Ethylene-α-olefin-nonconjugated polyene copolymer and method for producing the same

Abstract

To improve cold resistance and roll processability of an ethylene-α-olefin-nonconjugated polyene copolymer such as EBT while maintaining their high strength.SOLUTION: There is provided an ethylene-α-olefin-nonconjugated polyene copolymer (P) comprising structural units derived from ethylene [A], structural units derived from α-olefins [A2] having carbon numbers of 4 to 20, and structural units derived from nonconjugated polyene [A3], and containing structural units derived from 1-butene, wherein the ethylene-α-olefin-nonconjugated polyene copolymer (P) is specified in the following manner: the molar ratio [A1] / [A2] is 40 / 60 to 90 / 10, and the intrinsic viscosity [η] measured at 135°C in decalin is 5.0 to 7.0 dl / g, and the like. There is also provided a method for producing the same.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an ethylene-α-olefin-non-conjugated polyene copolymer and a method for producing the same. [Background technology]

[0002] Ethylene-α-olefin rubbers, such as ethylene-propylene copolymer rubber (EPR) and ethylene-propylene-diene copolymer rubber (EPDM), do not have unsaturated bonds in the main chain of their molecular structure, and therefore have superior heat aging resistance, weather resistance, and ozone resistance compared to general-purpose conjugated diene rubbers. They are therefore widely used in applications such as automotive parts, electrical wire materials, electrical and electronic parts, construction and civil engineering materials, and industrial parts.

[0003] Among these, ethylene-1-butene-ENB copolymer (hereinafter abbreviated as EBT) has excellent cold resistance and roll processability, but in some applications it lacks strength, and there is a demand for it to be made stronger.

[0004] One way to increase the strength is to increase the molecular weight of EBT, and EBT with a high intrinsic viscosity [η] (i.e., increased molecular weight) has already been proposed (Patent Document 1). The intrinsic viscosity [η] of EBT specifically shown in Patent Document 1 is 7.60 to 8.41. By adjusting the intrinsic viscosity to such a level, high strength can be achieved, but the roll processability is not sufficient, and improvement in this area is desired. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2015 / 122415 Summary of the Invention [Problem to be solved by the invention]

[0006] Therefore, the present inventors conducted research aimed at improving the cold resistance and roll processability of ethylene-α-olefin-non-conjugated polyene copolymers such as EBT while maintaining their high strength. As a result, they found that ethylene-α-olefin-non-conjugated polyene copolymers such as EBT with a specific intrinsic viscosity could achieve this objective, and thus arrived at the present invention. [Means for solving the problem]

[0007] The present invention includes any one of the following aspects [1] to

[14] . [1] An ethylene-α-olefin-non-conjugated polyene copolymer (P) having structural units derived from ethylene [A], structural units derived from at least one kind of α-olefin [A2] having 4 to 20 carbon atoms, and structural units derived from at least one kind of non-conjugated polyene [A3], wherein the structural units derived from the α-olefin [A2] having 4 to 20 carbon atoms include structural units derived from 1-butene, and the copolymer satisfies the following requirements (1) and (2): Requirement (1) The molar ratio [[A1] / [A2]] of the structural unit derived from ethylene [A1] to the structural unit derived from an α-olefin [A2] having 4 to 20 carbon atoms is 40 / 60 to 90 / 10. Requirement (2) The intrinsic viscosity [η] measured in decalin at 135°C is 5.0 to 7.0 dl / g.

[0008] [2] The ethylene-α-olefin-non-conjugated polyene copolymer (P) according to the above item [1] is characterized in that it further satisfies the following requirements (3) and (4): Requirement (3) The content of structural units derived from the non-conjugated polyene [A3] is 0.1 to 6.0 mol % (where the total of the structural units [A1], [A2] and [A3] is 100 mol %).

[0009] [3] The ethylene-α-olefin-non-conjugated polyene copolymer (P) according to the above [1] or [2], further characterized in that it satisfies the following requirement (4): Requirement (4) The B value represented by the following formula (i) is 1.20 or more. B value=([EX]+2[Y]) / [2×[E]×([X]+[Y])]···(i) Here, [E], [X], and [Y] represent the mole fractions of ethylene [A1], α-olefin [A2] having 4 to 20 carbon atoms, and non-conjugated polyene [A3], respectively, and [EX] represents the ethylene [A1]-α-olefin [A2] having 4 to 20 carbon atoms dyad sequence fraction.

[0010] [4] The ethylene-α-olefin-non-conjugated polyene copolymer (P) according to any one of the above [1] to [3], wherein the amount of oil extension is 50 to 150 parts by mass per 100 parts by mass of the ethylene-α-olefin-non-conjugated polyene copolymer (P).

[0011] [5] The ethylene-α-olefin-non-conjugated polyene copolymer (P) according to any one of the above [1] to [4], wherein the non-conjugated polyene [A3] contains only one partial structure selected from the group consisting of the following partial structural formulas (I) and (II) in total per molecule:

[0012] [ka]

[0013] [6] The ethylene-α-olefin-non-conjugated polyene copolymer (P) according to any one of the above [1] to [5], wherein the non-conjugated polyene [A3] is 5-ethylidene-2-norbornene (ENB).

[0014] [7] The ethylene-α-olefin-non-conjugated polyene copolymer (P) according to any one of the above [1] to [6], which has a tensile strength of 5 MPa or more as measured in accordance with JIS K6251.

[0015] [8] The ethylene-α-olefin-non-conjugated polyene copolymer (P) according to any one of [1] to [7] above, which has a permanent set (%) of 98% or less after being compressed to 25% in an atmosphere of -30°C for 24 hours in accordance with JIS K6262.

[0016] [9] The ethylene-α-olefin-non-conjugated polyene copolymer (P) according to any one of the above [1] to [8], which has a glass transition temperature (Tg) of −55° C. or lower.

[0017]

[10] A bridged metallocene compound (t) represented by the following general formula (1): and at least one compound (u) selected from the group consisting of an organometallic compound (u-1), an organoaluminum oxy compound (u-2), and a compound (u-3) that reacts with the bridged metallocene compound (t) to form an ion pair; The method for producing the ethylene-α-olefin-non-conjugated polyene copolymer (P) according to any one of the above [1] to [9], comprising copolymerizing ethylene, 1-butene (or, together with 1-butene, an α-olefin having 5 to 20 carbon atoms), or an α-olefin having 5 to 20 carbon atoms, and a non-conjugated polyene in the presence of an olefin polymerization catalyst containing

[0018] [ka]

[0019] R in general formula (1) 1 From R 14 In the above general formula (1), R 1 , R 2 , R3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 are each independently a hydrogen atom, a hydrocarbon group, a heteroatom-containing hydrocarbon group, or a silicon-containing group, and R 1 From R 4 Any two of the substituents up to R may be bonded to each other to form a ring, 5 From R 12 Any two of the substituents up to R may be bonded to each other to form a ring, 13 and R 14 may be bonded to each other to form a ring. Y in general formula (1) In the general formula (1), Y is a carbon atom, a silicon atom, a germanium atom, or a tin atom. M, Q, and j in general formula (1) In general formula (1), M is a Group 4 transition metal. Q is a halogen atom, a hydrocarbon group, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair, and when j is an integer of 2 or greater, Qs may be the same or different from one another.

[0020]

[11] The method for producing the ethylene-α-olefin-non-conjugated polyene copolymer (P) according to

[10] above, wherein the bridged metallocene compound (t) represented by the general formula (1) above is represented by the following general formula (2):

[0021] [ka]

[0022] In the above general formula (2), R 13 , R 14 , M, Q, and j are the same as in the general formula (1) above.

[0023]

[12] The method for producing the ethylene-α-olefin-non-conjugated polyene copolymer (P) according to either of

[10] or

[11] above, wherein M in general formula (1) or general formula (2) is a hafnium atom.

[0024]

[13] The method for producing the ethylene-α-olefin-non-conjugated polyene copolymer (P) according to any one of the above

[10] to

[12] , wherein in general formula (1) or general formula (2), Q is a methyl group and j is an integer of 2.

[0025]

[14] In general formula (1) or general formula (2), R 13 and R 14 and are both methoxy groups. [Effects of the Invention]

[0026] The ethylene-α-olefin-non-conjugated polyene copolymers, including EBT, produced by the present invention have improved cold resistance and roll processability while maintaining high strength, making them suitable for a wider range of applications. DETAILED DESCRIPTION OF THE INVENTION

[0027] The ethylene-α-olefin-non-conjugated polyene copolymer (P) of the present invention will be described below.

[0028] Ethylene-α-olefin-non-conjugated polyene copolymer (P) The ethylene-α-olefin-non-conjugated polyene copolymer (P) has structural units derived from ethylene [A], structural units derived from at least one kind of α-olefin [A2] having 4 to 20 carbon atoms, and structural units derived from at least one kind of non-conjugated polyene [A3], wherein the structural units derived from the α-olefin [A2] having 4 to 20 carbon atoms include structural units derived from 1-butene, and satisfies the following requirements (1) and (2): Requirement (1) The molar ratio [[A1] / [A2]] of the structural unit derived from ethylene [A1] to the structural unit derived from an α-olefin [A2] having 4 to 20 carbon atoms is 40 / 60 to 90 / 10. Requirement (2) The intrinsic viscosity [η] measured in decalin at 135°C is 5.0 to 7.0 dl / g.

[0029] The ethylene-α-olefin-non-conjugated polyene copolymer (P) of the present invention preferably further satisfies the following requirement (3). Requirement (3) The content of structural units derived from the non-conjugated polyene [A3] is 0.1 to 6.0 mol % (where the total of the structural units [A1], [A2] and [A3] is 100 mol %).

[0030] The ethylene-α-olefin-non-conjugated polyene copolymer (P) of the present invention preferably further satisfies the following requirement (4). Requirement (4) The B value represented by the following formula (i) is 1.20 or more. B value=([EX]+2[Y]) / [2×[E]×([X]+[Y])]···(i) Here, [E], [X], and [Y] represent the mole fractions of ethylene [A1], α-olefin [A2] having 4 to 20 carbon atoms, and non-conjugated polyene [A3], respectively, and [EX] represents the ethylene [A1]-α-olefin [A2] having 4 to 20 carbon atoms dyad sequence fraction. The α-olefin [A2] having 4 to 20 carbon atoms and the non-conjugated polyene [A3] may each be used alone or in combination of two or more.

[0031] α-Olefin [A2] The ethylene-α-olefin-non-conjugated polyene copolymer (P) of the present invention contains a structural unit derived from 1-butene as a structural unit derived from the α-olefin [A2] having 4 to 20 carbon atoms, and optionally further contains at least one or more α-olefins having 5 to 20 carbon atoms in combination.

[0032] Examples of the α-olefins [A2] having 5 to 20 carbon atoms that may be used in combination include 1-pentene, 1-hexene, 1-octene, 1-nonene, and 1-decene, which have a straight-chain structure without a side chain, as well as 1-nonadecene having 19 carbon atoms and 1-eicosene having 20 carbon atoms, and also 4-methyl-1-pentene, 9-methyl-1-decene, 11-methyl-1-dodecene, and 12-ethyl-1-tetradecene, which have a side chain. As the α-olefin having 5 to 20 carbon atoms that may be used in combination, an α-olefin having 5 to 10 carbon atoms is preferred, and 1-hexene, 1-octene, and the like are particularly preferred.

[0033] Non-conjugated polyene [A3] In the present invention, the non-conjugated polyene [A3] preferably contains only one partial structure selected from the group consisting of the following partial structural formulae (I) and (II) in one molecule.

[0034] [ka]

[0035] Specific examples of the non-conjugated polyenes [A3] include linear non-conjugated dienes such as 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, and 7-methyl-1,6-octadiene, and cyclic non-conjugated dienes such as cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene (ENB), and 5-methylene-2-norbornene. , 5-isopropylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, etc., and trienes such as 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,5-norbornadiene, 1,3,7-octatriene, 1,4,9-decatriene, 4,8-dimethyl-1,4,8-decatriene, and 4-ethylidene-8-methyl-1,7-nonadiene.

[0036] These non-conjugated polyenes [C] can be used alone or in combination of two or more. Among these, linear non-conjugated dienes such as 1,4-hexadiene, and cyclic non-conjugated dienes such as 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene are preferred, and cyclic non-conjugated dienes are more preferred, with 5-ethylidene-2-norbornene (ENB) and 5-vinyl-2-norbornene being even more preferred.

[0037] Examples of the ethylene-α-olefin-non-conjugated polyene copolymer (P) of the present invention include the following. Ethylene-1-butene-1,4-hexadiene copolymer, Ethylene-1-butene-1-octene-1,4-hexadiene copolymer, Ethylene-1-butene-5-ethylidene-2-norbornene copolymer, Ethylene-1-butene-1-octene-5-ethylidene-2-norbornene copolymer, Ethylene-1-butene-5-ethylidene-2-norbornene-5-vinyl-2-norbornene copolymer, Ethylene-1-butene-1-octene-5-ethylidene-2-norbornene-5-vinyl-2-norbornene copolymer.

[0038] The copolymer (P) may contain structural units derived from one or more biomass-derived monomers (biomass-derived ethylene [A1], α-olefin [A2] having 3 to 20 carbon atoms, and non-conjugated polyene [A3]). The copolymer (P) may contain structural units derived from one or more chemically recycled monomers (chemically recycled ethylene [A1], α-olefin [A2] having 3 to 20 carbon atoms, and non-conjugated polyene [A3]).

[0039] The requirements (1) to (4) that the ethylene-α-olefin-non-conjugated polyene copolymer (P) of the present invention must satisfy are described below. Regarding requirement (1) Requirement (1) specifies that the molar ratio [[A1] / [A2]] of the structural units derived from ethylene [A1] to the structural units derived from an α-olefin having 4 to 20 carbon atoms [A2] is 40 / 60 to 90 / 10.

[0040] The lower limit of this molar ratio ([A1] / [A2]) is preferably 45 / 55, more preferably 50 / 50, even more preferably 55 / 45, and particularly preferably 60 / 40. The upper limit of this molar ratio ([A1] / [A2]) is preferably 90 / 10, more preferably 85 / 15, even more preferably 80 / 20, and particularly preferably 75 / 25.

[0041] When the molar ratio (([A1] / [A2]) of the structural units derived from ethylene [A1] to the structural units derived from α-olefin [A2]) is within the above range, an ethylene-based copolymer having an excellent balance between rubber elasticity at low temperatures and tensile strength at room temperature can be obtained.

[0042] Regarding requirement (2) Requirement (2) specifies that the intrinsic viscosity [η] measured in decalin at 135°C is 5.0 to 7.0 dl / g.

[0043] The ethylene-α-olefin-non-conjugated polyene copolymer (P) of the present invention has an intrinsic viscosity [η] in the range of 5.0 to 7.0 dl / g, thereby improving cold resistance and roll processability while maintaining its high strength. This intrinsic viscosity [η] range of 5.0 to 7.0 dl / g is preferably 5.5 to 6.5 dl / g, more preferably 5.6 to 6.3 dl / g, and particularly preferably 5.6 to 6.0 dl / g.

[0044] Regarding requirement (3) Requirement (3) specifies that the content of the structural unit derived from the non-conjugated polyene [A3] is 0.1 to 6.0 mol %, where the total of the structural units [A1], [A2] and [A3] is 100 mol %.

[0045] In the ethylene-α-olefin-non-conjugated polyene copolymer (P) of the present invention, the content of structural units derived from the non-conjugated polyene [A3] is preferably in the range of 0.1 to 6.0 mol %, more preferably 0.3 to 4.0 mol %, even more preferably 0.5 to 3.0 mol %, particularly preferably 0.7 to 2.0 mol %, and even more preferably 1.0 to 1.5 mol %, based on 100 mol % of the total of the structural units [A1], [A2], and [A3].

[0046] Regarding requirement (4) Requirement (4) stipulates that the B value, expressed by the following formula (i), must be 1.20 or greater. B value=([EX]+2[Y]) / [2×[E]×([X]+[Y])]···(i)

[0047] Here, [E], [X], and [Y] represent the mole fractions of ethylene [A1], α-olefin [A2] having 4 to 20 carbon atoms, and non-conjugated polyene [A3], respectively, and [EX] represents the ethylene [A1]-α-olefin [A2] having 4 to 20 carbon atoms dyad sequence fraction.

[0048] The B value represented by the above formula (i) of the ethylene-α-olefin-non-conjugated polyene copolymer (P) of the present invention is preferably 1.20 or more, more preferably 1.20 to 1.80, and even more preferably 1.22 to 1.40.

[0049] If the B value of the ethylene-α-olefin-non-conjugated polyene copolymer (P) of the present invention is less than 1.20, the compression set at low temperatures will be large, and the balance between rubber elasticity at low temperatures and tensile strength at room temperature may not necessarily be excellent.

[0050] Furthermore, when the B value is within the above range, the monomer units constituting the ethylene-α-olefin-non-conjugated polyene copolymer (P) have high alternation and low crystallinity, which improves the processability and the sound insulation performance of the molded article obtained therefrom.

[0051] The B value specified in requirement (4) is an index showing the randomness of the sequence distribution of the copolymerization monomers in the ethylene-α-olefin-non-conjugated polyene copolymer (P), and [E], [X], [Y], and [EX] in the above formula (i) are 13 C-NMR spectrum was measured. JCRandall Macromolecules,15,353(1982), J.Ray Macromolecules,10,773(1977) This can be requested based on reports such as:

[0052] In addition, in the above requirement (1), the molar amounts of the structural units derived from ethylene [A1], the structural units derived from α-olefin [A2], and the structural units derived from non-conjugated polyene [A3] are 1 It can be determined by measuring the H-NMR spectrum and measuring the intensity.

[0053] Manufacturing method of ethylene-α-olefin-non-conjugated polyene copolymer (P) Specifically, the method for producing the ethylene-α-olefin-non-conjugated polyene copolymer (P) of the present invention includes the following steps: A bridged metallocene compound (t) represented by the following general formula (1): and at least one compound (u) selected from the group consisting of an organometallic compound (u-1), an organoaluminum oxy compound (u-2), and a compound (u-3) that reacts with the bridged metallocene compound (t) to form an ion pair; In the present invention, a method for producing an ethylene-α-olefin-non-conjugated polyene copolymer (P) is preferred, in which ethylene, 1-butene (or 1-butene together with an α-olefin having 5 to 20 carbon atoms), and a non-conjugated polyene are copolymerized in the presence of an olefin polymerization catalyst containing

[0054] [ka]

[0055] Bridged metallocene compounds (t) The bridged metallocene compound (t) is a compound represented by the above general formula (1).

[0056] R in general formula (1) 1 From R 14 In the above general formula (1), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 are each independently a hydrogen atom, a hydrocarbon group, a heteroatom-containing hydrocarbon group, or a silicon-containing group, and R 1 From R 4 Any two of the substituents up to R may be bonded to each other to form a ring, 5 From R 12 Any two of the substituents up to R may be bonded to each other to form a ring,13 and R 14 may be bonded to each other to form a ring.

[0057] R 1 From R 14 Examples of the hydrocarbon group in the formula (I) include a linear hydrocarbon group, a branched hydrocarbon group, a cyclic saturated hydrocarbon group, a cyclic unsaturated hydrocarbon group, and a group in which one or more hydrogen atoms of a saturated hydrocarbon group are substituted with a cyclic unsaturated hydrocarbon group.

[0058] The hydrocarbon group usually has 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms, and more preferably 1 to 10 carbon atoms. Examples of the linear hydrocarbon group include linear alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, and an n-decanyl group; and linear alkenyl groups such as an allyl group.

[0059] Examples of branched hydrocarbon groups include branched alkyl groups such as an isopropyl group, a tert-butyl group, a tert-amyl group, a 3-methylpentyl group, a 1,1-diethylpropyl group, a 1,1-dimethylbutyl group, a 1-methyl-1-propylbutyl group, a 1,1-propylbutyl group, a 1,1-dimethyl-2-methylpropyl group, and a 1-methyl-1-isopropyl-2-methylpropyl group.

[0060] Examples of cyclic saturated hydrocarbon groups include cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and methylcyclohexyl; and polycyclic groups such as norbornyl, adamantyl, and methyladamantyl.

[0061] Examples of cyclic unsaturated hydrocarbon groups include aryl groups such as phenyl, tolyl, naphthyl, biphenyl, phenanthryl, and anthracenyl; cycloalkenyl groups such as cyclohexenyl; and polycyclic unsaturated alicyclic groups such as 5-bicyclo[2.2.1]hept-2-enyl.

[0062] Examples of groups in which one or more hydrogen atoms of a saturated hydrocarbon group are substituted with a cyclic unsaturated hydrocarbon group include groups in which one or more hydrogen atoms of an alkyl group, such as a benzyl group, a cumyl group, a 1,1-diphenylethyl group, or a triphenylmethyl group, are substituted with an aryl group.

[0063] R 1 From R 14 Examples of the heteroatom-containing hydrocarbon group in include alkoxy groups such as methoxy and ethoxy, aryloxy groups such as phenoxy, and oxygen-containing hydrocarbon groups such as furyl; amino groups such as N-methylamino, N,N-dimethylamino, and N-phenylamino; nitrogen-containing hydrocarbon groups such as pyrryl; and sulfur-containing hydrocarbon groups such as thienyl. The number of carbon atoms in the heteroatom-containing hydrocarbon group is usually 1 to 20, preferably 2 to 18, and more preferably 2 to 15. However, silicon-containing groups are excluded from the heteroatom-containing hydrocarbon group.

[0064] R 1 From R 14 Examples of the silicon-containing group in the formula -Si(-R) include a trimethylsilyl group, a triethylsilyl group, a dimethylphenylsilyl group, a diphenylmethylsilyl group, and a triphenylsilyl group. 15 )(-R 16 )(-R 17 ) (wherein R 15 , R 16 , R 17 are each independently an alkyl group or a phenyl group having 1 to 15 carbon atoms.

[0065] R 1 From R 14 Any two of the substituents up to, for example, two adjacent substituents (e.g., R 1 and R 2 , R 2 and R 3 , R 3 and R 4 , R 5 and R 6 , R 6 and R7 , R 7 and R 8 , R 9 and R 10 , R 10 and R 11 , R 11 and R 12 , R 13 and R 14 ) may be bonded to each other to form a ring. The ring formation may occur at two or more positions in the molecule.

[0066] In this specification, examples of the ring (additional ring) formed by bonding two substituents together include an alicyclic ring, an aromatic ring, and a heterocyclic ring.Specific examples include a cyclohexane ring, a benzene ring, a hydrogenated benzene ring, a cyclopentene ring, a heterocyclic ring such as a furan ring, a thiophene ring, and the like, and corresponding hydrogenated heterocyclic rings, and preferred are a cyclohexane ring, a benzene ring, and a hydrogenated benzene ring.Furthermore, such a ring structure may further have a substituent such as an alkyl group on the ring.

[0067] R 5 , R 8 , R 9 and R 12 is preferably a hydrogen atom. 6 , R 7 , R 10 and R 11 is preferably a hydrogen atom, a hydrocarbon group, an oxygen atom-containing hydrocarbon group or a nitrogen atom-containing hydrocarbon group, and more preferably a hydrocarbon group. 6 and R 7 are bonded to each other to form a ring, and R 10 and R 11 may be bonded to each other to form a ring. Examples of the structure of the fluorenyl group moiety include those represented by the following structural formulas.

[0068] [ka]

[0069] R 13 and R14 is preferably a hydrocarbon group, a heteroatom-containing hydrocarbon group, or a silicon-containing group, and more preferably an aryl group or a substituted aryl group (an aryl group having a heteroatom-containing hydrocarbon group or a silicon-containing group).

[0070] Regarding Y in general formula (1) In the general formula (1), Y is a carbon atom, a silicon atom, a germanium atom, or a tin atom, and is preferably a carbon atom.

[0071] Regarding M, Q, and j in general formula (1) In general formula (1), M is a Group 4 transition metal, preferably Ti, Zr or Hf, more preferably Zr or Hf, and even more preferably Hf.

[0072] Q is a halogen atom, a hydrocarbon group, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair, and when j is an integer of 2 or greater, Qs may be the same or different from one another.

[0073] Examples of the halogen atom in Q include fluorine, chlorine, bromine, and iodine. Examples of the hydrocarbon group in Q include R 1 From R 14 Examples of the hydrocarbon group include the same groups as those in the above, and preferred are alkyl groups such as linear alkyl groups and branched alkyl groups.

[0074] Examples of the anionic ligand in Q include alkoxy groups such as methoxy and tert-butoxy; aryloxy groups such as phenoxy; carboxylate groups such as acetate and benzoate; sulfonate groups such as mesylate and tosylate; and amide groups such as dimethylamide, diisopropylamide, methylanilide, and diphenylamide.

[0075] Examples of the neutral ligand capable of coordinating with the lone electron pair in Q include organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, and diphenylmethylphosphine; and ethers such as tetrahydrofuran, diethyl ether, dioxane, and 1,2-dimethoxyethane.

[0076] At least one of Q is preferably a halogen atom or an alkyl group. j is an integer of 1 to 4, preferably 2. When j is an integer of 2 or more, Q may be the same or different from each other.

[0077] Bridged metallocene compound (t) represented by general formula (2) In the method for producing the ethylene-α-olefin-non-conjugated polyene copolymer (P) of the present invention, it is preferable to use a bridged metallocene compound (t) represented by the following general formula (2).

[0078] [ka]

[0079] In the above general formula (2), R 13 , R 14 , M, Q, and j are the same as in the general formula (1) above. Also, M is preferably a hafnium atom.

[0080] Furthermore, it is preferred that Q is a methyl group and j is an integer of 2. Also, R 13 and R 14 and preferably both are 4-methoxyphenyl groups. Specific examples of the bridged metallocene compound (t) include: the compounds listed on pages 29 to 43 of WO 2004 / 87775; the compounds listed on pages 9 to 37 of WO 2006 / 25540; Compounds listed in paragraph

[0117] of International Publication No. 2015 / 122414, The compounds listed in

[0143] of International Publication No. 2015 / 122415 may be mentioned.

[0081] Next, each compound of at least one compound (u) selected from the group consisting of an organometallic compound (u-1), an organoaluminum oxy compound (u-2) and a compound (u-3) that reacts with a bridged metallocene compound (t) to form an ion pair will be described.

[0082] Organometallic compound (u-1) As the organometallic compound (u-1), specifically, organometallic compounds of Groups 1, 2, 12, and 13 of the periodic table such as (u-1a), (u-1b), and (u-1c) shown in the following general formulas (3) to (5) are used.

[0083] (u-1a) R 18 m Al(OR 19 ) n H p X q ······General formula (3) (In general formula (3), R 18 and R 19 may be the same as or different from each other, and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, m is 0 < m ≤ 3, n is 0 ≤ n < 3, p is 0 ≤ p < 3, q is 0 ≤ q < 3, and m + n + p + q = 3.) An organoaluminum compound represented by

[0084] Examples of such compounds include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisobutylaluminum, and tri-n-octylaluminum, tricycloalkylaluminums, isobutylaluminum dichloride, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, methylaluminum dichloride, dimethylaluminum chloride, and diisobutylaluminum hydride.

[0085] (u-1b) M 2 AlR 20 4... General formula (4) (In general formula (4), M 2 indicates Li, Na, or K, and R 20 is a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4. A complex alkylation product of aluminum and a metal of Group 1 of the periodic table, represented by Such compounds include LiAl(C2H5)4, LiAl(C7H 15 ) 4 can be exemplified.

[0086] (u-1c) R 21 R 22 M 3 ...General formula (5) (In general formula (5), R 21 and R 22 may be the same or different and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms; M 3 is Mg, Zn or Cd. Dialkyl compounds containing a metal of Group 2 or 12 of the periodic table represented by

[0087] Among the above organometallic compounds (u-1), organoaluminum compounds such as triethylaluminum, triisobutylaluminum, tri-n-octylaluminum, etc. are preferred. Furthermore, such organometallic compounds (u-1) may be used singly or in combination of two or more.

[0088] Organoaluminum oxy compound (u-2) The organoaluminum oxy compound (u-2) may be a conventionally known aluminoxane, or may be a benzene-insoluble organoaluminum oxy compound such as those exemplified in JP-A No. 2-78687.

[0089] Conventionally known aluminoxanes can be produced, for example, by the following method, and are usually obtained as a solution in a hydrocarbon solvent. (a) A method in which an organoaluminum compound such as trialkylaluminum is added to a hydrocarbon medium suspension of a compound containing adsorbed water or a salt containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, or cerous chloride hydrate, to react the adsorbed water or water of crystallization with the organoaluminum compound. (b) A method in which water, ice, or water vapor is directly applied to an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether, or tetrahydrofuran. (c) A method in which an organoaluminum compound such as trialkylaluminum is reacted with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene, or toluene.

[0090] Specific examples of organoaluminum compounds used in preparing aluminoxanes include the same organoaluminum compounds as those exemplified as organoaluminum compounds belonging to the above (u-1a).

[0091] Of these, trialkylaluminum and tricycloalkylaluminum are preferred, and among these, trimethylaluminum and triisobutylaluminum are particularly preferred. The organoaluminum compounds as described above may be used singly or in combination of two or more.

[0092] The organoaluminum oxy compound (u-2) may also include boron-containing organoaluminum oxy compounds represented by the following general formula (6). (R 24 -)(R 25 -)Al-OB(-R 23 )-O-Al(-R 26 )(-R 27 ) ...General formula (6) (In general formula (6), R 23 represents a hydrocarbon group having 1 to 10 carbon atoms, and R 24 ~R 27may be the same or different and represent a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms.)

[0093] As the organoaluminum oxy compound (u-2), methylaluminoxane, which is commercially available and therefore easily available, and MMAO prepared from trimethylaluminum and triisobutylaluminum are preferred. Among these, MMAO, which has improved solubility in various solvents and storage stability, is particularly preferred.

[0094] A compound (u-3) that reacts with a bridged metallocene compound (t) to form an ion pair Examples of the compound (u-3) (hereinafter referred to as "ionizing ionic compound") that reacts with the bridged metallocene compound (t) to form an ion pair include Lewis acids, ionic compounds, borane compounds, and carborane compounds described in JP-T-1-501950, JP-T-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, and US Pat. No. 5,321,106. Further examples include heteropoly compounds and isopoly compounds. These ionizing ionic compounds may be used singly or in combination.

[0095] Specifically, the Lewis acid is BR 28 3(R 28 is a phenyl group which may have a substituent such as fluorine, a methyl group, or a trifluoromethyl group, or fluorine, and examples thereof include trifluoroboron, triphenylboron, tris(4-fluorophenyl)boron, tris(3,5-difluorophenyl)boron, tris(4-fluoromethylphenyl)boron, tris(pentafluorophenyl)boron, tris(p-tolyl)boron, tris(o-tolyl)boron, and tris(3,5-dimethylphenyl)boron.

[0096] Of the ionizing ionic compounds, the above-mentioned ionic compounds are preferred, and among them, triphenylcarbenium tetrakis(pentafluorophenyl)borate and N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate are more preferred. The ionizing ionic compounds may be used singly or in combination of two or more.

[0097] When the bridged metallocene compound (t) represented by the above general formula (1) is used as a catalyst, it shows very high polymerization activity in the production of ethylene-α-olefin-non-conjugated polyene copolymers (P) when used in combination with an organometallic compound (u-1) such as triisobutylaluminum, an organoaluminum oxy compound (u-2) such as methylaluminoxane, or an ionizing ionic compound (u-3) such as triphenylcarbenium tetrakis(pentafluorophenyl)borate.

[0098] Production of ethylene-α-olefin-non-conjugated polyene copolymer (P) The ethylene-α-olefin-non-conjugated polyene copolymer (P) of the present invention is produced by copolymerizing ethylene, 1-butene (or an α-olefin having 5 to 20 carbon atoms together with 1-butene), and a non-conjugated polyene in the presence of an olefin polymerization catalyst containing the bridged metallocene compound (t) and at least one compound (u) selected from the group consisting of the organometallic compound (u-1), the organoaluminum oxy compound (u-2), and the compound (u-3) that reacts with the bridged metallocene compound (t) to form an ion pair.

[0099] When copolymerizing ethylene, an α-olefin, and a non-conjugated polyene, the method of use and the order of addition of each component constituting the olefin polymerization catalyst can be selected arbitrarily, and either a liquid phase polymerization method such as solution (dissolution) polymerization or suspension polymerization, or a gas phase polymerization method can be used. It can also be implemented in

[0100] Specific examples of inert hydrocarbon media used in liquid phase polymerization include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene, alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane, aromatic hydrocarbons such as benzene, toluene, and xylene, and halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane. These may be used alone or in combination of two or more. Olefins themselves may also be used as solvents.

[0101] When using the above-mentioned olefin polymerization catalyst, the bridged metallocene compound (t) is usually used in an amount of 10 -12 ~10 -2 moles, preferably 10 -10 ~10 -8 It is used in molar amounts.

[0102] The ratios of the bridged metallocene compound (t), the organometallic compound (u-1), the organoaluminum oxy compound (u-2), and the compound (u-3) that reacts with the bridged metallocene compound (t) to form an ion pair are as follows:

[0103] That is, compound (u-1) is used in an amount such that the molar ratio of compound (u-1) to all transition metal atoms (M) in bridged metallocene compound (t) [(u-1) / M] is usually 0.01 to 50,000, preferably 0.05 to 10,000. Compound (u-2) is used in an amount such that the molar ratio of aluminum atoms in compound (u-2) to all transition metal atoms (M) in bridged metallocene compound (t) [(b-2) / M] is usually 10 to 50,000, preferably 20 to 10,000.

[0104] The compound (u-3) is used in an amount such that the molar ratio of the compound (u-3) to the transition metal atom (M) in the bridged metallocene compound (t) [(u-3) / M] is generally 1 to 20, preferably 1 to 15.

[0105] The polymerization temperature using such a copolymerization catalyst is usually in the range of -50 to +200°C, preferably 0 to 200°C, and more preferably 70 to 200°C. The polymerization pressure is usually normal pressure to 10 MPa gauge pressure, preferably normal pressure to 5 MPa gauge pressure, and the polymerization reaction can be carried out in any of batch, semi-continuous, and continuous systems. Furthermore, the polymerization can be carried out in two or more stages with different reaction conditions.

[0106] The molecular weight of the resulting ethylene-α-olefin-non-conjugated polyene copolymer (P) can be adjusted by adding hydrogen to the polymerization system or by changing the polymerization temperature. It can also be adjusted by the amount of the above-mentioned compound (u) used. Specific examples include triisobutylaluminum, methylaluminoxane, and diethylzinc. When hydrogen is added, the appropriate amount is approximately 0.001 to 100 nL per kg of olefin.

[0107] Compositions containing ethylene-α-olefin-non-conjugated polyene copolymers The ethylene-α-olefin-non-conjugated polyene copolymer (P) of the present invention is generally used as a composition (also referred to as a "rubber composition") blended with a softener, a filler, etc., and can be molded and crosslinked to obtain a desired molded product.

[0108] The amounts of these to be blended are generally 0.1 to 200 parts by weight of the softener and 1 to 300 parts by weight of the filler per 100 parts by weight of the ethylene-α-olefin-non-conjugated polyene copolymer (P) and other polymers (elastomers, rubbers, etc.) blended as needed.

[0109] In addition to softeners, fillers, and crosslinking agents (vulcanizing agents), other additives such as crosslinking aids, vulcanization accelerators, vulcanization aids, activators, moisture absorbents, heat stabilizers, weather stabilizers, antistatic agents, colorants, lubricants and thickeners, foaming agents and foaming aids may be compounded into the rubber composition depending on the intended use and purpose.

[0110] Furthermore, the ethylene-α-olefin-non-conjugated polyene copolymer (P) or a rubber composition containing it may be compounded with other elastomers, rubbers, etc., as required. When used as a rubber composition, the proportion of the ethylene-α-olefin-non-conjugated polyene copolymer (P) in the rubber composition is generally 20% by weight or more, preferably 30 to 90% by weight.

[0111] The rubber composition can be prepared by kneading the ethylene-α-olefin-non-conjugated polyene copolymer and other components, which are added as needed, at a desired temperature using a kneading machine such as a mixer, kneader, or roll. The ethylene-α-olefin-non-conjugated polyene copolymer (P) has excellent kneadability, which allows for the preparation of the rubber composition to be carried out smoothly.

[0112] Crosslinking agent Examples of crosslinking agents include those commonly used when crosslinking rubber, such as organic peroxides, phenolic resins, sulfur-based compounds, hydrosilicone-based compounds, amino resins, quinone or its derivatives, amine-based compounds, azo-based compounds, epoxy-based compounds, isocyanate-based compounds, etc. Among these, crosslinking agents (also called "vulcanizing agents") such as organic peroxides and sulfur-based compounds are preferred.

[0113] Examples of organic peroxides include dicumyl peroxide (DCP), di-tert-butyl peroxide, 2,5-di-(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexyne-3, 1,3-bis(tert-butylperoxyisopropyl)benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl-4,4-bis(tert-butylperoxy)valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butyl peroxybenzoate, tert-butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, and tert-butylcumyl peroxide.

[0114] When an organic peroxide is used as the crosslinking agent, it is preferable to use a crosslinking aid in combination. Examples of crosslinking aids include sulfur; quinone dioxime crosslinking aids such as p-quinone dioxime; acrylic crosslinking aids such as ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate; allyl crosslinking aids such as diallyl phthalate and triallyl isocyanurate; maleimide crosslinking aids; divinylbenzene; and metal oxides such as zinc oxide (e.g., ZnO#1 / Zinc Oxide Type 2 (JIS Standard (K-1410)), manufactured by Hakusui Tech Co., Ltd.), magnesium oxide, and zinc oxide (e.g., zinc oxide such as "META-Z102" (trade name, manufactured by Inoue Lime Industry Co., Ltd.)). The amount of crosslinking aid added is usually 0.5 to 10 moles, preferably 0.5 to 7 moles, and more preferably 1 to 5 moles, per mole of organic peroxide. When a sulfur-based compound is used as the crosslinking agent, it is preferable to use a vulcanization accelerator in combination.

[0115] Vulcanization aid The vulcanization aid is used when the crosslinking agent is a sulfur-based compound, and examples thereof include zinc oxide (e.g., ZnO#1 / zinc oxide type 2, manufactured by Hakusui Tech Co., Ltd.), magnesium oxide, and zinc oxide (e.g., zinc oxide such as "META-Z102" (trade name; manufactured by Inoue Lime Industry Co., Ltd.)).

[0116] The blending amount is usually 1 to 20 parts by weight per 100 parts by weight of the total of the ethylene-α-olefin-non-conjugated polyene copolymer (P) and other polymers (rubbers, etc.) that require crosslinking and are blended as needed.

[0117] Softener Specific examples of softeners include petroleum-based softeners such as process oil, lubricating oil, paraffin oil, liquid paraffin, petroleum asphalt, and Vaseline; coal tar-based softeners such as coal tar; fatty oil-based softeners such as castor oil, linseed oil, rapeseed oil, soybean oil, and coconut oil; waxes such as beeswax and carnauba wax; fatty acids or salts thereof such as ricinoleic acid, palmitic acid, stearic acid, barium stearate, and calcium stearate; naphthenic acid, pine oil, rosin, and derivatives thereof; synthetic polymeric substances such as terpene resins, petroleum resins, and coumarone-indene resins; ester-based softeners such as dioctyl phthalate and dioctyl adipate; and other softeners such as microcrystalline wax, liquid polybutadiene, modified liquid polybutadiene, hydrocarbon-based synthetic lubricating oils, tall oil, and sub(factice). Of these, petroleum-based softeners are preferred, and process oil is particularly preferred.

[0118] The amount of softener in the rubber composition is generally 2 to 150 parts by weight, preferably 50 to 150 parts by weight, per 100 parts by weight of the total of the ethylene-α-olefin-non-conjugated polyene copolymer (P) and other polymer (elastomer, rubber, etc.) components that are added as needed.

[0119] In particular, in order to fully utilize the improved cold resistance and roll processability of the ethylene-α-olefin-non-conjugated polyene copolymer (P) while maintaining the high strength of the ethylene-α-olefin-non-conjugated polyene copolymer (P), it is preferable to set the amount of oil extension to 50 to 150 parts by mass per 100 parts by mass of the ethylene-α-olefin-non-conjugated polyene copolymer (P).

[0120] inorganic fillers Specific examples of inorganic fillers that can be used include one or more of light calcium carbonate, heavy calcium carbonate, talc, clay, etc., and among these, heavy calcium carbonate such as "Whiten SB" (product name; Shiraishi Calcium Co., Ltd.) is preferred.

[0121] When the rubber composition contains an inorganic filler, the amount of inorganic filler is usually 2 to 50 parts by weight, preferably 5 to 50 parts by weight, per 100 parts by weight of the total of the ethylene-α-olefin-non-conjugated polyene copolymer (P) and other polymers (elastomers, rubbers, etc.) that are added as needed. When the amount is within the above range, the kneading processability of the rubber composition is excellent, and a molded product with excellent mechanical properties can be obtained.

[0122] Reinforcing agent Specific examples of the reinforcing agent include carbon black, carbon black surface-treated with a silane coupling agent, silica, calcium carbonate, activated calcium carbonate, finely divided talc, and differential silicic acid. When used, the amount of the reinforcing agent is generally 30 to 200 parts by weight, and preferably 50 to 180 parts by weight, per 100 parts by weight of the ethylene-α-olefin-non-conjugated polyene copolymer (P) and, if necessary, other polymers (elastomers, rubbers, etc.).

[0123] Anti-aging agent (stabilizer) The life of a molded article formed from a rubber composition can be extended by blending an antioxidant (stabilizer) into the rubber composition. Examples of such antioxidants include conventionally known antioxidants, such as amine-based antioxidants, phenol-based antioxidants, and sulfur-based antioxidants.

[0124] These antioxidants can be used alone or in combination of two or more, and the blending amount is usually 0.3 to 10 parts by weight, preferably 0.5 to 7.0 parts by weight, per 100 parts by weight of the ethylene-α-olefin-non-conjugated polyene copolymer (P) and other polymers (elastomers, rubbers, etc.). By adjusting the blending amount within this range, no blooming occurs on the surface of a molded article obtained from the resulting rubber composition, and furthermore, vulcanization inhibition can be suppressed.

[0125] Processing aids As the processing aid, a wide variety of processing aids that are generally compounded in rubber can be used.

[0126] The amount of the processing aid is usually 10 parts by weight or less, preferably 8.0 parts by weight or less, per 100 parts by weight of the ethylene-α-olefin-non-conjugated polyene copolymer (P) and polymers other than the ethylene-based copolymer (elastomer, rubber, etc.) contained in the rubber composition.

[0127] activator Specific examples of surfactants include amines such as di-n-butylamine, dicyclohexylamine, and monoelanolamine; surfactants such as diethylene glycol, polyethylene glycol, lecithin, triaryl methylate, and zinc compounds of aliphatic or aromatic carboxylic acids; zinc peroxide preparations; octadecyltrimethylammonium bromide, synthetic hydrotalcite, and special quaternary ammonium compounds.

[0128] When an activator is contained, the amount thereof is usually 0.2 to 10 parts by weight, preferably 0.3 to 5 parts by weight, per 100 parts by weight of the ethylene-α-olefin-non-conjugated polyene copolymer (P) and other polymers (elastomers, rubbers, etc.).

[0129] Molded body Molded articles, such as crosslinked molded articles and crosslinked foamed articles, obtained from the ethylene-α-olefin-non-conjugated polyene copolymer (P) of the present invention, crosslinked ethylene-α-olefin-non-conjugated polyene copolymer, or composition containing the ethylene-α-olefin-non-conjugated polyene copolymer can be used for various applications.

[0130] The ethylene-α-olefin-non-conjugated polyene copolymer (P) used in such a molded article preferably has a tensile strength of 5 MPa or more as measured in accordance with JIS K6251.

[0131] Furthermore, the ethylene-α-olefin-non-conjugated polyene copolymer (P) used in such a molded product preferably has a permanent set (%) of 98% or less, more preferably 95% or less, even more preferably 90% or less, particularly preferably 80% or less, and even more preferably less than 70% after being compressed to 25% in an atmosphere of -30°C for 24 hours in accordance with JIS K6262.

[0132] Furthermore, the ethylene-α-olefin-non-conjugated polyene copolymer (P) used in such a molded article preferably has a glass transition temperature (Tg) of −55° C. or lower. Specific examples of such molded articles include tire rubber, O-rings, industrial rolls, packing (e.g., condenser packing), gaskets, belts (e.g., heat insulation belts, copier belts), hoses (e.g., water hoses, brake reservoir hoses, radiator hoses), waterproof rubber, sponges (e.g., weatherstrip sponges, heat insulation sponges, protect sponges, micro-foam sponges), cables (ignition cables, cab tire cables, high-tension cables), electric wire coating materials (high-voltage electric wire coating materials, low-voltage electric wire coating materials, marine electric wire coating materials), glass run channels, color skin materials, paper feed rolls, roofing sheets, and the like, and these articles are used in a wide range of applications. [Example]

[0133] The present invention will be explained in more detail below based on examples, but the present invention is not limited to these examples.

[0134] [Synthesis Example 1] Catalyst-a1 Synthesis of First, according to the method described in WO2015 / 122415 [bis(4-methoxyphenyl)methylene (η 5 -cyclopentadienyl)(η 5 -2,3,6,7-tetramethylfluorenyl)] Hafnium dichloride This was then reacted with methyllithium according to the method described in Example 86 of JP-A-7-53618 to obtain the following: Catalyst-a1 was synthesized. Catalyst-a1 [bis(4-methoxyphenyl)methylene (η 5 -cyclopentadienyl)(η 5 -2,3,6,7-tetramethylfluorenyl)] Hafnium dimethyl

[0135] [Synthesis Example 2] catalyst-a2 Synthesis of In a nitrogen atmosphere, place in a 100 ml Schlenk tube. Bis(4-methoxyphenyl) (Cyclopentadienyl)(2,3,6,7-tetramethylfluorenyl) methane 272 mg (0.531 mmol) of the compound, 20 ml of dehydrated toluene, and 90 μL (1.1 mmol) of THF were added sequentially. Next, while cooling in an ice bath, 0.68 ml (1.1 mmol) of a 1.63 M n-butyllithium / hexane solution was gradually added, and the mixture was stirred at 45°C for 5 hours, yielding a red solution. The solvent was distilled off under reduced pressure, and 20 ml of dehydrated diethyl ether was added to return the solution to a red color. While cooling in a methanol / dry ice bath, 164 mg (0.511 mmol) of hafnium tetrachloride was added, and the mixture was stirred for 16 hours while gradually raising the temperature to room temperature, yielding a yellow slurry. The solid obtained by distilling off the solvent under reduced pressure was brought into a glove box, washed with hexane, and then extracted with dichloromethane. The solid obtained by distilling off the solvent under reduced pressure was dissolved in a small amount of dichloromethane, added with hexane, and recrystallized at -20°C. The precipitated solid was collected, washed with hexane, and dried under reduced pressure to obtain the yellow solid shown below. Catalyst-a2 275 mg (0.362 mmol, 70.8%) was obtained. catalyst-a2 [bis(4-methoxyphenyl)methylene (η 5 -cyclopentadienyl)(η 5 -2,3,6,7-tetramethylfluorenyl)] Hafnium dichloride catalyst-a2 The identification of the compound 1 H-NMR and FD-MS spectra were used.

[0136] [Example 1] Copolymer production A polymerization reaction of ethylene, 1-butene, and 5-ethylidene-2-norbornene (ENB) was carried out continuously at 85°C using a 300 L volume polymerization vessel equipped with a stirring blade.

[0137] Hexane (feed rate: 50.5 L / h) was used as the polymerization solvent and continuously supplied to the polymerization reactor so that the ethylene feed rate was 4.2 g / h, the 1-butene feed rate was 4.7 kg / h, the ENB feed rate was 432 g / h, and the hydrogen feed rate was 5.2 NL / h.

[0138] The polymerization pressure was kept at 1.7 MPaG and the polymerization temperature at 85°C. Catalyst-a1 [bis(4-methoxyphenyl)methylene (η 5 -cyclopentadienyl)(η 5 -2,3,6,7-tetramethylfluorenyl)] Hafnium dimethyl The feed rate was 0.0056 mmol / h. Triphenylcarbenium tetrakis(pentafluorophenyl)borate (CB-3) as a cocatalyst and triisobutylaluminum (TiBA) as an organoaluminum compound were continuously fed to the polymerization reactor at a feed rate of 0.035 mmol / h and 13 mmol / h, respectively.

[0139] In this way, a solution containing 6.0 mass% of ethylene-1-butene-ENB copolymer formed from ethylene, 1-butene, and ENB was obtained. A small amount of methanol was added to the polymerization reaction mixture withdrawn from the bottom of the polymerization reactor to terminate the polymerization reaction. 100 mass parts of paraffin oil were added to 100 mass parts of ethylene-1-butene-ENB copolymer, and the ethylene-1-butene-ENB copolymer was separated from the solvent by steam stripping and then dried under reduced pressure at 80°C overnight.

[0140] By the above procedure, ethylene-1-butene-ENB copolymer formed from ethylene, butene, and ENB was obtained at a rate of 2.5 kg / h. Its intrinsic viscosity [η] was 5.7 g / dl.

[0141] 200 parts by weight of the obtained ethylene-1-butene-ENB copolymer was wound around an 8-inch roll (surface temperature of front roll: 50°C, surface temperature of rear roll: 50°C, rotation speed of front roll: 16 rpm, rotation speed of rear roll: 18 rpm), and 4.5 parts by weight of 2,5-dimethyl-2,5-di-tert-butylperoxy)hexane (40% masterbatch, trade name: Perhexa 25B-40, manufactured by NOF Corporation) as a crosslinking agent and 0.75 parts by weight of divinylbenzene (trade name: DVB810, manufactured by Nippon Steel Chemical & Material Co., Ltd.) as a crosslinking coagent were added, followed by kneading for 10 minutes to obtain a compound.

[0142] [Example 2] Copolymer production A polymerization reaction of ethylene, 1-butene, and 5-ethylidene-2-norbornene (ENB) was carried out continuously at 75°C using a 300 L volume polymerization vessel equipped with a stirring blade.

[0143] Hexane (feed rate: 46.5 L / h) was used as the polymerization solvent and continuously supplied to the polymerization reactor so that the ethylene feed rate was 4.2 g / h, the 1-butene feed rate was 9.8 kg / h, the ENB feed rate was 612 g / h, and the hydrogen feed rate was 3.4 NL / h.

[0144] The polymerization pressure was kept at 1.7 MPaG and the polymerization temperature at 75°C. Catalyst-a1 [bis(4-methoxyphenyl)methylene (η 5 -cyclopentadienyl)(η 5 -2,3,6,7-tetramethylfluorenyl)] Hafnium dimethyl The feed rate of the cocatalyst triphenylcarbenium tetrakis(pentafluorophenyl)borate (CB-3) was 0.038 mmol / h, and the feed rate of the organoaluminum compound triisobutylaluminum (TiBA) was 13 mmol / h.

[0145] In this way, a solution containing 5.7% by mass of ethylene-1-butene-ENB copolymer formed from ethylene, 1-butene, and ENB was obtained. A small amount of methanol was added to the polymerization reaction mixture withdrawn from the bottom of the polymerization reactor to terminate the polymerization reaction. 75 parts by mass of paraffin oil was added to 100 parts by mass of ethylene-1-butene-ENB copolymer, and the ethylene-1-butene-ENB copolymer was separated from the solvent by steam stripping and then dried under reduced pressure at 80°C overnight.

[0146] By the above procedure, ethylene-1-butene-ENB copolymer formed from ethylene, butene, and ENB was obtained at a rate of 2.5 kg / h. Its intrinsic viscosity [η] was 5.8 g / dl.

[0147] 175 parts by weight of the resulting ethylene-1-butene-ENB copolymer was wound around an 8-inch roll (front roll surface temperature 50°C, rear roll surface temperature 50°C, front roll rotation speed 16 rpm, rear roll rotation speed 18 rpm), and 25 parts by weight of paraffin oil (Idemitsu Kosan Co., Ltd., trade name: Diana Process Oil PW-100), 4.5 parts by weight of 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane (40% masterbatch, trade name: Perhexa 25B-40, NOF Corporation) as a crosslinking agent, and 0.75 parts by weight of divinylbenzene (Nippon Steel Chemical & Material Co., Ltd., trade name: DVB810) as a crosslinking coagent were added and kneaded for 10 minutes to obtain a blend.

[0148] Comparative Example 1 Using a 300 L volume polymerization vessel equipped with a stirring blade, a continuous polymerization reaction of ethylene, 1-butene, and 5-ethylidene-2-norbornene (ENB) was carried out at 95°C. Hexane (feed rate: 41.0 L / h) was used as the polymerization solvent and continuously supplied to the polymerization reactor so that the ethylene feed rate was 4.2 g / h, the 1-butene feed rate was 10.0 kg / h, the ENB feed rate was 580 g / h, and the hydrogen feed rate was 1.8 NL / h.

[0149] The polymerization pressure was kept at 1.6 MPaG and the polymerization temperature at 95°C. catalyst-a2 [bis(4-methoxyphenyl)methylene (η 5 -cyclopentadienyl)(η 5 -2,3,6,7-tetramethylfluorenyl)] Hafnium dichloride The cocatalyst triphenylcarbenium tetrakis(pentafluorophenyl)borate (C6H5)3CB(C6F5)4 (CB-3) was continuously fed to the polymerization reactor at a feed rate of 0.125 mmol / h, and the organoaluminum compound triisobutylaluminum (TiBA) was continuously fed to the polymerization reactor at a feed rate of 10 mmol / h.

[0150] In this way, a solution containing 12.0 mass% of ethylene-1-butene-ENB copolymer formed from ethylene, 1-butene, and ENB was obtained. A small amount of methanol was added to the polymerization reaction mixture withdrawn from the bottom of the polymerization reactor to terminate the polymerization reaction. 30 mass parts of paraffin oil were added per 100 mass parts of ethylene-1-butene-ENB copolymer, and the ethylene-1-butene-ENB copolymer was separated from the solvent by steam stripping and then dried under reduced pressure at 80°C overnight.

[0151] By the above procedure, ethylene-1-butene-ENB copolymer formed from ethylene, butene, and ENB was obtained at a rate of 5.0 kg / h. The intrinsic viscosity [η] of the obtained ethylene-1-butene-ENB copolymer was 3.6 g / dl.

[0152] 130 parts by weight of the resulting ethylene-1-butene-ENB copolymer was wound around an 8-inch roll (front roll surface temperature 50°C, rear roll surface temperature 50°C, front roll rotation speed 16 rpm, rear roll rotation speed 18 rpm), and 70 parts by weight of paraffin oil (Idemitsu Kosan Co., Ltd., trade name: Diana Process Oil PW-100), 4.5 parts by weight of 2,5-dimethyl-2,5-di-tert-butylperoxy)hexane (40% masterbatch, trade name: Perhexa 25B-40, NOF Corporation) as a crosslinking agent, and 0.75 parts by weight of divinylbenzene (Nippon Steel Chemical & Material Co., Ltd., trade name: DVB810) as a crosslinking coagent were added and kneaded for 10 minutes to obtain a blend.

[0153] Comparative Example 2 Keltan® 5469C, an ethylene-propylene-5-ethylidene-2-norbornene copolymer (EPDM) with a Mooney viscosity of ML 1+4 (125°C): 52, ethylene content: 58%, ENB content: 4.5%, oil extension amount: 100 phr) was used.

[0154] 200 parts by weight of Keltan (registered trademark) 5469C was wound around an 8-inch roll (surface temperature of front roll: 50°C, surface temperature of rear roll: 50°C, rotation speed of front roll: 16 rpm, rotation speed of rear roll: 18 rpm), and 4.5 parts by weight of 2,5-dimethyl-2,5-di-tert-butylperoxy)hexane (40% masterbatch, trade name: Perhexa 25B-40, manufactured by NOF Corporation) as a crosslinking agent and 0.75 parts by weight of divinylbenzene (trade name: DVB810, manufactured by Nippon Steel Chemical & Material Co., Ltd.) as a crosslinking aid were added, and the mixture was kneaded for 10 minutes to obtain a compound.

[0155] The following evaluations were carried out on the ethylene-1-butene-ENB copolymers and ethylene-propylene-5-ethylidene-2-norbornene copolymers (EPDM) obtained in Examples 1 and 2 and Comparative Examples 1 and 2. The results are shown in Table 1.

[0156] [Physical Properties] Intrinsic viscosity [η] (dl / g) To measure the intrinsic viscosity [η] (dl / g) of the copolymer, 1 g of the copolymer was shredded, and then subjected to Soxhlet extraction using methyl ethyl ketone at 80°C for 3 hours, followed by drying under reduced pressure overnight at 80°C. The intrinsic viscosity [η] (dl / g) of the copolymer was measured using a fully automatic intrinsic viscometer manufactured by Rigo Co., Ltd. at a temperature of 135°C and a measurement solvent of decalin.

[0157] Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) For the measurement of the weight-average molecular weight (Mw) and molecular weight distribution (Mw / Mn), 1 g of copolymer was shredded, subjected to Soxhlet extraction using methyl ethyl ketone at 80°C for 3 hours, and then dried under reduced pressure at 80°C overnight.

[0158] The ethylene-1-octene copolymer was analyzed by gel permeation chromatography (GPC) to obtain the polystyrene equivalent molecular weight (M1-PSt) of each fraction. [η]i-PSt·Mi-PSt=[η]i-EPR·Mi-EPR, [η]i-PSt=1.37×10-4Mi-PSt0.686, and [η]i-EPR=7.2×10-4Mi-EPR0.667 The molecular weight was converted into an EPR-equivalent molecular weight Mi-EPR using the following formula: The molecular weight distribution (Mw / Mn) was calculated using the EPR-equivalent molecular weight.

[0159] Gel permeation chromatography (GPC) was performed using a Waters Alliance GPC-2000 gel permeation chromatograph as follows. Two TSKgel GNH6-HT and two TSKgel GNH6-HTL columns were used. Each column had a diameter of 7.5 mm and a length of 300 mm. The column temperature was 140°C. The mobile phase consisted of o-dichlorobenzene (Wako Pure Chemical Industries, Ltd.) and 0.025 wt% BHT (Takeda Pharmaceutical Co., Ltd.) as an antioxidant. The flow rate was 1.0 mL / min. The sample concentration was 15 mg / 10 mL, the sample injection volume was 500 μL, and a differential refractometer was used as the detector. Tosoh polystyrene standards with molecular weights of Mw<1000 and Mw>4×10 were used, while those with molecular weights of 1000≦Mw≦4×10 were used. Pressure Chemical Co., Ltd. products were used.

[0160] [Strength] Tensile strength [MPa] The blends obtained in Examples 1 and 2 and Comparative Examples 1 and 2 were cut into sheets to prepare uncrosslinked sheets having a thickness of 2 mm. The uncrosslinked sheets were then pressed at 170°C for 15 minutes using a 100-ton press molding machine to prepare crosslinked sheets (thickness 2 mm).

[0161] Using the obtained crosslinked sheet (thickness 2 mm), a tensile test was carried out in accordance with JIS K6251 under the following conditions to measure the tensile strength at break (tensile stress at break (TB)) (MPa). (Test conditions) Measurement temperature: -30℃ Test speed: 500mm / Sample shape: JIS No. 3 Grip distance: 55 mm Distance between gauge lines: 20mm Testing machine: Strograph TD Evaluation Criteria A: 7MPa or more B: 5MPa or more but less than 7MPa C: Less than 5 MPa

[0162] [Cold resistance] Low temperature compression set (CS) [%] The compounds obtained in Examples 1 and 2 and Comparative Examples 1 and 2 were vulcanized at 170°C for 20 minutes using a press molding machine equipped with a cylindrical mold to prepare right cylindrical test pieces (vulcanizates) with a thickness of 12.7 mm and a diameter of 29 mm.

[0163] The compression set test was carried out in accordance with JIS K6262 using the obtained right cylindrical test piece (vulcanized product) by compressing it by 25% in an atmosphere of -30°C for 24 hours, and then determining the permanent set (%) after release.

[0164] The smaller the permanent set, the better the low-temperature properties. Evaluation Criteria A: Less than 70% B: 70% or more and 98% or less C: Over 98%

[0165] Glass transition temperature (Tg) [℃] The glass transition temperature (Tg) of the copolymer was measured by shredding 1 g of the copolymer, subjecting it to Soxhlet extraction using methyl ethyl ketone at 80°C for 3 hours, and then drying the copolymer under reduced pressure at 80°C overnight.

[0166] The glass transition temperature (Tg) of the copolymer was determined by DSC measurement under the following conditions. Using a differential scanning calorimeter (RDC220, manufactured by SII), approximately 10 mg of sample was placed in a nitrogen atmosphere. The temperature was raised from 30°C to 200°C at a rate of 50°C / min under atmospheric pressure and maintained at that temperature for 10 minutes. The temperature was then further cooled to -100°C at a rate of 10°C / min and held at that temperature for 5 minutes. After that, the temperature was increased to 200°C at a rate of 10°C / min.

[0167] The glass transition temperature (Tg) is determined by the change in specific heat during the second heating, which causes the DSC curve to bend. The baseline is sensed as a parallel shift. The temperature at the intersection of the line and the tangent to the point where the slope is maximum at the bend is the glass transition temperature (Tg ) was decided. Evaluation Criteria A: Tg is below -59°C B: Tg is above -59°C and below -55°C C: Tg exceeds -55°C

[0168] Roll processability 200 g of the copolymer was wound around a 6-inch roll (front roll 18 rpm, back roll 15 rpm) heated to 50° C., and the winding property and surface condition were observed. Evaluation was made according to the following criteria. Evaluation Criteria A: Rubber is wrapped around the roll and the surface is glossy B: The rubber wraps around the roll, but the surface is rough. C: Rubber does not wrap around the roll and kneading is not possible

[0169] [Table 1]

Claims

1. The ethylene-α-olefin-non-conjugated polyene copolymer (P) has structural units derived from ethylene [A], structural units derived from at least one type of α-olefin [A2] having 4 to 20 carbon atoms, and structural units derived from at least one type of non-conjugated polyene [A3], wherein the structural units derived from the α-olefin [A2] having 4 to 20 carbon atoms include structural units derived from 1-butene, and satisfies the following requirements (1) and (2): Requirement (1) The molar ratio [[A1] / [A2]] of the structural unit derived from ethylene [A1] to the structural unit derived from an α-olefin [A2] having 4 to 20 carbon atoms is 40 / 60 to 90 / 10. Requirement (2) The intrinsic viscosity [η] measured in decalin at 135° C. is 5.0 to 7.0 dl / g.

2. The ethylene-α-olefin-non-conjugated polyene copolymer (P) according to claim 1, further satisfying the following requirement (3): Requirement (3) The content of structural units derived from the non-conjugated polyene [A3] is 0.1 to 6.0 mol % (where the total of the structural units [A1], [A2] and [A3] is 100 mol %).

3. The ethylene-α-olefin-non-conjugated polyene copolymer (P) according to claim 1, further satisfying the following requirement (4): Requirement (4) The B value represented by the following formula (i) is 1.20 or more. B value = ([EX]+2[Y]) / [2×[E]×([X]+[Y])]...(i) Here, [E], [X], and [Y] represent the mole fractions of ethylene [A1], the α-olefin [A2] having 4 to 20 carbon atoms, and the non-conjugated polyene [A3], respectively, and [EX] represents the ethylene [A1]-α-olefin [A2] having 4 to 20 carbon atoms dyad chain fraction.

4. The ethylene / α-olefin / non-conjugated polyene copolymer (P) according to claim 1, wherein the amount of oil extension is 50 to 150 parts by mass per 100 parts by mass of the ethylene / α-olefin / non-conjugated polyene copolymer (P).

5. The ethylene / α-olefin / non-conjugated polyene copolymer (P) according to claim 1, wherein the non-conjugated polyene [A3] contains only one partial structure selected from the group consisting of the following partial structural formulas (I) and (II) in total per molecule: 【Chemical 1】

6. The ethylene / α-olefin / non-conjugated polyene copolymer (P) according to claim 5, wherein the non-conjugated polyene [A3] is 5-ethylidene-2-norbornene (ENB).

7. The ethylene / α-olefin / non-conjugated polyene copolymer (P) according to claim 1, which has a tensile strength of 5 MPa or more as measured in accordance with JIS K6251.

8. The ethylene / α-olefin / non-conjugated polyene copolymer (P) according to claim 1, which has a permanent set (%) of 98% or less after being compressed to a compression amount of 25% in an atmosphere of −30°C for 24 hours in accordance with JIS K6262.

9. The ethylene / α-olefin / non-conjugated polyene copolymer (P) according to claim 1, which has a glass transition temperature (Tg) of −55° C. or lower.

10. A bridged metallocene compound (t) represented by the following general formula (1): and at least one compound (u) selected from the group consisting of an organometallic compound (u-1), an organoaluminum oxy compound (u-2), and a compound (u-3) that reacts with the bridged metallocene compound (t) to form an ion pair; The method for producing the ethylene / α-olefin / non-conjugated polyene copolymer (P) according to claim 1, wherein ethylene, 1-butene (or, together with 1-butene, an α-olefin having 5 to 20 carbon atoms), or an α-olefin having 5 to 20 carbon atoms, and a non-conjugated polyene are copolymerized in the presence of an olefin polymerization catalyst containing 【Chemistry 2】 R 1 to R 14 in general formula (1) In the above general formula (1), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 and R 14 are each independently a hydrogen atom, a hydrocarbon group, a heteroatom-containing hydrocarbon group, or a silicon-containing group, and R 1 From R 4 Any two of the substituents may be bonded to each other to form a ring, and R 5 From R 12 Any two of the substituents may be bonded to each other to form a ring, and R 13 and R 14 may be bonded to each other to form a ring. Y in general formula (1) In the general formula (1), Y is a carbon atom, a silicon atom, a germanium atom, or a tin atom. M, Q, and j in general formula (1) In the general formula (1), M is a Group 4 transition metal. Q is a halogen atom, a hydrocarbon group, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair, and when j is an integer of 2 or more, Qs may be the same or different from each other.

11. The method for producing an ethylene / α-olefin / non-conjugated polyene copolymer (P) according to claim 8, wherein the bridged metallocene compound (t) represented by the general formula (1) is represented by the following general formula (2): 【Chemistry 3】 In the above general formula (2), R 13 , R 14 , M, Q, and j are the same as in the general formula (1) above.

12. The method for producing an ethylene / α-olefin / non-conjugated polyene copolymer (P) according to claim 11, wherein in general formula (2), M is a hafnium atom.

13. The method for producing an ethylene / α-olefin / non-conjugated polyene copolymer (P) according to claim 11, wherein in general formula (2), Q is a methyl group and j is an integer of 2.

14. In general formula (2), R 13 and R 14 and are both methoxy groups.

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