl ether were added to a reaction flask and 2.5 mL (4 mmol) of a 1.6 M butyllithium-in-hexane solution were added dropwise at -78°C. After stirring at temperature Petition 870230061875, dated 07 / 14 / 2023, page 26 / 42 23 / 34 ambient temperature (25°C) for 6 hours, the temperature was reduced to -40°C and 0.466 g (2 mmol) of zirconium tetrachloride was slowly added. Stirring was carried out overnight. Filtration was performed and the resulting solid was washed with diethyl ether. A product was recrystallized with dichloromethane. Yield: 45% by weight.
[00110] H1-NMR (CDCb, 400 MHz): δppm 6.75 (q, 4H), 2.51 (d, 12H), 1.82 (s, 6H).
[00111] Preparatory Example 2
[00112] Synthesis of metallic compound 4
[00113] The same synthesis method as for metal compound 1 was employed, except that bis(2,5-dimethylcyclopentadithiophene)-dimethylsilicon was replaced by 2 mmol of bis(cyclopentadithiophene)-dimethylsilicon. Yield: 57% by weight.
[00114] H1-NMR (CDCh, 400 MHz): δppm 7.15 (d, 4H), 7.10 (d, 4H), 1.80 (s, 6H).
[00115] Preparatory Example 3
[00116] Synthesis of metallic compound 2.
[00117] 1.02 g (2 mmol) of bis(2-methyl-5-n-propyl-3-(9-phenantryl)-6-hydrocyclopenta[2,3-b]thiophene-6)-dimethylsilicon and 50 mL of diethyl ether were added to a reaction flask and 2.5 mL (4 mmol) of a 1.6 M butyllithium-in-hexane solution were added dropwise at -78°C. After stirring at room temperature (25°C) for 6 hours, 0.466 g (2 mmol) of zirconium tetrachloride was added slowly. Stirring was carried out overnight. Filtration was performed and the resulting solid was washed with diethyl ether. A filtrate was drained to yield a target product. Yield: 56% by weight.
[00118] H1-NMR (CDCb, 400 MHz): 5ppm 7.15-8.90 (m, 18H), 6.62 (s, 2H), 1.15-2.95 (m, 14H), 1.08 (s, 6H), 0.92 (t, 6H).
[00119] Preparatory Example 4
[00120] Synthesis of metallic compound 3
[00121] The same synthesis method for a metallic compound 5 was adopted, except that 2 mmol of bis(2-methyl-5-ethyl-3-(9-phenantryl)-6-hydrocyclopenta[2,3-b]thiophene-6)-dimethylsilicon Petition 870230061875, dated 07 / 14 / 2023, p. 27 / 42 24 / 34 were used instead of bis(2,5-dimethyl-3-phenyl-6-hydrocyclopenta[2,3-b]thiophene-6)-dimethylsilicon. Yield: 61% by weight.
[00122] H1-NMR (CDCI3, 400 MHz): 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).
[00123] Examples 1-6 were used to illustrate the ethylene polymer and the method of preparing it according to the present disclosure.
[00124] Example 1
[00125] A 500 mL stainless steel reactor was subjected to total nitrogen replacement and then to total hydrogen replacement. 120 g of toluene, 8 mL of methylaluminoxane (a 10% by weight solution in toluene), and 25.0 g of butadiene were added, followed by 0.44 kg / cm²G of hydrogen. A liquid phase and a gas phase were saturated with 7.8 kg / cm²G of ethylene at 60°C. Then, 5 μmol of a metallic compound 1 previously dissolved in toluene was added to initiate polymerization. Ethylene gas was continuously supplied to maintain a total pressure of 7.8 kg / cm²G. After 15 minutes of polymerization, a small amount of methanol was added to terminate the reaction. The resulting product was poured into a large quantity of ethanol, to which hydrochloric acid (HCl concentration was 0.2% by weight) was added for precipitation. A 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 obtain the ethylene copolymer according to the present disclosure. The specific experimental conditions are listed in Table 1 and the test results of the property parameters of the prepared ethylene copolymer are listed in Table 2.
[00126] Comparative Example 1
[00127] An ethylene copolymer was prepared by the same method as in Example 1, except that instead of using methylaluminoxane, 2.5 mL of a triisobutylaluminum n-hexane solution (the triisobutylaluminum concentration was 1 M) and 0.03 mmol of Petition 870230061875, dated 07 / 14 / 2023, page 28 / 42 25 / 34 trityl-tetrakis(pentafluorophenyl)borate was dissolved in toluene along with metal compound 1, to be added to a polymerization reactor. The specific experimental conditions are listed in Table 1 and the test results of the property parameters of the prepared ethylene copolymer are listed in Table 2.
[00128] Comparative Example 2
[00129] An ethylene copolymer was prepared by the same method as in Comparative Example 1, except that metal compound 1 was replaced by a comparative metal compound 1. The specific experimental conditions are listed in Table 1 and the test results of the property parameters of the prepared ethylene copolymer are listed in Table 2.
[00130] Comparative Example 3
[00131] An ethylene copolymer was prepared by the same method as Example 1, except that the metallic compound 1 was replaced by the comparative metallic compound 1. The specific experimental conditions are listed in Table 1 and the test results of the property parameters of the prepared ethylene copolymer are listed in Table 2.
[00132] Example 2
[00133] An ethylene copolymer was prepared by the same method as Example 1, except that metal compound 1 was replaced by metal compound 2, and the property parameters of the prepared ethylene copolymer are listed in Table 2.
[00134] Comparative Example 4
[00135] An ethylene copolymer was prepared by the same method as Example 2, except that, instead of using methylaluminoxane, 2.5 mL of a triisobutylaluminum n-hexane solution (the triisobutylaluminum concentration was 1 M) was used and 0.03 mmol of trityl-tetrakis(pentafluorophenyl)borate was dissolved in toluene along with metal compound 2 to be added to the polymerization reactor. The specific experimental conditions are listed in Table 1 and the test results of the property parameters of the prepared ethylene copolymer are listed in Table 2. Petition 870230061875, dated 07 / 14 / 2023, page 29 / 42 26 / 34
[00136] Comparative Example 5
[00137] An ethylene copolymer was prepared by the same method as in Example 2, except that the metallic compound 2 was replaced by a comparative metallic compound 2. The specific experimental conditions are listed in Table 1 and the test results of the property parameters of the prepared ethylene copolymer are listed in Table 2.
[00138] Example 3
[00139] A 500 mL stainless steel reactor was subjected to total nitrogen replacement and then to total hydrogen replacement. 120 g of toluene, 7.5 mL of MAO (a 10% by weight solution in toluene), and 35 g of butadiene were added. 0.44 kg / cm²g of hydrogen was then added, and a liquid phase and a gas phase were saturated with 7.8 kg / cm²g of ethylene at 60°C. Then, 5 μmol of the metal compound 2, previously dissolved in toluene, was added to initiate polymerization. Ethylene gas was supplied continuously to maintain a total pressure of 7.8 kg / cm²g. After 15 minutes of polymerization, a small amount of methanol was added to terminate the reaction. The resulting product was poured into a large quantity of ethanol to which hydrochloric acid (0.2% by weight, hydrochloric acid being expressed as HCl) was added, causing precipitation. A copolymer was then separated by filtration and washed with ethanol.The washed copolymer was dried in a vacuum oven until the weight was no longer reduced to obtain the ethylene copolymer according to the present disclosure. The specific experimental conditions are listed in Table 1 and the test results of the property parameters of the prepared ethylene copolymer are listed in Table 2.
[00140] Comparative Example 6
[00141] An ethylene copolymer was prepared by the same method as in Example 3, except that the metallic compound 2 was replaced by the comparative metallic compound 2. The specific experimental conditions are listed in Table 1 and the test results of the property parameters of the prepared ethylene copolymer are listed in Table 2.
[00142] Example 4 Petition 870230061875, dated 07 / 14 / 2023, pages 30 / 42 27 / 34
[00143] An ethylene copolymer was prepared by the same method as in Example 1, except that metal compound 1 was replaced by metal compound 3. The specific experimental conditions are listed in Table 1 and the test results of the property parameters of the prepared ethylene copolymer are listed in Table 2.
[00144] Comparative Example 7
[00145] An ethylene copolymer was prepared by the same method as Example 3, except that, instead of using methylaluminoxane, 2.5 mL of a triisobutylaluminum n-hexane solution (the triisobutylaluminum concentration was 1 M) was used and 0.03 mmol of trityl-tetrakis(pentafluorophenyl)borate was dissolved in toluene along with metal compound 3 to be added to the polymerization reactor. The specific experimental conditions are listed in Table 1 and the test results of the property parameters of the prepared ethylene copolymer are listed in Table 2.
[00146] Comparative Example 8
[00147] An ethylene copolymer was prepared by the same method as in Example 3, except that the metallic compound 3 was replaced by a comparative metallic compound 3. The specific experimental conditions are listed in Table 1 and the test results of the property parameters of the prepared ethylene copolymer are listed in Table 2.
[00148] Comparative Example 9
[00149] An ethylene copolymer was prepared by the same method as in Example 3, except that the metallic compound 3 was replaced by a comparative metallic compound 3. The specific experimental conditions are listed in Table 1 and the test results of the property parameters of the prepared ethylene copolymer are listed in Table 2.
[00150] Example 5
[00151] An ethylene copolymer was prepared by the same method as in Example 1, except that metal compound 1 was replaced by metal compound 4. The specific experimental conditions are listed in Table 1 and the test results of the parameters Petition 870230061875, dated 07 / 14 / 2023, pages 31 / 42 28 / 34 properties of the prepared ethylene copolymer are listed in Table 2.
[00152] Comparative Example 10
[00153] An ethylene copolymer was prepared by the same method as Example 5, except that, instead of using methylaluminoxane, 2.5 mL of a triisobutylaluminum n-hexane solution (the triisobutylaluminum concentration was 1 M) was used and 0.03 mmol of trityl-tetrakis(pentafluorophenyl)borate was dissolved in toluene along with metal compound 4 to be added to the polymerization reactor. The specific experimental conditions are listed in Table 1 and the test results of the property parameters of the prepared ethylene copolymer are listed in Table 2.
[00154] Comparative Example 11
[00155] An ethylene copolymer was prepared by the same method as in Example 5, except that the metallic compound 4 was replaced by a comparative metallic compound 4. The specific experimental conditions are listed in Table 1 and the test results of the property parameters of the prepared ethylene copolymer are listed in Table 2.
[00156] Example 6
[00157] An ethylene copolymer was prepared by the same method as in Example 1, except that metal compound 1 was replaced by metal compound 4. The specific experimental conditions are listed in Table 1 and the test results of the property parameters of the prepared ethylene copolymer are listed in Table 2.
[00158] Comparative Example 12
[00159] An ethylene copolymer was prepared by the same method as in Example 6, except that the metallic compound 4 was replaced by a comparative metallic compound 5. The specific experimental conditions are listed in Table 1 and the test results of the property parameters of the prepared ethylene copolymer are listed in Table 2.
[00160] Comparative Example 13 Petition 870230061875, dated 07 / 14 / 2023, pages 32 / 42 29 / 34
[00161] An ethylene copolymer was prepared by the same method as in Example 6, except that the metallic compound 4 was replaced by a comparative metallic compound 6. The specific experimental conditions are listed in Table 1 and the test results of the property parameters of the prepared ethylene copolymer are listed in Table 2. Table 1 No. Metallic compound MAO mL Triisobutylaluminum mL Trityl-tetrakis(pentafluorophenyl)borate mmol Butadiene g Ethylene kg / cm2G Hydrogen kg / cm2G No. Quantity of use pmol Example 1 1 5 8 - - 25.0 7.8 0.44 Example Comparative 1 1 5 - 2.5 0.03 25.0 7.8 0.44 Example Comparative 2 Metallic compound comparative 1 5 - 2.5 0.03 25.0 7.8 0.44 Example Comparative 3 Metallic compound comparative 1 5 8 - - 25.0 7.8 0.44 Example 2 2 5 8 - - 25.0 7.8 0.44 Example Comparative 4 2 5 2.5 0.03 25.0 7.8 Comparative Example 5 Comparative metallic compound 2 5 8 - - 25.0 7.8 0.44 Example 3 2 5 7.5 - - 35.0 7.8 0.44 Comparative Example 6 Comparative metallic compound 2 5 7.5 - - 35.0 7.8 0.44 Example 4 3 5 8 - - 25.0 7.8 0.44 Comparative Example 7 3 5 - 2.5 0.03 25.0 7.8 0.44 Comparative Example 8 Comparative metallic compound 3 5 - 2.5 0.03 25.0 7.8 0.44 Comparative Example 9 Comparative metallic compound 3 5 8 - - 25.0 7.8 0.44 Example 5 4 5 8 - - 25.0 7.8 0.44 Comparative Example 10 4 5 - 2.5 0.Comparative Example 11 Metallic Compound Comparative 4 5 8 - - 25.0 7.8 0.44 Example 6 4 5 8 - - 25.0 12 0.44 Example Compound 5 8 - - 25.0 7.8 0.44 Petition 870230061875, dated 07 / 14 / 2023, pages 33 / 42 30 / 34 Comparative 12 metallic comparative 5 Example Comparative 13 Metallic compound comparative 6 5 8 - - 25.0 7.8 0.44 Petition 870230061875, dated 07 / 14 / 2023, pages 34 / 42 31 / 34 Table 2 No. Yield g Activity kg / (mmol / h) Mw Mn Mw / Mn Melting point °C Glass transition temperature °C Content of conjugated diene structural unit mol% Vinyl content mol% Cyclopropane ring content mol% Cyclopentane ring content mol% % molar content of 1,4-structure % molar content of 1,3-structure Example 1 6.5 5.2 138000 52000 2.7 - -30 31.3 21.6 4.07 5.63 0 0 Comparative Example 1 6.0 4.80 127000 47500 2.7 29 -35 23 14.95 4.14 3.91 0 0 Comparative Example 2 4.5 3.60 Example 3: 4.8 3.84 62000 30200 2.1 120 -38 9.9 5.2 3.5 1.2 0 0 Example 2: 0.8 0.64 45600 19800 2.3 - -29 34.13 25.6 5.46 3.07 0 0 Example 4: 0.6 0.48 38000 17500 2.2 - -31 23 15.87 2.99 4.14 0 0 Example 5: 0.7 0.56 41000 19000 Example 3: 0.8 0.64 41000 20500 2.0 - -22 31 26.35 2.17 2.48 0 0 Example 6: 0.6 0.48 37000 17500 2.1 35 -33 14 9.8 2.24 1.96 0 0 Example 4: 3.1 2.48 48000 16800 2.Example Comparative: 9 - -30 33.57 23.5 5.71 4.36 0 0 Example Comparative: 7 2.8 2.24 42500 15600 2.7 - -33 17 9.86 3.74 3.4 0 0 Example Comparative: 8 2.4 1.92 41000 14500 2.8 30 -35 13 7.15 3.25 2.6 0 0 Example Comparative: 9 3.0 2.4 45000 23000 2.0 32 -36 16 8.2 4.6 3.2 0 0 Example 5 5.8 4.64 49000 26000 1.9 - -28 31.54 20.5 4.10 6.94 0 0 Comparative Example 10 5.2 4.16 35000 16700 2.1 34 -32 15 9.0 1.95 4.05 0 0 Comparative Example 11 4.1 3.28 35000 17000 2.1 120 -39 11 4.8 2.9 3.3 0 0 Example 6 6.3 5.04 59000 38000 1.6 - -29 31.2 23.4 5.30 2.50 0 0 Comparative Example 12 12.0 9.60 230000 100000 2.3 105 - 4.51 0 1.04 3.47 0 Example 2.5 2.00 120000 57000 2.1 102 - 6 0.12 1.5 4.38 0 0. Petition 870230061875, dated 07 / 14 / 2023, pages 35 / 42 32 / 34 Comparative 13 Petition 870230061875, dated 07 / 14 / 2023, pages 36 / 42 33 / 34
[00162] The results in Table 2 confirmed that the ethylene copolymer according to the present disclosure not only has an increased molecular weight and a narrow molecular weight distribution index, but also has an increased content of conjugated diene structural units, while the ethylene copolymer backbone is substantially free of unsaturated groups. The results in Table 2 also confirmed that the olefin polymerization method according to the present disclosure reveals that not only can the ethylene copolymer according to the present disclosure be prepared, but also increased catalytic activity can be obtained, thus increasing production efficiency.
[00163] Test Examples 1-2
[00164] The ethylene copolymers prepared in Examples 2 and 4 were respectively mixed with carbon black, peroxide, and vulcanizing aid in an open mill according to the formulas shown in Table 3. The vulcanization properties of the mixtures were tested using an MDR vulcanizer purchased from Alpha Technology Company at a temperature of 160°C, and a vulcanization rate was evaluated, with a test time of 20 min. The test results are listed in Table 4.
[00165] Examples of Comparative Testing 1-2
[00166] The vulcanization properties of ethylene copolymers prepared in Comparative Examples 5 and 9 were tested respectively using the same method as in Examples of Tests 1-2, and the test results are shown in Table 4. Table 3 No. Example Test 1 Example Comparative Test 1 Example Test 2 Example Comparative Test 2 Source and quantity of ethylene copolymer use Example 2 100 parts by weight (phr) Example Comparative 5 100 phr Example 4 100 phr Example Comparative 9 100 phr Quantity of carbon black N550 use 15 phr 15 phr 15 phr 15 phr Quantity of dicumyl peroxide use 5 phr 5 phr 5 phr 5 phr Quantity of triallylisocyanurate use 1 phr 1 phr 1 phr 1 phr Table 4 Petition 870230061875, dated 07 / 14 / 2023, pages 37 / 42 34 / 34 No. Example of Test 1 Example of Comparative Test 1 Example of Test 2 Example of Comparative Test 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
[00167] As can be seen from the vulcanization property test results in Table 4, the ethylene copolymer according to the present disclosure has a faster torque increase during vulcanization, a faster vulcanization rate and a higher degree of vulcanization.
[00168] The preferred embodiments of this disclosure are described above in detail, but this disclosure is not limited to them. Within the range of technical concepts of this disclosure, the technical solution of this disclosure may be subject to various simple variations, including the combination of various technical features in any other suitable manner, and these simple variations and combinations shall also be regarded as the contents disclosed by this disclosure, all falling within the scope of protection of this disclosure.
Claims
1. Ethylene copolymer, characterized by comprising an ethylene structural unit derived from ethylene and a conjugated diene structural unit derived from a conjugated diene; based on the total amount of ethylene copolymer, the content of the conjugated diene structural unit is 30-45 mol% and the content of a 1,2-polymerized vinyl structural unit formed by 1,2-polymerization of the conjugated diene and having side-chain double bonds is 20-40 mol%; the total amount of a 1,2-polymerized structural unit is 95 mol% or more, based on the total amount of the conjugated diene structural unit in the ethylene copolymer, and the ethylene copolymer has an average molecular weight of 30,000 to 300.000, in which the molecular weight and molecular weight distribution index are determined by gel permeation chromatography using monodisperse polystyrene as a standard; the microstructure composition of the ethylene copolymer is determined by nuclear magnetic resonance spectroscopy.
2. Ethylene copolymer according to claim 1, characterized in that the content of the 1,2-polymerized vinyl structural unit is 20-35 mol% based on the total amount of ethylene copolymer; preferably the content of the 1,2-polymerized vinyl structural unit is 21-30 mol%, based on the total amount of ethylene copolymer.
3. Ethylene copolymer according to claim 1 or 2, characterized in that the content of the 1,2-polymerized vinyl structural unit is 55-90% based on the content of the conjugated diene structural unit; the content of the 1,2-polymerized vinyl structural unit is preferably 60-88% based on the content of the conjugated diene structural unit, or the content of the 1,2-polymerized vinyl structural unit is 63-85%, based on the content of the conjugated diene structural unit.
4. Ethylene copolymer according to any one of claims 1 to 3, Petition 870260039023, dated 04 / 27 / 2026, page 19 / 29 2 / 8 characterized in that the total amount of the 1,2-polymerized structural unit is 98 mol% based on the total amount of the conjugated diene structural unit in the ethylene copolymer or the total amount of the 1,2-polymerized structural unit is 100 mol% based on the total amount of the conjugated diene structural unit in the ethylene copolymer.
5. Ethylene copolymer according to any one of claims 1 to 4, characterized in that the content of the conjugated diene structural unit is 30-40 mol% based on the total amount of ethylene copolymer or the content of the conjugated diene structural unit is 30-35 mol% based on the total amount of ethylene copolymer.
6. Ethylene copolymer according to any one of claims 1 to 5, characterized in that the molar ratio of a 1,2-cyclopentane ring structural unit to a 1,2-cyclopropane ring structural unit in the conjugated diene structural unit of the copolymer is 0.1-3:1; or 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 0.3-2.5:1, 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 0.4-2:1; The molar ratio of the 1,2-cyclopentane ring structural unit to the 1,2-cyclopropane ring structural unit in the conjugated diene copolymer structural unit is 0.5-1.8:
1.
7. Ethylene copolymer according to any one of claims 1 to 6, characterized in that the ethylene copolymer has an average molecular weight of 30,000 to 250,000; wherein the ethylene copolymer has a weight-average molecular weight of 30,000 to 200,000; wherein the ethylene copolymer has a weight-average molecular weight of 40,000 to 150,000; wherein the copolymer has a molecular weight distribution index of 3.5 or less; wherein the copolymer has a molecular weight distribution index of 3.2 or less; wherein the copolymer has a molecular weight distribution index of 1.5-3.
8. Ethylene copolymer according to any one of claims 1 to 7, characterized in that the glass transition temperature of the ethylene copolymer is in the range of -50°C to -15°C, wherein the glass transition temperature is determined by differential scanning calorimetry; or the glass transition temperature of the ethylene copolymer is in the range of -40°C to -20°C, wherein the glass transition temperature is determined by differential scanning calorimetry.
9. Ethylene copolymer, according to any one of claims 1 to 8, characterized in that the conjugated diene is butadiene.
10. Method for the preparation of the ethylene copolymer being defined according to claim 1, containing the contact of ethylene with a conjugated diene in the presence of a polymerization catalyst, characterized in that the polymerization catalyst comprises a component A and a component B, component A is selected from metal compounds represented by formula 1, XL1 / X1 L2 X2 (Formula 1) in formula 1, M is a metal atom selected from a Group IVB, X1 and X2 are the same or different, and each is independently a halogen atom, Petition 870260039023, dated 04 / 27 / 2026, p. 21 / 29 4 / 8 Rb is a divalent group containing an element from Group IVA, Li and L2 are the same or different, and each is selected independently from groups represented by formulas 3 to 6, Ra3 Ra1 Ra5 (^3) Formula 4 Petition 870260039023, dated 27 / 04 / 2026, page.22 / 29 5 / 8 in formula 3, Ra1, Ra2, Ra3, Ra4 and Ra5 are the same or different and are each independently a hydrogen atom or C1-C20 alkyl, in formula 4, Rb1, Rb2, Rb3, Rb4 and Rb5 are the same or different, and are each independently a hydrogen atom or C1-C20 alkyl, in formula 5, Rc1, Rc2, Rc3 and Rc4 are the same or different and are each independently a hydrogen atom or C1-C20 alkyl, and Petition 870260039023, dated 04 / 27 / 2026, page 23 / 29 6 / 8 in formula 6, Rd1, Rd2, Rd3 and Rd4 are the same or different, and are each independently a hydrogen atom or C1-C20 alkyl; and component B comprises an aluminoxane.
11. Method according to claim 10, characterized in that in formula 1, M is a zirconium atom; and / or in Formula 1, Xi and X2 are each independently a chlorine atom.
12. Method according to claims 10 or 11, characterized in that in formula 1, Rb is a divalent group containing silicon, preferably a divalent group represented by formula 2, R1 ------Si-----I r2 (Formula 2) in formula 2, R1 and R2 are the same or different, and each is an independent Ci-Cio alkyl.
13. Method according to claim 10, characterized in that component A is one or two or more selected metallic compounds, represented by formulas 7 to 10: Formula 8 Petition 870260039023, dated 04 / 27 / 2026, page 24 / 29 7 / 8 14. Method according to any one of claims 10 to 13, characterized in that the molar ratio of component A to component B is 1:0.1-5000.
15. Method according to any one of claims 10 to 14, characterized in that component A is used in an amount of 0.1–100 μmol relative to 1 mol of the conjugated diene.
16. Method according to any one of claims 10 to 15, characterized in that the conjugated diene is butadiene.
17. Method according to any one of claims 10 to 16, characterized in that the contact is carried out at a temperature of -50°C to 150°C and the ethylene pressure is 0-100 MPa, the pressure being considered in terms of gauge pressure.
18. Method according to any one of claims 10 to 17, characterized in that the contact is made in the presence of a molecular weight regulator, the molecular weight regulator being used in a certain amount so that the prepared ethylene copolymer has an average molecular weight of 30,000 to 300,000, or 30,000 to 250,000, or 30,000 to 200,000, or 40,000 to 150,000.
19. Composition comprising an ethylene copolymer and a crosslinking agent, characterized in that the ethylene copolymer is the ethylene copolymer according to any one of claims 1 to 9.
20. Crosslinked polymer characterized by being formed by crosslinking the ethylene copolymer according to any one of claims 1 to 9.
21. Tire characterized by having at least one constituent element comprising ethylene copolymer according to any one of claims 1 to 9, the composition according to claim 19, or the crosslinked polymer according to claim 20.