Ethylene·alpha-olefin copolymer and method for producing the same

Abstract

One embodiment of the present application relates to an ethylene · alpha-olefin copolymer or a production method for the ethylene · alpha-olefin copolymer, the ethylene · alpha-olefin copolymer (A) having a structural unit (i) derived from ethylene and a structural unit (ii) derived from an alpha-olefin having 3 to 10 carbon atoms, and satisfying specific requirements (A1) to (A4).

Description

Technical Field

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

[0002] Ethylene-α-olefin copolymers such as ethylene-propylene copolymers, ethylene-1-butene copolymers, and ethylene-1-octene copolymers are widely used in rubber products. In addition, modified ethylene-α-olefin copolymers obtained by modifying terminally unsaturated ethylene-α-olefin copolymers can introduce new properties, thus broadening their applications as modifiers (Patent Document 1).

[0003] However, in conventional methods for producing terminally unsaturated homopolymers, there is a problem that the catalysts suitable for introducing unsaturated groups vary depending on the type of monomer, making it difficult to obtain terminally unsaturated ethylene-α-olefin copolymers. Furthermore, even if unsaturated groups are successfully introduced to the ends, it remains difficult to obtain terminally unsaturated ethylene-α-olefin copolymers with the desired composition and molecular weight.

[0004] Existing technical documents Patent documents Patent Document 1: Japanese Patent Application Publication No. 2015-193806 Summary of the Invention

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

[0006] Methods for solving problems The following are examples of methods of the present invention.

[0007] [1] An ethylene-α-olefin copolymer (A) having structural units (i) derived from ethylene and structural units (ii) derived from α-olefins having 3 to 10 carbon atoms, and satisfying the following requirements (A1) to (A4): (A1) Relative to the total content of the aforementioned structural unit (i) and the aforementioned structural unit (ii) of 100 mol%, the content of the aforementioned structural unit (i) is 30 to 70 mol%, and the content of the aforementioned structural unit (ii) is 30 to 70 mol%. (A2) The number-average molecular weight (Mn) was determined by gel permeation chromatography (GPC) and converted using polystyrene. A The range is 300-4000; (A3) The weight-average molecular weight (Mw) and number-average molecular weight (Mn) were determined by gel permeation chromatography (GPC) and converted using polystyrene. A The ratio of Mw / MnA The value ranges from 1.0 to 5.0. (A4) relative to passing 13 The content of vinyl terminus is greater than 60% when the sum of the integrated intensities of the signals obtained by C-NMR for vinyl terminus, vinylidene terminus, disubstituted olefin terminus, trisubstituted olefin terminus, and saturated terminus is 100%.

[0008] [2] The ethylene-α-olefin copolymer (A) as described in item [1], wherein, in the aforementioned element (A3), the weight-average molecular weight (Mw) and number-average molecular weight (Mn) obtained by gel permeation chromatography and converted from polystyrene are determined. A The ratio of Mw / Mn A The value ranges from 1.0 to 4.0.

[0009] [3] The ethylene-α-olefin copolymer (A) as described in item [1] or [2] also satisfies the following requirement (A5): (A5) relative to passing 1 The content of the vinyl terminus is greater than 70% when the sum of the integrated intensities of the signals of the vinyl terminus, vinylidene terminus, disubstituted olefin terminus, and trisubstituted olefin terminus obtained by H-NMR is 100%.

[0010] [4] The ethylene-α-olefin copolymer (A) as described in any one of items [1] to [3] also satisfies the following requirement (A6): (A6) Through 1 Number-average molecular weight (Mn) obtained by H-NMR B ) and the number-average molecular weight (Mn) measured by gel permeation chromatography (GPC) A The ratio of Mn B / Mn A The value is between 0.50 and 1.4.

[0011] [5] The ethylene-α-olefin copolymer (A) as described in any one of items [1] to [4] is contained in a macromonomer, coating, primer, modifier or coating material.

[0012] [6] A method for manufacturing an ethylene-α-olefin copolymer (A), which is a method for obtaining an ethylene-α-olefin copolymer (A) as described in any one of items [1] to [4], the aforementioned manufacturing method comprising 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].

[0013] [Chemical Formula 1] (In formula [1], X is independently selected from groups consisting of hydrogen atoms, monovalent hydrocarbon groups with 1 to 20 carbon atoms, halogen atoms and their combinations, which can form fused rings or part of a ring system.) R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 and R 12 Each is independently a hydrogen atom or a monovalent hydrocarbon group with 1 to 20 carbon atoms. 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 germanylene group. If Q includes a silylene or germanylene group, it may have a hydrocarbon group having 1 to 20 carbon atoms. Invention Effects According to one embodiment of the present invention, it is possible to provide ethylene-α-olefin copolymers with high terminal unsaturation, low molecular weight and narrow molecular weight distribution. Detailed Implementation

[0014] The following is a detailed description of one embodiment of the present invention.

[0015] <Ethylene-α-olefin copolymer (A)> An embodiment of the present invention relates to an ethylene-α-olefin copolymer (A) having structural units (i) derived from ethylene and structural units (ii) derived from α-olefins having 3 to 10 carbon atoms, and satisfying the following requirements (A1) to (A4).

[0016] Examples of α-olefins with 3 to 10 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and 1-decene, with α-olefins having 3 to 8 carbon atoms being preferred, α-olefins having 3 to 5 carbon atoms being more preferred, and propylene being even more preferred. α-olefins with 3 to 10 carbon atoms are preferred in terms of exhibiting excellent shear stability as a lubricant or viscosity index improver.

[0017] <Requirements (A1)> Regarding the ethylene-α-olefin copolymer (A), relative to the total content of the aforementioned structural unit (i) and the aforementioned structural unit (ii) of 100 mol%, the content of the aforementioned structural unit (i) is 30 to 70 mol%, preferably 35 to 65 mol%, more preferably 40 to 60 mol%, and even more preferably 45 to 55 mol%, and the content of the aforementioned structural unit (ii) is 30 to 70 mol%, preferably 35 to 65 mol%, more preferably 40 to 60 mol%, and even more preferably 45 to 55 mol%.

[0018] If the contents of structural units (i) and (ii) are within the aforementioned range, they are preferred in terms of exhibiting excellent temperature and viscosity characteristics as a lubricating oil base or viscosity index improver.

[0019] The ethylene-α-olefin copolymer (A) has at least one structural unit derived from an α-olefin having 3 to 10 carbon atoms, or may have two or more structural units derived from an α-olefin having 3 to 10 carbon atoms.

[0020] The monomers constituting the ethylene-α-olefin copolymer (A), namely ethylene and α-olefins with 3 to 10 carbon atoms, can each be monomers derived from fossil fuels or biomass, for example. One of these monomers can be used alone, or two or more can be used together.

[0021] <Requirement (A2)> The number-average molecular weight (Mn) of ethylene-α-olefin copolymer (A) was determined by gel permeation chromatography (GPC) and converted using polystyrene. A The number average molecular weight (Mn) is 300-4000, preferably 300-3500, more preferably 300-3000, even more preferably 300-2000, even more preferably 400-2000, and even more preferably 418-1980. A Within the aforementioned range, it is preferable to improve the solubility of macromonomers in hydrocarbon solvents. Number-average molecular weight (Mn) A The value can be obtained using the method described in the examples.

[0022] <Requirements (A3)> The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of ethylene-α-olefin copolymer (A) were determined by gel permeation chromatography (GPC) and converted using polystyrene. A The ratio of Mw / Mn A The weight-average molecular weight (Mw) is 1.0~5.0, preferably 1.0~4.0, more preferably 1.2~3.8, further preferably 1.4~3.6, particularly preferably 1.6~3.4, particularly more preferably 1.7~3.2, and particularly further preferably 1.81~3.02. If the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are... A The ratio of Mw / Mn A Within the aforementioned range, it is preferred in terms of reducing non-volatile substances and improving processability as a modifier. Weight-average molecular weight (Mw) and number-average molecular weight (Mn) A The ratio of Mw / Mn A The value can be obtained using the method described in the examples.

[0023] <Requirements (A4)> The passage relative to ethylene-α-olefin copolymer (A) 13 Assuming the sum of 100% of the integrated intensities of the signals from the vinyl terminus, vinylidene terminus, disubstituted olefin terminus, trisubstituted olefin terminus, and saturated terminus obtained by C-NMR, the content of the vinyl terminus is greater than 60%, preferably greater than 60% and less than 100%, more preferably greater than 60% and less than 95%, further preferably greater than 60% and less than 90%, particularly preferably greater than 60% and less than 85%, and particularly further preferably more than 61% and less than 77%. If the content of the vinyl terminus is within the aforementioned range, a higher content of highly reactive vinyl terminus is preferred, thus improving the reaction efficiency of the macromonomer. The content of the vinyl terminus, vinylidene terminus, disubstituted olefin terminus, trisubstituted olefin terminus, and saturated terminus can be determined by the method described in the examples.

[0024] An embodiment of the present invention relates to an ethylene-α-olefin copolymer (A) that preferably satisfies at least one of the following requirements (A5) to (A6).

[0025] <Requirements (A5)> The passage relative to ethylene-α-olefin copolymer (A) 1 Assuming the sum of 100% of the integrated intensities of the signals from the vinyl-terminal, vinylene-terminal, disubstituted olefin-terminal, and trisubstituted olefin-terminal obtained by H-NMR, the content of the vinyl-terminal is greater than 70%, preferably greater than 70% and less than 100%, more preferably greater than 70% and less than 95%, further preferably greater than 70% and less than 90%, particularly preferably more than 75% and less than 85%, and particularly even more preferably more than 77% and less than 81%. If the content of the vinyl-terminal is within the aforementioned range, a higher content of highly reactive vinyl-terminals is preferred, thus improving the reaction efficiency of the macromonomer. The content of the vinyl-terminal, vinylene-terminal, disubstituted olefin-terminal, and trisubstituted olefin-terminal can be determined by the method described in the examples.

[0026] <Requirements (A6)> The passage of ethylene-α-olefin copolymer (A) 1 Number-average molecular weight (Mn) obtained by H-NMR B ) and the number-average molecular weight (Mn) measured by gel permeation chromatography (GPC) A The ratio of Mn B / Mn AThe number average molecular weight (Mn) is 0.50 to 1.4, 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 The ratio of Mn B / Mn A Within the aforementioned range, fewer saturated terminals and a higher content of unsaturated terminals make it preferable for improving the reaction efficiency of macromonomers. Number-average molecular weight (Mn) B ) and number-average molecular weight (Mn) A The ratio of Mn B / Mn A The value can be obtained using the method described in the examples.

[0027] <Method for manufacturing ethylene-α-olefin copolymer (A)> The method for manufacturing ethylene-α-olefin copolymer (A) is not particularly limited. For example, it can be manufactured by copolymerizing ethylene with at least one of α-olefins having 3 to 10 carbon atoms in the presence of a catalyst for olefin polymerization. Preferably, it includes a step of polymerizing the 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].

[0028] The polymerization temperature is preferably 60~130°C, more preferably 65~125°C, even more preferably 70~120°C, and particularly preferably 70~115°C. If the polymerization temperature is within the aforementioned range, it is preferable that the molecular weight of the resulting polymer can be controlled within the range described in requirement (A2).

[0029] As an activator, for example, at least one compound (b) selected from organometallic compounds (b-1), organoaluminum oxide compounds (b-2), and compounds (b-3) that can react with formula [1] to form ion pairs can be cited.

[0030] As organometallic compounds (b-1) (but excluding organoaluminum oxide compounds (b-2)), examples include trialkylaluminum, triethylaluminum, triisobutylaluminum, tri-n-octylaluminum, trialkylaluminum, tricycloalkylaluminum, isobutylaluminum dichloride, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, methylaluminum dichloride, dimethylaluminum chloride, diisobutylaluminum hydrogenate, and other organoaluminum compounds.

[0031] As organoaluminum oxides (b-2), examples include previously known aluminum oxides.

[0032] As compounds (b-3) that can react with formula [1] to form ion pairs, examples include Lewis acids, ionic compounds, borane compounds and carborane compounds described in Japanese Patent Application Publications No. 1-501950, 1-502036, 3-179005, 3-179006, 3-207703, 3-207704, US Patent No. 5321106, International Publication No. 2015 / 122415, etc.

[0033] [Chemical Formula 2] In formula [1], X is independently selected from groups consisting of hydrogen atoms, monovalent hydrocarbon groups with 1 to 20 carbon atoms, halogen atoms, and combinations thereof, which can form fused rings or part of a ring system. R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 and R 12 Each is independently a hydrogen atom or a monovalent hydrocarbon group with 1 to 20 carbon atoms. Q is at least one crosslinking group selected from the group consisting of divalent hydrocarbon groups, methylene silyl groups, and methylene germanyl groups having 1 to 20 carbon atoms. If Q includes methylene silyl or methylene germanyl groups, it may have hydrocarbon groups having 1 to 20 carbon atoms.

[0034] X Examples of monovalent hydrocarbon groups with 1 to 20 carbon atoms include methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl, isopropyl, sec-butyl, tert-butyl, isobutyl, isopentyl, neopentyl, tert-pentyl, allyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclooctenyl, norbornyl, bicyclo[2.2.2]octane-1-yl, 1-adamantyl, 2-adamantyl, benzyl, diphenylmethyl, cumyl, 1, 1-Diphenylethyl, triphenylmethyl, 2-phenylethyl, 3-phenylpropyl, cinnamyl, phenyl, tolyl, xylyl, mesitylelel, cumenyl, 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 4-tert-butylphenyl, 3,5-di-tert-butylphenyl, 4-adamantylphenyl, naphthyl, biphenyl, terphenyl, binatyl, phenanthryl, anthracene, ferrocene, vinyl, allyl, propenyl, isopropenyl, butenyl, hexenyl, cyclohexenyl, octenyl, etc.

[0035] Among the monovalent hydrocarbon groups having 1 to 20 carbon atoms, methyl, ethyl, 1-propyl, 1-butyl, 1-pentyl, 1-hexyl, 1-heptyl, 1-octyl, isopropyl, sec-butyl, tert-butyl, isobutyl, isopentyl, neopentyl, and tert-pentyl are preferred, with methyl being more preferred.

[0036] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine, with chlorine being preferred.

[0037] R1~R 12 》 Examples of monovalent hydrocarbon groups with 1 to 20 carbon atoms include the aforementioned monovalent hydrocarbon groups, preferably monovalent hydrocarbon groups with 1 to 10 carbon atoms, and more preferably monovalent hydrocarbon groups with 1 to 8 carbon atoms.

[0038] Examples of monovalent hydrocarbon groups with 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.

[0039] The aforementioned R1 and R7 are each preferably alkyl groups such as methyl, ethyl, 1-propyl, isopropyl, 1-butyl, isobutyl, tert-butyl, 1-pentyl, neopentyl, 1-hexyl, cyclohexyl, and 1-octyl, more preferably methyl, ethyl, 1-propyl, isopropyl, 1-butyl, isobutyl, and tert-butyl, further preferably methyl, ethyl, 1-propyl, and isopropyl, and particularly preferably methyl.

[0040] The aforementioned R2 and R8 are each preferably hydrogen atoms, methyl, ethyl, 1-propyl, isopropyl, 1-butyl, isobutyl, tert-butyl, 1-pentyl, neopentyl, 1-hexyl, cyclohexyl, octyl, more preferably hydrogen atoms, methyl, ethyl, 1-propyl, isopropyl, 1-butyl, isobutyl, tert-butyl, further preferably hydrogen atoms, methyl, ethyl, 1-propyl, isopropyl, particularly preferably hydrogen atoms, 1-propyl.

[0041] The aforementioned R3 and R9 are each preferably hydrogen atoms, methyl, ethyl, 1-propyl, isopropyl, 1-butyl, isobutyl, tert-butyl, 1-pentyl, neopentyl, 1-hexyl, cyclohexyl, 1-octyl, phenyl, tolyl, or xylyl; more preferably hydrogen atoms, methyl, ethyl, 1-propyl, isopropyl, 1-butyl, isobutyl, tert-butyl, hydrogen atoms, methyl, ethyl, propyl, isopropyl, 1-butyl, isobutyl, tert-butyl, phenyl, tolyl, or xylyl; even more preferably hydrogen atoms, methyl, ethyl, 1-propyl, isopropyl, phenyl, tolyl, or xylyl; and particularly preferably hydrogen atoms or phenyl.

[0042] The aforementioned R4, R5, R6, R 10 R 11 and R 12 Each of the following is preferably an alkyl group, such as hydrogen atom, methyl, ethyl, 1-propyl, isopropyl, 1-butyl, isobutyl, tert-butyl, 1-pentyl, neopentyl, 1-hexyl, cyclohexyl, or 1-octyl; more preferably, hydrogen atom, methyl, ethyl, 1-propyl, isopropyl, 1-butyl, isobutyl, or tert-butyl; even more preferably, hydrogen atom, methyl, ethyl, 1-propyl, or isopropyl; and particularly preferably, hydrogen atom.

[0043] Q Examples of divalent hydrocarbon groups with 1 to 20 carbon atoms include methylene, vinyl, propenyl, phenylene, and naphthylene.

[0044] Examples of methylene silyl groups having 1 to 20 carbon atoms include methyl methylene silyl, dimethyl methylene silyl, diethyl methylene silyl, diisopropyl methylene silyl, di(cyclohexyl) methylene silyl, methyl(phenyl) methylene silyl, diphenyl methylene silyl, trimethylmethylene methylene, etc.

[0045] Examples of methylene germanyl groups having a hydrocarbon group having 1 to 20 carbon atoms include methyl methylene germanyl, dimethyl methylene germanyl, diethyl methylene germanyl, diisopropyl methylene germanyl, di(cyclohexyl) methylene germanyl, methyl(phenyl) methylene germanyl, diphenyl methylene germanyl, and trimethylgermylmethylene.

[0046] Of the aforementioned Q, methylene silane is preferred, having a hydrocarbon group having 1 to 20 carbon atoms, and dimethyl methylene silane is more preferred.

[0047] Examples of metallocene compounds represented by the aforementioned general formula [1] include, for example, dimethylsilyl bis(2-methyl-4-phenylindenyl) hafnium chloride and dimethylsilyl bis(2-methyl-3-propylindenyl) hafnium chloride.

[0048] The polymerization pressure is typically atmospheric pressure to 10 MPa gauge pressure, preferably atmospheric pressure to 8 MPa gauge pressure, more preferably atmospheric pressure to 6 MPa gauge pressure, even more preferably atmospheric pressure to 4 MPa gauge pressure, and particularly preferably atmospheric pressure to 2 MPa gauge pressure. Copolymerization can be carried out in any of the following methods: batch, semi-continuous, or continuous.

[0049] The reaction time (mean residence time when copolymerization is carried out by a continuous method) varies depending on factors such as catalyst concentration and polymerization temperature, and can be appropriately selected. It is typically 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 hours. Polymerization can also be carried out in two or more stages with different reaction conditions.

[0050] The molecular weight of the resulting ethylene-α-olefin copolymer (A) can also be adjusted by changing the hydrogen concentration and polymerization temperature in the polymerization system. Additionally, it can be adjusted by the amount of catalyst used. When adding hydrogen to the polymerization system, an amount of approximately 0.001 to 5,000 NL relative to the amount of ethylene-α-olefin copolymer produced per kg is appropriate.

[0051] The amount of terminal unsaturation in the obtained ethylene-α-olefin copolymer (A) can be increased by minimizing the amount of hydrogen added.

[0052] The metallocene compounds represented by the aforementioned general formula [1] can be used alone or in combination of two or more.

[0053] <Uses> Ethylene-α-olefin copolymer (A) can be used in applications such as macromonomers, coatings, primers, modifiers, and coating materials.

[0054] As a macromolecular monomer, it can be used, for example, in the manufacture of modified copolymers such as graft copolymers.

[0055] Examples of coatings include lacquer types, urethane types, acrylic types, alkyd types, epoxy types, and polyester types.

[0056] Examples of primers include thermoplastic polyolefin resins, thermoplastic polyurethane resins / urea resins, and thermosetting polyester resins / melamine resins / epoxy resins.

[0057] Examples of modifiers include lubricating oil modifiers and surface modifiers.

[0058] Examples of coating materials include fluorine-based and silicone-based materials.

[0059] [Example] The following describes one embodiment of the present invention in more detail based on examples, but the present invention is not limited to these examples.

[0060] <GPC-based weight-average molecular weight (Mw) and number-average molecular weight (Mn) 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 The value can be obtained using the following method.

[0061] [Sample pretreatment] 30 mg of the resin prepared 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 as the analytical sample.

[0062] [GPC Analysis] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) were calculated using gel permeation chromatography (GPC) in the form of polystyrene molecular weight conversion. A The molecular weight distribution curve was obtained. Based on the calculated weight-average molecular weight (Mw) and number-average molecular weight (Mn)... A Calculate the molecular weight distribution (Mw / Mn) A ).

[0063] [Measurement conditions] Apparatus used for analysis: Gel permeation chromatograph HLC-8321 GPC / HT (manufactured by TOSOH). Analysis device: Empower2 data processing software (Waters Corporation, registered trademark) Chromatographic columns: 2 TSKgel GMH6-HT columns and 2 TSKgel GMH6-HTL columns (all 7.5 mm in diameter × 30 cm in length, TOSOH). Column temperature: 140℃ 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) Molecular weight conversion: PS conversion / standard conversion method <Structural Analysis of Polymers> The polymer of the resin described in the examples is obtained by... 13 C-NMR and 1 The structure was analyzed by H-NMR as follows.

[0064] 《 13 C-NMR [Measurement conditions] Measurement apparatus: Bruker BioSpin AVANCE 3 cryo-500 nuclear magnetic resonance spectrometer Measurement nucleus: 13 C (125MHz) Measurement mode: Single-pulse proton broadband decoupling Pulse width: 45° (5.00μs) Points: 64k Measurement range: 250ppm (-55~195ppm) Repeat time: 29.0 seconds Total number of times: 128 Determination solvent: o-dichlorobenzene / benzene-d6 (4 / 1v / v) Sample concentration: ca. 100 mg / 0.6 mL Measurement temperature: 120℃, window function: exponential (BF: 1.0Hz) Chemical shift reference: δδ signal (29.73 ppm) [Calculation of the content of vinyl terminals in all terminals] After the above 13 In the C-NMR spectra obtained, vinyl terminals, vinylidene terminals, disubstituted olefin terminals, trisubstituted olefin terminals, and saturated terminals were observed. The content of vinyl terminals among all terminals was calculated based on the integrated intensity of each signal.

[0065] [Chemical Formula 3] In each formula, the dashed line represents the bond with atoms other than hydrogen atoms.

[0066] Peaks for carbon atoms a~e were observed in the vicinity of the following locations.

[0067] • Peaks for carbon atoms a and a': 115 ppm • Peak of carbon atom b: 110 ppm • Peak for carbon atom C: 130 ppm • Peak for carbon atom d: 132 ppm • Peak of carbon atom electron: 23 ppm • Peak of carbon atom e'~e'''': 12ppm The quantitative formula for the content of vinyl ends in all the ends is as follows.

[0068] The percentage of vinyl terminals in all terminals (%) = 100 × {integral intensity of signal a + integral intensity of signal a' / [{integral intensity of signal a + integral intensity of signal a' + integral intensity of signal b + (integral intensity of signal c / 2) + integral intensity of signal d + (integral intensity of signal e / 2) + integral intensity of signal e' + integral intensity of signal e'' + integral intensity of signal e''' + integral intensity of signal e''''} / 2]} 《 1 H-NMR [Measurement conditions] Measurement apparatus: JEOL ECX400P nuclear magnetic resonance spectrometer Measurement nucleus: 1 H (400MHz) Measurement mode: Single pulse Pulse width: 45° (5.25μs) Points: 32k Measurement range: 20 ppm (-4 to 16 ppm) Repeat time: 7.0 seconds Total number of times: 64 Solvent for determination: o-dichlorobenzene-d4 Sample concentration: ca. 20 mg / 0.6 mL Measurement temperature: 120℃ Window function: Exponential (BF: 0.12Hz) Chemical shift reference: o-dichlorobenzene (7.1 ppm).

[0069] [Calculation of ethylene and propylene content] After the above 1 In the 1H-NMR spectrum, ethylene and propylene units were observed in the main chain. The ethylene and propylene contents were calculated based on the integrated intensity of each signal.

[0070] [Chemical Formula 4] In each formula, the dashed line represents the bond with atoms other than hydrogen atoms.

[0071] Peaks for each hydrogen atom from α to γ ​​were observed in the range described below.

[0072] • Peak of hydrogen α atom: 0.95ppm~1.4ppm • Peak of hydrogen atom β: 0.95ppm~1.4ppm • Peak of hydrogen atom γ: 1.4ppm~1.7ppm Furthermore, since the peaks of α and β cannot be distinguished, the peak of γ is used to calculate the integral intensity of α.

[0073] The quantitative formulas for ethylene and propylene content are as follows.

[0074] Ethylene content (mol%) = 100 × [(integral intensity of signal: α + integral intensity of signal: β - 2 × integral intensity of signal: γ) / 4] / {[(integral intensity of signal: α + integral intensity of signal: β - 2 × integral intensity of signal: γ) / 4] + integral intensity of signal: γ} Propylene content (mol%) = 100 × integrated intensity of signal: γ / {[(integral intensity of signal: α + integrated intensity of signal: β - 2 × integrated intensity of signal: γ) / 4] + integrated intensity of signal: γ} [Calculation of the content of vinyl terminals in unsaturated terminals] After the above 1 The 1H-NMR spectra observed included vinyl terminals, vinylidene terminals, disubstituted olefin terminals, and trisubstituted olefin terminals. It should be noted that, unlike... 13 C-NMR, 1 In H-NMR measurements, it is impossible to distinguish the saturated ends from the ethylene and propylene units in the main chain. The content of vinyl ends in the unsaturated ends is calculated based on the integrated intensity of each signal.

[0075] [Chemical Formula 5] In each formula, the dashed line represents the bond with atoms other than hydrogen atoms.

[0076] Peaks I to IV of each hydrogen atom were observed in the vicinity of the following locations.

[0077] • 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 at carbon atom III: 5.3 ppm • Peak at carbon atom IV: 4.9 ppm Furthermore, since the peaks of IV and I' cannot be distinguished, the peak of I is used to calculate the integral intensity of IV.

[0078] The quantitative formula for the content of vinyl ends in unsaturated terminals is as follows.

[0079] The percentage of vinyl terminals in the unsaturated terminals (%) = 100 × the integral intensity of signal I / [the integral intensity of signal I + (the integral intensity of signal II / 2) + (the integral intensity of signal III / 2) + (the integral intensity of signal I' + the integral intensity of signal IV - the integral intensity of signal I × 2)] 〔pass 1 Number-average molecular weight (Mn) obtained by H-NMR B ) Assuming each chain has one unsaturated group, through 1 ¹H-NMR calculations were performed. The degree of polymerization of the ethylene and propylene units in the main chain was calculated based on the integrated intensity of each signal attributed to the ethylene and propylene units in the main chain, and the integrated intensity of each signal attributed to all unsaturated ends. The molecular weight was calculated by multiplying each degree of polymerization by the molecular weights of the ethylene and propylene units, i.e., 28 and 42, respectively.

[0080] The degree of polymerization of the ethylene unit = [(integral intensity of signal α + integral intensity of signal β - 2 × integral 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' + integral intensity of signal IV - integral intensity of signal I × 2)] The degree of polymerization of the propylene unit = the integral intensity of signal γ / [the integral intensity of signal I + (the integral intensity of signal II / 2) + (the integral intensity of signal III / 2) + (the integral intensity of signal I' + the integral intensity of signal IV - the integral intensity of signal I × 2)] 〔pass 1 Number-average molecular weight (Mn) obtained by H-NMR B ) and the number-average molecular weight (Mn) obtained by GPC A The ratio of Mn B / Mn A ) use 1 The number-average molecular weight (Mn) was determined by H-NMR. B The number-average molecular weight (Mn) was calculated using gel permeation chromatography (GPC) in the form of polystyrene molecular weight conversion. A Based on the calculated number-average molecular weight (Mn) B ) and number-average molecular weight (Mn) A ), calculation through 1 Number-average molecular weight (Mn) obtained by H-NMR B ) and the number-average molecular weight (Mn) obtained by GPC A The ratio of Mn B / Mn A ).

[0081] Due to the passage 1 Number-average molecular weight (Mn) obtained by H-NMR B The saturation ends were not considered, therefore the molecular weight was overestimated. Therefore, if... 1 Number-average molecular weight (Mn) obtained by H-NMR B) and the number-average molecular weight (Mn) obtained by GPC A The ratio of Mn B / Mn A If the value increases, it indicates the presence of more saturated terminals.

[0082] [Example 1] The dimethylsilyl bis(2-methyl-4-phenylindene) hafnium dichloride used as a catalyst was synthesized by a known method.

[0083] 250 mL of xylene was added to a 500 mL glass reactor that had undergone nitrogen replacement. The reactor was kept at 110 °C. While stirring the inside of the polymerizer at 600 rpm, ethylene and propylene were continuously supplied at 120 L / h and 54 L / h, respectively, to saturate the liquid and gas phases. Under a continuous supply of ethylene and propylene, 1.0 mL (1.0 mmol) of a toluene solution of triisobutylaluminum (1.0 mol / L) and 2.5 mL (0.005 mmol) of a toluene solution of dimethylsilyl bis(2-methyl-4-phenylindenyl) hafnium dichloride (0.002 mol / L) were added, followed by 2.0 mL (0.020 mmol) of a toluene solution of triphenylcarbenium tetrakis(pentafluorophenyl)borate (hereinafter also referred to as Ph3CB(C6F5)4). Polymerization was carried out at 110 °C for 16 minutes under normal pressure. The polymerization was stopped by adding a small amount of isobutanol. The resulting polymerization reaction solution was washed with dilute hydrochloric acid, and the solvent of the separated organic layer was removed by vacuum distillation, thereby obtaining the ethylene-propylene copolymer. The copolymer was dried under reduced pressure at 130 °C for 10 hours to obtain 0.66 g. Regarding the obtained copolymer, Mw=2650, Mn A =1160, Mw / Mn A =2.28, ethylene content = 49 mol%, propylene content = 51 mol%, through 13 The vinyl end content of the combined unsaturated and saturated ends, as determined by C-NMR, was 77%. The properties of the resulting copolymer are shown in Table 1.

[0084] [Example 2] 500 ml of xylene was added to a 1.0 L glass reactor. Ethylene was added at a rate of 78 L / h, and propylene at a rate of 44 L / h. Nitrogen was continuously supplied at a rate of 52 L / h to saturate both the liquid and gas phases. A 1.0 mol / L solution of triisobutylaluminum in toluene was added to 0.10 mL (0.10 mmol). Polymerization was then carried out in the same manner as in Example 1 to obtain 8.45 g of ethylene-propylene copolymer. Regarding the obtained copolymer, Mw = 3850, Mn... A =1280, Mw / Mn A =3.01, Ethylene content = 50 mol%, Propylene content = 50 mol%, through 13 The vinyl end content of the combined unsaturated and saturated ends, as determined by C-NMR, was 63%. The properties of the resulting copolymer are shown in Table 1.

[0085] [Example 3] 1.0 mL (0.010 mmol) of a toluene solution (10 mmol / L) of triphenylcarbazide tetra(pentafluorophenyl)borate was added, and polymerization was carried out at 115 °C for 16 minutes under normal pressure. Otherwise, polymerization was performed in the same manner as in Example 2, yielding 4.49 g of ethylene-propylene copolymer. For the obtained copolymer, Mw = 2870, Mn... A =1140, Mw / Mn A =2.52, ethylene content = 45 mol%, propylene content = 55 mol%, through 13 The vinyl end content of the combined unsaturated and saturated ends, as determined by C-NMR, was 65%. The properties of the resulting copolymer are shown in Table 1.

[0086] [Example 4] The dimethylsilyl bis(2-methyl-3-propylindene) hafnium dichloride used as a catalyst was synthesized using the example described in Japanese Patent Publication No. 2014-513735 and the method described in Brant, P. Organometallics 2016, 35, 2836-2839. 250 mL of xylene was added to a 500 mL glass reactor, which was then maintained at 100 °C. While stirring the polymerizer at 600 rpm, ethylene and propylene were continuously supplied at 48 L / h and 84 L / h, respectively, to saturate the liquid and gas phases. Under continuous ethylene and propylene supply, 0.10 mL (0.10 mmol) of a toluene solution of triisobutylaluminum (1.0 mol / L) and 1 mL (0.002 mmol) of a toluene solution of dimethylsilylbis(2-methyl-3-propylindene) hafnium dichloride (0.002 mol / L) were added, followed by 0.8 mL (0.008 mmol) of a toluene solution of triphenylcarbium tetra(pentafluorophenyl)borate (10 mmol / L). Polymerization was carried out at 100 °C for 10 minutes under normal pressure. Polymerization was stopped by adding a small amount of isobutanol. The resulting polymerization solution was washed with dilute hydrochloric acid, and the solvent of the separated organic layer was removed by vacuum distillation, thereby obtaining the ethylene-propylene copolymer. The copolymer was dried under reduced pressure at 130 °C for 10 hours, yielding 3.62 g. For the obtained copolymer, Mw = 755, Mn... A =418, Mw / Mn A =1.81, ethylene content = 53 mol%, propylene content = 47 mol%, through 13 The vinyl end content of the combined unsaturated and saturated ends, as determined by C-NMR, was 61%. The properties of the resulting copolymer are shown in Table 1.

[0087] [Example 5] 250 mL of toluene was added to a 500 mL glass reactor, and the reactor was maintained at 70 °C. While stirring the reactor at 600 rpm, ethylene was continuously fed at 54 L / h and propylene at 78 L / h. The polymerization time was set to 25 minutes. Otherwise, polymerization was carried out in the same manner as in Example 4, yielding 16.1 g of ethylene-propylene copolymer. Regarding the obtained copolymer, Mw = 5970, Mn... A =1980, Mw / Mn A =3.02, Ethylene content = 55 mol%, Propylene content = 45 mol%, through 13 The vinyl terminus content in all the ends after merging the unsaturated and saturated ends, as determined by C-NMR, was 64%. The properties of the resulting copolymer are shown in Table 1.

[0088] [Comparative Example 1] 1.0 L of toluene was added to a 2.0 L glass reactor, 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 dimethylsilyl bis(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 triphenylcarbium tetra(pentafluorophenyl)borate (10 mmol / L). Polymerization was carried out at 90 °C for 16 min under normal pressure. Otherwise, polymerization was carried out in the same manner as in Example 1 to obtain 24.0 g of ethylene-propylene copolymer. For the obtained copolymer, Mw = 18200, Mn... A =5270, Mw / Mn A =3.45, ethylene content = 46 mol%, propylene content = 54 mol%, through 13 The vinyl end content of the combined unsaturated and saturated ends, as determined by C-NMR, was 40%. The properties of the resulting copolymer are shown in Table 1.

[0089] [Comparative Example 2] 300 mL of toluene was added to a 500 mL glass reactor, and the reactor was maintained at 50 °C. While stirring the polymerizer at 600 rpm, ethylene and propylene were continuously supplied at 9.9 L / h and 98.4 L / h, respectively, until the liquid and gas phases were saturated. 5.0 mL (5.0 mmol) of a toluene solution (1.00 mol / L) of modified methylaluminoxane (hereinafter, MMAO) prepared by Tosoh Finechem Corporation was added, followed by 2.5 mL (0.005 mmol) of a toluene solution (0.002 mol / L) of bis(cyclopentadienyl)zirconium(IV) dichloride prepared by FUJIFILMWako Pure Chemical Corporation. Polymerization was carried out at 50 °C for 30 minutes under normal pressure. The polymerization was stopped by adding a small amount of isobutanol. The resulting polymerization solution was washed with dilute hydrochloric acid, and the solvent in the separated organic layer was removed by vacuum distillation, thus obtaining the ethylene-propylene copolymer. The copolymer was dried under reduced pressure at 130°C for 10 hours, yielding 1.83 g. Regarding the obtained copolymer, Mw = 3030, Mn... A =1140, Mw / Mn A =2.66, ethylene content = 49 mol%, propylene content = 51 mol%, through 13 The content of vinyl ends after the merging of unsaturated and saturated ends, as determined by C-NMR, was 0%. The properties of the obtained copolymer are shown in Table 1.

[0090] [Table 1]

Claims

1. An ethylene-α-olefin copolymer (A), having structural units (i) derived from ethylene and structural units (ii) derived from α-olefins having 3 to 10 carbon atoms, and satisfying the following requirements (A1) to (A4): (A1) Relative to a total content of 100 mol% of the structural unit (i) and the structural unit (ii), the content of the structural unit (i) is 30-70 mol%, and the content of the structural unit (ii) is 30-70 mol%. (A2) The number-average molecular weight (Mn) was determined by gel permeation chromatography and converted using polystyrene. A The range is 300-4000; (A3) The weight-average molecular weight (Mw) and number-average molecular weight (Mn) were determined by gel permeation chromatography and converted using polystyrene. A The ratio of Mw / Mn A The value ranges from 1.0 to 5.

0. (A4) relative to passing 13 The content of vinyl terminus is greater than 60% when the sum of the integrated intensities of the signals obtained by C-NMR for vinyl terminus, vinylidene terminus, disubstituted olefin terminus, trisubstituted olefin terminus, and saturated terminus is 100%.

2. The ethylene-α-olefin copolymer (A) as described in claim 1, wherein, In requirement (A3), the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are determined by gel permeation chromatography and converted using polystyrene. A The ratio of Mw / Mn A The value ranges from 1.0 to 4.

0.

3. The ethylene-α-olefin copolymer (A) as described in claim 1, further satisfies the following requirement (A5): (A5) relative to passing 1 The content of the vinyl terminus is greater than 70% when the sum of the integrated intensities of the signals of the vinyl terminus, vinylidene terminus, disubstituted olefin terminus, and trisubstituted olefin terminus obtained by H-NMR is 100%.

4. The ethylene-α-olefin copolymer (A) as described in claim 1, further satisfies the following requirement (A6): (A6) Through 1 Number-average molecular weight (Mn) obtained by H-NMR B ) and the number-average molecular weight (Mn) determined by gel permeation chromatography A The ratio of Mn B / Mn A The value is between 0.50 and 1.

4.

5. The ethylene-α-olefin copolymer (A) according to any one of claims 1 to 4, comprising a macromonomer, coating, primer, modifier or coating material.

6. A method for manufacturing an ethylene-α-olefin copolymer (A), which is a method for obtaining the ethylene-α-olefin copolymer (A) according to any one of claims 1 to 4, said method comprising 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], [Chemical Formula 1] In formula [1], X is independently selected from groups consisting of hydrogen atoms, monovalent hydrocarbon groups with 1 to 20 carbon atoms, halogen atoms, and combinations thereof, which can form fused rings or part of a ring system. R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 and R 12 Each is independently a hydrogen atom or a monovalent hydrocarbon group with 1 to 20 carbon atoms. Q is at least one crosslinking group selected from the group consisting of divalent hydrocarbon groups, methylene silyl groups, and methylene germanyl groups having 1 to 20 carbon atoms. If Q includes methylene silyl or methylene germanyl groups, it may have hydrocarbon groups having 1 to 20 carbon atoms.

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