Ethylene / α-olefin copolymer and method for producing same

Abstract

One embodiment of the present invention relates to an ethylene / α-olefin copolymer or a method for producing the ethylene / α-olefin copolymer. The ethylene / α-olefin copolymer (A) has a structural unit (i) derived from ethylene and a structural unit (ii) derived from an α-olefin having 3-10 carbon atoms, and satisfies specific requirements (A1) to (A4).

Description

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

[0001] One embodiment of the present invention relates to an ethylene / α-olefin copolymer or a method for producing the ethylene / α-olefin copolymer.

[0002] Ethylene-α-olefin copolymers such as ethylene-propylene copolymer, ethylene-1-butene copolymer, and ethylene-1-octene copolymer are widely used in rubber products, etc. Furthermore, modified ethylene-α-olefin copolymers obtained by modifying terminally unsaturated ethylene-α-olefin copolymers are widely used as modifiers because they can introduce new properties (Patent Document 1).

[0003] However, conventional methods for producing terminally unsaturated homopolymers have had the problem that it is difficult to obtain a terminally unsaturated ethylene / α-olefin copolymer because the catalyst suitable for introducing an unsaturated group varies depending on the type of monomer. Moreover, even if an unsaturated group can be introduced into the terminal, it is difficult to obtain a terminally unsaturated ethylene / α-olefin copolymer having the desired composition and molecular weight.

[0004] Japanese Patent Application Laid-Open No. 2015-193806

[0005] One embodiment of the present invention provides an ethylene / α-olefin copolymer having a high rate of terminal unsaturation, a low molecular weight, and a narrow molecular weight distribution.

[0006] Examples of embodiments of the present invention are given below.

[0007] [1] An ethylene / α-olefin copolymer (A) having a structural unit (i) derived from ethylene and a structural unit (ii) derived from an α-olefin having 3 to 10 carbon atoms, and satisfying the following requirements (A1) to (A4): (A1) the content of the structural unit (i) is 30 to 70 mol % and the content of the structural unit (ii) is 30 to 70 mol % relative to 100 mol % of the total content of the structural unit (i) and the structural unit (ii); (A2) the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) and calculated in terms of polystyrene is 0.01 to 0.1; A(A3) The weight average molecular weight (Mw) and number average molecular weight (Mn) obtained by gel permeation chromatography (GPC) in terms of polystyrene are 300 to 4000; A ) and the ratio (Mw / Mn A ) is 1.0 to 5.0; (A4) 13 [2] The content of vinyl end groups is more than 60% relative to the total integrated intensity of the signals of vinyl end groups, vinylidene end groups, di-substituted olefin end groups, tri-substituted olefin end groups, and saturated end groups determined by C-NMR. [2] The above-mentioned requirement (A3) is that the weight average molecular weight (Mw) and number average molecular weight (Mn) obtained by gel permeation chromatography and converted into polystyrene equivalents are A ) and the ratio (Mw / Mn A [3] The ethylene / α-olefin copolymer (A) according to item [1] or [2], further satisfying the following requirement (A5): (A5) 1 [4] The ethylene / α-olefin copolymer (A) according to any one of items [1] to [3], further satisfying the following requirement (A6): (A6) wherein the content of vinyl terminals is more than 70% relative to the total integrated intensity of the signals of vinyl terminals, vinylidene terminals, di-substituted olefin terminals, and tri-substituted olefin terminals determined by H-NMR. 1 The number average molecular weight (Mn B ) and the number average molecular weight (Mn A ) to the ratio (Mn B / Mn A) is 0.50 or more and 1.4 or less. [5] The ethylene / α-olefin copolymer (A) according to any one of items [1] to [4] is contained in a macromer, paint, primer, modifier, or coating material. [6] A method for producing the ethylene / α-olefin copolymer (A) according to any one of items [1] to [4], the method comprising polymerizing an olefin at a temperature of 60 to 130°C in the presence of an activator and at least one metallocene compound represented by the following general formula [1]: (In formula [1], each X is independently selected from the group consisting of a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, and a combination thereof, and may form a fused ring or a part of a ring system with each other; R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 and R 12 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and Q is at least one bridging group selected from the group consisting of a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group, and a germylene group, and when Q contains a silylene group or a germylene group, it may also contain a hydrocarbon group having 1 to 20 carbon atoms.

[0008] According to one embodiment of the present invention, it is possible to provide an ethylene / α-olefin copolymer having a high rate of terminal unsaturation, a low molecular weight, and a narrow molecular weight distribution.

[0009] One embodiment of the present invention will be described in detail below. <Ethylene / α-olefin copolymer (A)> The ethylene / α-olefin copolymer (A) according to one embodiment of the present invention has a structural unit (i) derived from ethylene and a structural unit (ii) derived from an α-olefin having 3 to 10 carbon atoms, and satisfies the following requirements (A1) to (A4).

[0010] Examples of α-olefins having 3 to 10 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and 1-decene, and are preferably α-olefins having 3 to 8 carbon atoms, more preferably α-olefins having 3 to 5 carbon atoms, and even more preferably propylene. α-olefins having 3 to 10 carbon atoms are preferred in that they exhibit excellent shear stability as lubricating oils or viscosity index improvers.

[0011] <Requirement (A1)> The ethylene-α-olefin copolymer (A) has a content of the structural unit (i) of 30 to 70 mol%, preferably 35 to 65 mol%, more preferably 40 to 60 mol%, and even more preferably 45 to 55 mol%, relative to the total content of the structural units (i) and (ii) (100 mol%), and a content of the structural unit (ii) of 30 to 70 mol%, preferably 35 to 65 mol%, more preferably 40 to 60 mol%, and even more preferably 45 to 55 mol%. Having the contents of the structural units (i) and (ii) within these ranges is preferred in that the copolymer exhibits excellent temperature and viscosity characteristics as a lubricating base oil or viscosity index improver.

[0012] The ethylene / α-olefin copolymer (A) has at least one structural unit derived from an α-olefin having 3 to 10 carbon atoms, and may have two or more structural units derived from α-olefins having 3 to 10 carbon atoms. The ethylene and α-olefins having 3 to 10 carbon atoms, which are monomers constituting the ethylene / α-olefin copolymer (A), may each be, for example, a monomer derived from a fossil fuel or a monomer derived from biomass, and these monomers may be used alone or in combination of two or more.

[0013] <Requirement (A2)> The number average molecular weight (Mn) of the ethylene / α-olefin copolymer (A) measured by gel permeation chromatography (GPC) and calculated in terms of polystyrene AThe number average molecular weight (Mn) is 300 to 4000, preferably 300 to 3500, even more preferably 300 to 3000, even more preferably 300 to 2000, particularly preferably 400 to 2000, and especially preferably 418 to 1980. A It is preferable that the number average molecular weight (Mn) is within the above range in that the solubility of the macromonomer in hydrocarbon solvents is improved. A ) can be determined by the method described in the Examples.

[0014] <Requirement (A3)> The weight average molecular weight (Mw) and number average molecular weight (Mn) of the ethylene-α-olefin copolymer (A) measured by gel permeation chromatography (GPC) and calculated in terms of polystyrene are A ) and the ratio (Mw / Mn A ) is 1.0 to 5.0, preferably 1.0 to 4.0, more preferably 1.2 to 3.8, even more preferably 1.4 to 3.6, particularly preferably 1.6 to 3.4, particularly preferably 1.7 to 3.2, and especially preferably 1.81 to 3.02. A ) and the ratio (Mw / Mn A When the weight average molecular weight (Mw) and the number average molecular weight (Mn) are within the above range, the modifier is favorable in terms of reducing non-volatile substances and improving processability. A ) and the ratio (Mw / Mn A ) can be determined by the method described in the Examples.

[0015] <Requirement (A4)> Ethylene / α-olefin copolymer (A) 13The content of vinyl groups is greater than 60%, preferably greater than 60% but not greater than 100%, more preferably greater than 60% but not greater than 95%, even more preferably greater than 60% but not greater than 90%, particularly preferably greater than 60% but not greater than 85%, and even more preferably 61% or greater but not greater than 77% relative to the total integrated intensity of the signals of vinyl groups, vinylidene groups, disubstituted olefin groups, trisubstituted olefin groups, and saturated groups determined by C-NMR. A content of vinyl groups within the above range is preferred in terms of improving the reaction efficiency of the macromonomer because the content of highly reactive vinyl groups is high. The contents of vinyl groups, vinylidene groups, disubstituted olefin groups, trisubstituted olefin groups, and saturated groups can be determined by the methods described in the Examples.

[0016] The ethylene / α-olefin copolymer (A) according to one embodiment of the present invention preferably satisfies at least one of the following requirements (A5) to (A6):

[0017] <Requirement (A5)> Ethylene / α-olefin copolymer (A) 1 The content of vinyl groups is greater than 70%, preferably greater than 70% and less than 100%, more preferably greater than 70% and less than 95%, even more preferably greater than 70% and less than 90%, particularly preferably 75% to 85%, and even more preferably 77% to 81%. A vinyl group end content within the above range is preferred in terms of improving the reaction efficiency of the macromonomer because the content of highly reactive vinyl groups is high. The contents of vinyl groups, vinylidene groups, disubstituted olefin ends, and trisubstituted olefin ends can be determined by the methods described in the Examples.

[0018] <Requirement (A6)> The ethylene / α-olefin copolymer (A) 1 The number average molecular weight (Mn B ) and the number average molecular weight (Mn A ) to the ratio (Mn B / Mn A The number average molecular weight (Mn) is 0.50 or more and 1.4 or less, preferably 0.55 to 1.35, more preferably 0.60 to 1.30, even more preferably 0.65 to 1.25, particularly preferably 0.70 to 1.10, and even more preferably 0.75 to 0.98. B ) and number average molecular weight (Mn A ) to the ratio (Mn B / Mn A If the number average molecular weight (Mn) is within the above range, the saturated terminal content is low and the content of unsaturated terminals is high, which is preferable in terms of improving the reaction efficiency of the macromonomer. B ) and number average molecular weight (Mn A ) to the ratio (Mn B / Mn A ) can be determined by the method described in the Examples.

[0019] <Method for Producing Ethylene / α-Olefin Copolymer (A)> The method for producing the ethylene / α-olefin copolymer (A) is not particularly limited. For example, the ethylene / α-olefin copolymer (A) can be produced by copolymerizing ethylene and at least one α-olefin having 3 to 10 carbon atoms in the presence of an olefin polymerization catalyst. Preferably, the method includes a step of polymerizing an olefin at a temperature of 60 to 130° C. in the presence of an activator and at least one metallocene compound represented by the following general formula [1]:

[0020] The polymerization temperature is preferably 60 to 130° C., more preferably 65 to 125° C., more preferably 70 to 120° C., and particularly preferably 70 to 115° C. A polymerization temperature within the above range is preferred because it allows the molecular weight of the resulting polymer to be controlled within the range described in requirement (A2).

[0021] Examples of the activator include at least one compound (b) selected from organometallic compounds (b-1), organoaluminum oxy compounds (b-2), and compounds (b-3) that react with the formula [1] to form an ion pair.

[0022] Examples of the organometallic compound (b-1) (excluding the organoaluminum oxy compound (b-2)) include organoaluminum compounds such as 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.

[0023] Examples of the organoaluminum oxy compound (b-2) include conventionally known aluminoxanes.

[0024] Examples of the compound (b-3) that reacts with the formula [1] 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, U.S. Pat. No. 5,321,106, and WO 2015 / 122415.

[0025]

[0026] In formula [1], X's are each independently selected from the group consisting of a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, and combinations thereof, and may form a condensed ring or a part of a ring system together, and R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 and R 12 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and Q is at least one crosslinking group selected from the group consisting of a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group, and a germylene group, and when Q contains a silylene group or a germylene group, it may also contain a hydrocarbon group having 1 to 20 carbon atoms.

[0027] <X> Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a 1-propyl group, a 1-butyl group, a 1-pentyl group, a 1-hexyl group, a 1-heptyl group, a 1-octyl group, an isopropyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, an allyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclooctenyl group, a norbornyl group, a bicyclo[2.2.2]octan-1-yl group, a 1-adamantyl group, a 2-adamantyl group, a benzyl group, a benzhydryl group, and a cumyl group. Examples of such alkyl groups include a 1,1-diphenylethyl group, a trityl group, a 2-phenylethyl group, a 3-phenylpropyl group, a cinnamyl group, a phenyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group, a 2,6-di-iso-propylphenyl group, a 2,4,6-tri-iso-propylphenyl group, a 4-tert-butylphenyl group, a 3,5-di-tert-butylphenyl group, a 4-adamantylphenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a binaphthyl group, a phenanthryl group, an anthracenyl group, a ferrocenyl group, a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, a hexenyl group, a cyclohexenyl group, and an octenyl group. Among the monovalent hydrocarbon groups having 1 to 20 carbon atoms, a methyl group, an ethyl group, a 1-propyl group, a 1-butyl group, a 1-pentyl group, a 1-hexyl group, a 1-heptyl group, a 1-octyl group, an isopropyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, an isopentyl group, a neopentyl group, and a tert-pentyl group are preferred, and a methyl group is more preferred.

[0028] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine, with chlorine being preferred.

[0029] <R1 to R 12>> Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include the monovalent hydrocarbon groups described above, preferably monovalent hydrocarbon groups having 1 to 10 carbon atoms, and more preferably monovalent hydrocarbon groups having 1 to 8 carbon atoms. Examples of the monovalent hydrocarbon group having 1 to 8 carbon atoms include alkyl groups such as methyl, ethyl, 1-propyl, isopropyl, 1-butyl, isobutyl, tert-butyl, 1-pentyl, neopentyl, 1-hexyl, cyclohexyl, and 1-octyl; aryl groups such as phenyl, tolyl, and xylyl; aralkyl groups such as benzyl and 2-phenylethyl; and alkenyl groups such as vinyl, allyl, propenyl, isopropenyl, butenyl, hexenyl, cyclohexenyl, and octenyl. R1 and R7 are each independently preferably an alkyl group such as a methyl group, an ethyl group, a 1-propyl group, an isopropyl group, a 1-butyl group, an isobutyl group, a tert-butyl group, a 1-pentyl group, a neopentyl group, a 1-hexyl group, a cyclohexyl group, or a 1-octyl group, more preferably a methyl group, an ethyl group, a 1-propyl group, an isopropyl group, a 1-butyl group, an isobutyl group, or a tert-butyl group, still more preferably a methyl group, an ethyl group, a 1-propyl group, or an isopropyl group, and particularly preferably a methyl group. R2 and R8 are each independently preferably a hydrogen atom, a methyl group, an ethyl group, a 1-propyl group, an isopropyl group, a 1-butyl group, an isobutyl group, a tert-butyl group, a 1-pentyl group, a neopentyl group, a 1-hexyl group, a cyclohexyl group, or an octyl group, more preferably a hydrogen atom, a methyl group, an ethyl group, a 1-propyl group, an isopropyl group, a 1-butyl group, an isobutyl group, or a tert-butyl group, still more preferably a hydrogen atom, a methyl group, an ethyl group, a 1-propyl group, or an isopropyl group, and particularly preferably a hydrogen atom or a 1-propyl group.R3 and R9 are each independently preferably a hydrogen atom, a methyl group, an ethyl group, a 1-propyl group, an isopropyl group, a 1-butyl group, an isobutyl group, a tert-butyl group, a 1-pentyl group, a neopentyl group, a 1-hexyl group, a cyclohexyl group, a 1-octyl group, a phenyl group, a tolyl group, or a xylyl group, more preferably a hydrogen atom, a methyl group, an ethyl group, a 1-propyl group, an isopropyl group, a 1-butyl group, an isobutyl group, a tert-butyl group, a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a 1-butyl group, an isobutyl group, a tert-butyl group, a phenyl group, a tolyl group, or a xylyl group, still more preferably a hydrogen atom, a methyl group, an ethyl group, a 1-propyl group, an isopropyl group, a phenyl group, a tolyl group, or a xylyl group, and particularly preferably a hydrogen atom or a phenyl group. 10 , R 11 and R 12 are each independently preferably a hydrogen atom, or an alkyl group such as a methyl group, an ethyl group, a 1-propyl group, an isopropyl group, a 1-butyl group, an isobutyl group, a tert-butyl group, a 1-pentyl group, a neopentyl group, a 1-hexyl group, a cyclohexyl group, or a 1-octyl group; more preferably a hydrogen atom, a methyl group, an ethyl group, a 1-propyl group, an isopropyl group, a 1-butyl group, an isobutyl group, or a tert-butyl group; still more preferably a hydrogen atom, a methyl group, an ethyl group, a 1-propyl group, or an isopropyl group; and particularly preferably a hydrogen atom.

[0030] <Q> Examples of divalent hydrocarbon groups having 1 to 20 carbon atoms include methylene, ethylene, propylene, phenylene, and naphthylene groups.

[0031] Examples of silylene groups having a hydrocarbon group having 1 to 20 carbon atoms include a methylsilylene group, a dimethylsilylene group, a diethylsilylene group, a di-isopropylsilylene group, a di(cyclohexyl)silylene group, a methyl(phenyl)silylene group, a diphenylsilylene group, and a trimethylsilylmethylene group.

[0032] Examples of germylene groups having a hydrocarbon group having 1 to 20 carbon atoms include a methylgermylene group, a dimethylgermylene group, a diethylgermylene group, a di-isopropylgermylene group, a di(cyclohexyl)germylene group, a methyl(phenyl)germylene group, a diphenylgermylene group, and a trimethylgermylmethylene group.

[0033] Among the above Q groups, a silylene group having a hydrocarbon group of 1 to 20 carbon atoms is preferred, and a dimethylsilylene group is more preferred.

[0034] Examples of the metallocene compound represented by the general formula [1] include dimethylsilylbis(2-methyl-4-phenylindenyl)hafnium dichloride and dimethylsilylbis(2-methyl-3-propylindenyl)hafnium dichloride.

[0035] The polymerization pressure is usually normal pressure to 10 MPa gauge pressure, preferably normal pressure to 8 MPa gauge pressure, more preferably normal pressure to 6 MPa gauge pressure, still more preferably normal pressure to 4 MPa gauge pressure, and particularly preferably normal pressure to 2 MPa gauge pressure. The copolymerization can be carried out by any of a batch system, a semi-continuous system, and a continuous system.

[0036] The reaction time (average residence time when the copolymerization reaction is carried out by a continuous method) varies depending on conditions such as catalyst concentration and polymerization temperature, and can be appropriately selected, but is usually 1 minute to 3 hours, preferably 5 minutes to 2.5 hours, more preferably 6 minutes to 2.0 hours, even more preferably 7 minutes to 1.0 hour, and particularly preferably 8 minutes to 0.5 hour. Furthermore, the polymerization can be carried out in two or more stages with different reaction conditions.

[0037] The molecular weight of the resulting ethylene / α-olefin copolymer (A) can be adjusted by changing the hydrogen concentration in the polymerization system or the polymerization temperature. It can also be adjusted by the amount of catalyst component used. When hydrogen is added to the polymerization system, the amount is suitably about 0.001 to 5,000 NL per kg of the ethylene / α-olefin copolymer produced.

[0038] The amount of terminal unsaturation in the resulting ethylene / α-olefin copolymer (A) can be increased by minimizing the amount of hydrogen added.

[0039] The metallocene compounds represented by the general formula [1] may be used singly or in combination of two or more.

[0040] <Uses> The ethylene / α-olefin copolymer (A) is used, for example, in macromers, paints, primers, modifiers, coating materials, and the like.

[0041] As a macromer, it is used, for example, in the production of modified copolymers such as graft copolymers.

[0042] Examples of paints include lacquer-based, urethane-based, acrylic-based, alkyd-based, epoxy-based, and polyester-based paints.

[0043] Examples of primers include thermoplastic polyolefin resins, thermoplastic polyurethane resin / urea resins, and thermosetting polyester resin / melamine resin / epoxy resins.

[0044] Modifiers include, for example, lubricant modifiers and surface modifiers.

[0045] Examples of coating materials include fluorine-based and silicone-based materials.

[0046] Hereinafter, one embodiment of the present invention will be described in more detail based on examples, but the present invention is not limited to these examples in any way.

[0047] <Weight average molecular weight (Mw) and number average molecular weight (Mn) measured by GPC A ) and molecular weight distribution (Mw / Mn A )> The weight average molecular weight (Mw) and number average molecular weight (Mn) of the ethylene / α-olefin copolymers described in the examples A ) and molecular weight distribution (Mw / Mn A ) was determined by the following method.

[0048] [Sample Pretreatment] 30 mg of the resin produced in the example was dissolved in 20 ml of o-dichlorobenzene at 145° C., and the solution was then filtered through a sintered filter with a pore size of 1.0 μm to prepare an analytical sample.

[0049] [GPC Analysis] Gel permeation chromatography (GPC) was used to determine the weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of polystyrene molecular weight. A The weight average molecular weight (Mw) and number average molecular weight (Mn) were calculated to obtain a molecular weight distribution curve. A ) to obtain the molecular weight distribution (Mw / Mn A ) was calculated.

[0050] [Measurement conditions] Measuring device: Gel permeation chromatograph HLC-8321 GPC / HT type (manufactured by Tosoh Corporation) Analyzing device: Data processing software Empower2 (Waters, registered trademark) Column: Two TSKgel GMH6-HT and two TSKgel GMH6-HTL (both 7.5 mm diameter x 30 cm length, Tosoh Corporation) Column temperature: 140°C Mobile phase: o-dichlorobenzene (containing 0.025% BHT) Detector: Differential refractometer Flow rate: 1 mL / min Sample concentration: 0.15% (w / v) Injection volume: 0.4 mL Sampling time interval: 0.5 seconds Column calibration: Monodisperse polystyrene (Tosoh Corporation) Molecular weight conversion: PS conversion / standard conversion method

[0051] <Structural analysis of polymer> The polymer of the resin described in the examples is 13 C-NMR and 1 The structure was analyzed by H-NMR as follows:

[0052] << 13 C-NMR≫ [Measurement conditions] Measurement device: AVANCE3 cryo-500 nuclear magnetic resonance device manufactured by Bruker Biospin Measurement nuclei: 13C (125 MHz) Measurement mode: Single pulse proton broadband decoupling Pulse width: 45° (5.00 μsec) Number of points: 64k Measurement range: 250 ppm (-55 to 195 ppm) Repetition time: 29.0 seconds Number of accumulations: 128 Measurement solvent: o-dichlorobenzene / benzene-d6 (4 / 1 v / v) Sample concentration: ca. 100 mg / 0.6 mL Measurement temperature: 120 °C, Window function: exponential (BF: 1.0 Hz) Chemical shift reference: δδ signal (29.73 ppm)

[0053] [Calculation of the content of vinyl group terminals in all terminals] 13 The C-NMR spectrum showed vinyl end groups, vinylidene end groups, di-substituted olefin end groups, tri-substituted olefin end groups, and saturated end groups. The content of vinyl end groups in all end groups was calculated from the integrated intensity of each signal.

[0054]

[0055] In each formula, dashed lines indicate bonds to atoms other than hydrogen atoms. The peaks of carbon atoms a to e are observed near the following: Peaks of carbon atoms a and a': 115 ppm Peak of carbon atom b: 110 ppm Peak of carbon atom c: 130 ppm Peak of carbon atom d: 132 ppm Peak of carbon atom e: 23 ppm Peaks of carbon atoms e' to e''': 12 ppm

[0056] The quantitative formula for determining the content of vinyl groups in all terminals is as follows: Content (%) of vinyl groups in all terminals = 100 × {integrated intensity of signal a + integrated intensity of signal a' / [{integrated intensity of signal a + integrated intensity of signal a' + integrated intensity of signal b + (integrated intensity of signal c / 2) + integrated intensity of signal d + (integrated intensity of signal e / 2) + integrated intensity of signal e' + integrated intensity of signal e" + integrated intensity of signal e'" + integrated intensity of signal e""} / 2]}

[0057] << 1 H-NMR≫ [Measurement conditions] Measurement device: JEOL ECX400P nuclear magnetic resonance device Measurement nuclei:1 H (400 MHz) Measurement mode: Single pulse Pulse width: 45° (5.25 μsec) Number of points: 32k Measurement range: 20 ppm (-4 to 16 ppm) Repetition time: 7.0 seconds Number of integrations: 64 Measurement solvent: o-dichlorobenzene-d ４ Sample concentration: ca. 20 mg / 0.6 mL Measurement temperature: 120° C. Window function: exponential (BF: 0.12 Hz) Chemical shift reference: o-dichlorobenzene (7.1 ppm).

[0058] [Calculation of ethylene and propylene content] 1 In the spectrum obtained by H-NMR measurement, ethylene units and propylene units in the main chain are observed. The ethylene and propylene contents were calculated from the integrated intensity of each signal.

[0059]

[0060] In each formula, dashed lines indicate bonds to atoms other than hydrogen atoms. The peaks of each hydrogen atom α to γ ​​are observed near the following ranges. - Hydrogen atom α peak: 0.95 ppm to 1.4 ppm - Hydrogen atom β peak: 0.95 ppm to 1.4 ppm - Hydrogen atom γ peak: 1.4 ppm to 1.7 ppm Furthermore, since the α and β peaks cannot be separated, the integrated intensity of α is calculated using the γ peak. The quantitative formulas for ethylene and propylene content are as follows: Ethylene content (mol %) = 100 × [(integrated intensity of signal: α + integrated intensity of signal: β - 2 × integrated intensity of signal: γ) / 4] / {[(integrated intensity of signal: α + integrated intensity of signal: β - 2 × integrated intensity of signal: γ) / 4] + integrated intensity of signal: γ} Propylene content (mol %) = 100 × integrated intensity of signal: γ / {[(integrated intensity of signal: α + integrated intensity of signal: β - 2 × integrated intensity of signal: γ) / 4] + integrated intensity of signal: γ}

[0061] [Calculation of the content of vinyl group terminals in unsaturated terminals] 1In the spectrum obtained by H-NMR measurement, vinyl group terminals, vinylidene group terminals, di-substituted olefin terminals, and tri-substituted olefin terminals are observed. 13 Unlike C-NMR 1 In the H-NMR measurement, the saturated terminals could not be distinguished from the ethylene and propylene units of the main chain. The content of vinyl groups in the unsaturated terminals was calculated from the integrated intensity of each signal.

[0062]

[0063] In each formula, dashed lines indicate bonds to atoms other than hydrogen atoms. The peaks of each of hydrogen atoms I to IV are observed near the following: Peak of carbon atom I: 5.9 ppm Peak of carbon atom I': 4.9 ppm Peak of carbon atom II: 4.6 ppm Peak of carbon atom III: 5.3 ppm Peak of carbon atom IV: 4.9 ppm Furthermore, since the peaks of IV and I' cannot be distinguished, the integrated intensity of IV is calculated using the peak of I. The quantitative formula for the content of vinyl group ends in unsaturated ends is as follows: Content (%) of vinyl group ends in unsaturated ends = 100 × integrated intensity of signal I / [integrated intensity of signal I + (integrated intensity of signal II / 2) + (integrated intensity of signal III / 2) + (integrated intensity of signal I' + integrated intensity of signal IV - integrated intensity of signal I × 2)]

[0064] [ 1 The number average molecular weight (Mn B ) Assuming one unsaturated group per chain, 1The molecular weight was calculated by H-NMR. The degree of polymerization of the ethylene unit and propylene unit in the main chain was calculated from the integrated intensity of each signal attributed to the ethylene unit and propylene unit in the main chain and the integrated intensity of each signal attributed to all unsaturated terminals. For each degree of polymerization, the molecular weight was calculated from the product of the molecular weights of the ethylene unit and propylene unit, 28 and 42. Degree of polymerization of ethylene units = [(integral intensity of signal α + integrated intensity of signal β - 2 × integrated intensity of signal γ) / 4] / [integral intensity of signal I + (integral intensity of signal II / 2) + (integral intensity of signal III / 2) + (integral intensity of signal I' + integrated intensity of signal IV - integrated intensity of signal I × 2)] Degree of polymerization of propylene units = integrated intensity of signal γ / [integral intensity of signal I + (integral intensity of signal II / 2) + (integral intensity of signal III / 2) + (integral intensity of signal I' + integrated intensity of signal IV - integrated intensity of signal I × 2)]

[0065] [ 1 The number average molecular weight (Mn B ) and the number average molecular weight (Mn A ) ratio (Mn B / Mn A ) 1 The number average molecular weight (Mn B ) was measured, and the number average molecular weight (Mn A The number average molecular weight (Mn B ) and number average molecular weight (Mn A )from, 1 The number average molecular weight (Mn B ) and the number average molecular weight (Mn A ) ratio (Mn B / Mn A ) was calculated. 1 The number average molecular weight (Mn B ) does not take saturated ends into account, so the molecular weight is estimated to be large. 1 The number average molecular weight (Mn B) and the number average molecular weight (Mn A ) ratio (Mn B / Mn A ) indicates the presence of many saturated ends.

[0066] [Example 1] The catalyst dimethylsilylbis(2-methyl-4-phenylindenyl)hafnium dichloride was synthesized by a known method. 250 mL of xylene was placed in a 500 mL glass reactor that had been thoroughly purged with nitrogen. Then, while maintaining the temperature at 110°C and stirring the inside of the polymerization reactor at 600 rpm, ethylene and propylene were continuously fed at 120 L / h and 54 L / h, respectively, until the liquid and gas phases were saturated. While continuously supplying ethylene and propylene, 1.0 mL (1.0 mmol) of a toluene solution of triisobutylaluminum (1.0 mol / L), 2.5 mL (0.005 mmol) of a toluene solution of dimethylsilylbis(2-methyl-4-phenylindenyl)hafnium dichloride (0.002 mol / L), and then 2.0 mL (0.020 mmol) of a toluene solution of triphenylcarbenium tetrakis(pentafluorophenyl)borate (hereinafter also referred to as PhCB(CF)) (10 mmol / L) were added, and polymerization was carried out at 110°C for 16 minutes under atmospheric pressure. The polymerization was terminated by adding a small amount of isobutanol. The resulting polymerization reaction solution was washed with dilute hydrochloric acid, and the organic layer obtained after separation was evaporated under reduced pressure to obtain an ethylene-propylene copolymer. The copolymer was dried under reduced pressure at 130°C for 10 hours to obtain 0.66 g. The resulting copolymer had a Mw of 2650 and a Mn A =1160, Mw / Mn A = 2.28, ethylene content = 49 mol%, propylene content = 51 mol%, 13 The content of vinyl groups in the total terminals, including unsaturated and saturated terminals, measured by C-NMR was 77%. The physical properties of the obtained copolymer are shown in Table 1.

[0067] [Example 2] 500 ml of xylene was placed in a 1.0 L glass reactor, and 78 L / h of ethylene and 44 L / h of propylene were added. Nitrogen gas was continuously fed at 52 L / h to saturate the liquid and gas phases. Polymerization was carried out in the same manner as in Example 1, except that the amount of triisobutylaluminum in toluene (1.0 mol / L) was 0.10 mL (0.10 mmol), to obtain 8.45 g of an ethylene-propylene copolymer. The obtained copolymer had a Mw of 3850 and a Mn A =1280, Mw / Mn A = 3.01, ethylene content = 50 mol%, propylene content = 50 mol%, 13 The content of vinyl groups in the total terminals, including unsaturated and saturated terminals, measured by C-NMR was 63%. The physical properties of the obtained copolymer are shown in Table 1.

[0068] [Example 3] Polymerization was carried out in the same manner as in Example 2, except that 1.0 mL (0.010 mmol) of a toluene solution of triphenylcarbenium tetrakis(pentafluorophenyl)borate (10 mmol / L) was added and the polymerization was carried out at 115°C under normal pressure for 16 minutes, to obtain 4.49 g of an ethylene-propylene copolymer. The resulting copolymer had a Mw of 2870 and a Mn A =1140, Mw / Mn A = 2.52, ethylene content = 45 mol%, propylene content = 55 mol%, 13 The content of vinyl groups in the total terminals, including unsaturated and saturated terminals, measured by C-NMR was 65%. The physical properties of the obtained copolymer are shown in Table 1.

[0069] [Example 4] Dimethylsilylbis(2-methyl-3-propylindenyl)hafnium dichloride used as a catalyst was synthesized by the method described in the examples of JP-A No. 2014-513735 and in Brant, P., Organometallics 2016, 35, 2836-2839. 250 mL of xylene was placed in a 500 mL glass reactor, and then ethylene and propylene were continuously fed at 48 L / h and 84 L / h, respectively, while maintaining the temperature at 100°C and stirring the inside of the polymerization reactor at 600 rpm, until the liquid phase and gas phase were saturated. While continuously supplying ethylene and propylene, 0.10 mL (0.10 mmol) of a toluene solution of triisobutylaluminum (1.0 mol / L), 1 mL (0.002 mmol) of a toluene solution of dimethylsilylbis(2-methyl-3-propylindenyl)hafnium dichloride (0.002 mol / L), and then 0.8 mL (0.008 mmol) of a toluene solution of triphenylcarbenium tetrakis(pentafluorophenyl)borate (10 mmol / L) were added, and polymerization was carried out at atmospheric pressure and 100°C for 10 minutes. The polymerization was terminated by adding a small amount of isobutanol. The resulting polymerization reaction solution was washed with dilute hydrochloric acid, and the organic layer obtained by separation was evaporated under reduced pressure to obtain an ethylene-propylene copolymer. The copolymer was dried under reduced pressure at 130°C for 10 hours to obtain 3.62 g. The resulting copolymer had a Mw of 755 and a Mn A =418, Mw / Mn A = 1.81, ethylene content = 53 mol%, propylene content = 47 mol%, 13 The content of vinyl groups in the total terminals, including unsaturated and saturated terminals, measured by C-NMR was 61%. The physical properties of the obtained copolymer are shown in Table 1.

[0070] [Example 5] A glass reactor having an internal volume of 500 mL was charged with 250 mL of toluene, and then polymerization was carried out in the same manner as in Example 4, except that ethylene at 54 L / h and propylene at 78 L / h were continuously fed while maintaining the temperature at 70°C and stirring the inside of the polymerization reactor at 600 rpm, and the polymerization time was set to 25 minutes, to obtain 16.1 g of an ethylene-propylene copolymer. The obtained copolymer had a Mw of 5970 and a Mn A =1980, Mw / Mn A = 3.02, ethylene content = 55 mol%, propylene content = 45 mol%, 13 The content of vinyl groups in the total terminals, including unsaturated and saturated terminals, measured by C-NMR was 64%. The physical properties of the obtained copolymer are shown in Table 1.

[0071] Comparative Example 1: A 2.0 L glass reactor was charged with 1.0 L of toluene and 4.0 mL (4.0 mmol) of a toluene solution of triisobutylaluminum (1.0 mol / L) was added. 10 mL (0.02 mmol) of a toluene solution of dimethylsilylbis(2-methyl-4-phenylindenyl)hafnium dichloride (0.002 mol / L) was added, followed by 8.0 mL (0.080 mmol) of a toluene solution of triphenylcarbenium tetrakis(pentafluorophenyl)borate (10 mmol / L), and polymerization was carried out at 90°C for 16 minutes under atmospheric pressure. Except for these changes, polymerization was carried out in the same manner as in Example 1, yielding 24.0 g of an ethylene-propylene copolymer. The resulting copolymer had a Mw of 18,200 and a Mn A =5270, Mw / Mn A = 3.45, ethylene content = 46 mol%, propylene content = 54 mol%, 13 The content of vinyl groups in the total terminals, including unsaturated and saturated terminals, measured by C-NMR was 40%. The physical properties of the obtained copolymer are shown in Table 1.

[0072] [Comparative Example 2] 300 mL of toluene was placed in a 500 mL glass reactor, and the reactor was maintained at 50 ° C. with stirring at 600 rpm. Ethylene and propylene were continuously fed at 9.9 L / h and 98.4 L / h, respectively, while the ethylene and propylene were continuously fed. 5.0 mL (5.0 mmol) of a toluene solution (1.00 mol / L) of modified methylaluminoxane (hereinafter also referred to as MMAO) manufactured by Tosoh Fine Chemical Co., Ltd. was added, followed by 2.5 mL (0.005 mmol) of a toluene solution (0.002 mol / L) of bis(cyclopentadienyl)zirconium (IV) dichloride manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., and polymerization was carried out at 50 ° C. for 30 minutes under normal pressure. The polymerization was terminated by adding a small amount of isobutanol. The resulting polymerization reaction solution was washed with dilute hydrochloric acid, and the organic layer was separated and the solvent was removed by distillation under reduced pressure to obtain an ethylene-propylene copolymer. The copolymer was dried under reduced pressure at 130°C for 10 hours to obtain 1.83 g of the copolymer. The resulting copolymer had a Mw of 3030 and a Mn A =1140, Mw / Mn A = 2.66, ethylene content = 49 mol%, propylene content = 51 mol%, 13 The total content of vinyl groups at the unsaturated and saturated ends measured by C-NMR was 0%. The physical properties of the copolymer obtained are shown in Table 1.

[0073]

Claims

1. An ethylene / α-olefin copolymer (A) having a structural unit (i) derived from ethylene and a structural unit (ii) derived from an α-olefin having 3 to 10 carbon atoms, and satisfying the following requirements (A1) to (A4): (A1) the content of the structural unit (i) is 30 to 70 mol % and the content of the structural unit (ii) is 30 to 70 mol % relative to 100 mol % of the total content of the structural unit (i) and the structural unit (ii); (A2) the number average molecular weight (Mn) measured by gel permeation chromatography and calculated in terms of polystyrene is 1.25%. A (A3) The weight average molecular weight (Mw) and number average molecular weight (Mn) obtained by gel permeation chromatography and converted into polystyrene are 300 to 4000; A ) and the ratio (Mw / Mn A ) is 1.0 to 5.0; (A4) 13 The content of vinyl groups is more than 60% relative to 100% of the total integrated intensity of the signals of vinyl groups, vinylidene groups, di-substituted olefinic ends, tri-substituted olefinic ends and saturated ends determined by C-NMR.

2. The requirement (A3) above is that the weight average molecular weight (Mw) and number average molecular weight (Mn) are measured by gel permeation chromatography and converted into polystyrene equivalents. A ) and the ratio (Mw / Mn A 2. The ethylene / α-olefin copolymer (A) according to claim 1, wherein the α-olefin copolymer (A) is 1.0 to 4.

0.

3. The ethylene / α-olefin copolymer (A) according to claim 1, which further satisfies the following requirement (A5): (A5) 1 The content of vinyl groups is more than 70% relative to 100% of the total integrated intensity of the signals of vinyl groups, vinylidene groups, di-substituted olefin groups, and tri-substituted olefin groups determined by H-NMR.

4. The ethylene / α-olefin copolymer (A) according to claim 1, which further satisfies the following requirement (A6): (A6) 1 The number average molecular weight (Mn B ) and the number average molecular weight (Mn A ) and the ratio (Mn B / Mn A ) is 0.50 or more and 1.4 or less.

5. The ethylene / α-olefin copolymer (A) according to any one of claims 1 to 4, which is contained in a macromer, paint, primer, modifier or coating material.

6. A method for producing the ethylene / α-olefin copolymer (A) according to any one of claims 1 to 4, comprising the step of polymerizing an olefin at a temperature of 60 to 130°C in the presence of an activator and at least one metallocene compound represented by the following general formula [1]: (In formula [1], each X is independently selected from the group consisting of a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, and a combination thereof, and may form a fused ring or a part of a ring system with each other; R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 and R 12 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and Q is at least one bridging group selected from the group consisting of a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group, and a germylene group, and when Q contains a silylene group or a germylene group, it may also contain a hydrocarbon group having 1 to 20 carbon atoms.

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