Catalyst for cyclic olefin copolymerization and method for producing cyclic olefin copolymer

Abstract

To provide a catalyst for cyclic olefin copolymerization.SOLUTION: A catalyst for cyclic olefin copolymerization is used in the copolymerization of a cyclic olefin and at least one of an ethylene and an α-olefin. The catalyst for cyclic olefin copolymerization includes a metallocene compound and an alkylmetalloxane compound including an alkylaluminoxane constitutional unit and an alkylgalloxane constitutional unit.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a catalyst for cyclic olefin copolymerization and a method for producing a cyclic olefin copolymer. [Background technology]

[0002] A method has been proposed in which ethylene and / or an α-olefin having 3 to 20 carbon atoms and a cyclic olefin compound are copolymerized using a non-bridged half-metallocene compound and an aluminoxane compound (see, for example, Patent Documents 1 and 2). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2000-302811 [Patent Document 2] Japanese Patent Application Laid-Open No. 2007-063409 Summary of the Invention [Problem to be solved by the invention]

[0004] An object of one aspect of the present disclosure is to provide a catalyst for cyclic olefin copolymerization and a method for producing a cyclic olefin copolymer. [Means for solving the problem]

[0005] Specific means for solving the above problems are as follows, and the present invention includes the following aspects. A first aspect is a catalyst for copolymerizing cyclic olefins, comprising a metallocene compound and an alkylmetalloxane compound containing an alkylaluminoxane structural unit and an alkylgalloxane structural unit. The catalyst for copolymerizing cyclic olefins is used for copolymerizing a cyclic olefin with at least one member selected from the group consisting of ethylene and an α-olefin.

[0006] A second aspect is a method for producing a cyclic olefin copolymer, which comprises contacting the cyclic olefin copolymerization catalyst with a cyclic olefin and at least one selected from the group consisting of ethylene and an α-olefin. [Effects of the Invention]

[0007] According to one aspect of the present disclosure, a catalyst for cyclic olefin copolymerization and a method for producing a cyclic olefin copolymer can be provided. DETAILED DESCRIPTION OF THE INVENTION

[0008] As used herein, the term "process" refers not only to an independent process but also to processes that cannot be clearly distinguished from other processes, as long as the intended purpose of the process is achieved. Furthermore, the content of each component in a composition refers to the total amount of the components present in the composition, unless otherwise specified, when the composition contains multiple substances corresponding to the component. Furthermore, the term "metallocene compound" as used herein encompasses organometallic complexes having two cyclopentadienyl anions and organometallic complexes having one cyclopentadienyl anion, i.e., so-called half-metallocene compounds. Hereinafter, embodiments of the present invention will be described in detail. However, the embodiments described below are intended to exemplify the cyclic olefin copolymerization catalyst and the method for producing a cyclic olefin copolymer, in order to embody the technical concept of the present invention. The present invention is not limited to the cyclic olefin copolymerization catalyst and the method for producing a cyclic olefin copolymer shown below.

[0009] Cyclic olefin copolymerization catalyst The catalyst for cyclic olefin copolymerization contains a metallocene compound and an alkylmetalloxane compound containing an alkylaluminoxane structural unit and an alkylgalloxane structural unit, and is used for copolymerizing a cyclic olefin with at least one olefin selected from the group consisting of ethylene and an α-olefin.

[0010] By using a metallocene compound as a main catalyst in combination with an alkylmetalloxane compound as a co-catalyst, it is possible to efficiently carry out a copolymerization reaction of a cyclic olefin with at least one of ethylene and an α-olefin.

[0011] Metallocene Compounds The catalyst for cyclic olefin copolymerization contains at least one metallocene compound. The metallocene compound has one or two cyclopentadienyl anions reacted with η 5 - is an organometallic complex having η as a ligand. Metals constituting the metallocene compound include Group 4 elements such as zirconium, titanium, and hafnium, and Group 5 elements such as vanadium, niobium, and tantalum. From the viewpoint of polymerization activity, the metal constituting the metallocene compound preferably contains at least one of zirconium and titanium, and it is also preferable that the metallocene compound is zirconocene or titanocene. 5 The -ligand is not limited to the cyclopentadienyl anion itself, but may be a cyclopentadienyl anion having a substituent, such as an indenyl anion or a pentamethylcyclopentadienyl anion. 5 The metallocene compound may be a η-ligand. 5 In addition to the -ligand, it may have a hydrogen atom or a substituent, such as a halogen atom (e.g., chlorine or bromine), an alkyl group (e.g., methyl, ethyl, or isopropyl), an aryl group (e.g., phenyl), a substituted silyl group (e.g., trimethylsilyl), or an alkoxy group (e.g., methoxy, ethoxy, or isopropoxy).

[0012] The metallocene compound may be, for example, a compound represented by the following formula (1). Cp n ML (m-n) (1)

[0013] In the formula, Cp represents a cyclopentadienyl group which may have a substituent. M represents a transition metal atom of Group 4 or Group 5. L represents at least one selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, an amide group, a diketonato group, a silyl group, and a silylalkyl group. m represents the valence of the transition metal M, and n represents 1 or 2.

[0014] Examples of the substituent in Cp include an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group (arylalkyl group) having 7 to 12 carbon atoms, an alkylaryl group having 7 to 12 carbon atoms, and an alkylsilyl group having 1 to 10 carbon atoms. Specific examples of Cp include a methylcyclopentadienyl group, an ethylcyclopentadienyl group, a phenylcyclopentadienyl group, a benzylcyclopentadienyl group, a trimethylsilylcyclopentadienyl group, a 1,2-dimethylcyclopentadienyl group, a 1,3-dimethylcyclopentadienyl group, a 1,2,3-trimethylcyclopentadienyl group, a 1,2,4-trimethylcyclopentadienyl group, a pentamethylcyclodienyl group, and an indenyl group. n is 1 or 2 and represents the coordination number of Cp. When n is 2, Cp's may be the same or different.

[0015] M represents a transition metal atom of Group 4 or 5, and specific examples include titanium, zirconium, hafnium, vanadium, niobium, and tantalum. M is preferably at least one selected from zirconium and titanium. m is the valence value of the transition metal M.

[0016] L represents at least one selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an amido group, a diketonato group, a silyl group, and a silylalkyl group. When a plurality of L's are present, they may be the same or different from each other.

[0017] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and t-butyl groups. Examples of alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, and t-butoxy groups. Examples of aryl groups include phenyl and tolyl groups, examples of aryloxy groups include phenoxy groups, and examples of aralkyl groups include benzyl groups.

[0018] Examples of the amide group include an amide group, a methylamide group, an ethylamide group, a butylamide group, an anilide group, a dimethylamide group, a diethylamide group, a trimethylsilylamide group, a trimethylsilylmethylamide group, a bis(trimethylsilyl)amide group, a bis(diphenylsilyl)amide group, etc. Examples of the silyl group and the silylalkyl group include a trimethylsilyl group, a triphenylsilyl group, a tris(trimethylsilyl)silyl group, a (trimethylsilyl)methyl group, a bis(trimethylsilyl)methyl group, etc.

[0019] The diketonato group is a bidentate ligand because coordination to the central metal M is carried out by two carbonyl groups. Specific examples of diketone compounds that can form such diketonato groups include 2,4-pentanedione, 3,5-heptanedione, 2,6-dimethyl-3,5-heptanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 3-phenyl-2,4-pentanedione, 1,3-diphenyl-1,3-propanedione, 1-phenyl-1,3-butanedione, 1,1,1,2,2,3,3-heptafluoro-7,7-dimethyl-4,6-octanedione, 1,1,1-trifluoro-2,4-pentanedione, and 1,1,1,5,5,5-hexafluoro-2,4-pentanedione.

[0020] Specific examples of the metallocene compound include those described in International Publication No. WO2010 / 055652, International Publication No. WO2004 / 081064, JP-A-3-163088, JP-A-2000-302811, etc. The metallocene compounds may be used singly or in combination of two or more.

[0021] Alkylmetalloxane Compounds The catalyst for cyclic olefin copolymerization contains at least one alkylmetalloxane compound. The alkylmetalloxane compound contains an alkylaluminoxane structural unit and an alkylgalloxane structural unit. When the alkylmetalloxane compound contains both the alkylaluminoxane structural unit and the alkylgalloxane structural unit, a copolymer containing structural units derived from a cyclic olefin can be efficiently obtained when combined with a metallocene compound. Furthermore, since the alkylmetalloxane compound has low solubility in solvents, it is expected to suppress adhesion (fouling) of the polymer obtained by copolymerization to the reactor.

[0022] The alkylaluminoxane structural unit is represented, for example, by the following partial structural formula (1), and the alkylgalloxane structural unit is represented, for example, by the following partial structural formula (2).

[0023] [ka]

[0024] In the formula, R 1 and R 2 R each independently represents an alkyl group having 1 to 6 carbon atoms. 1 or R 2The alkyl group represented by the formula (I) may be either linear or branched. The alkyl group may also have a ring structure. Specific examples of alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, propyl, isopropyl, cyclopropyl, butyl, sec-butyl, tert-butyl, cyclobutyl, cyclopropylmethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, cyclopentyl, cyclopropylethyl, hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, and cyclohexyl. R 1 or R 2 The alkyl group preferably has 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms, from the viewpoint of polymerization activity.

[0025] The alkylmetalloxane compound may contain the alkylaluminoxane structural unit and the alkylgalloxane structural unit in a block structure or randomly. The alkylaluminoxane structural unit and the alkylgalloxane structural unit constituting the alkylmetalloxane compound may each be of only one type, or may be a combination of two or more types. When the alkylaluminoxane structural unit or the alkylgalloxane structural unit is a combination of two or more types, for example, alkylaluminoxane structural units or alkylgalloxane structural units having different alkyl groups can be combined.

[0026] In the alkylmetalloxane compound, the ratio of the total number of alkylgalloxane structural units to the total number of alkylaluminoxane structural units contained therein is, from the viewpoint of polymerization activity, for example, 0.001 or more, preferably 0.002 or more, more preferably 0.003 or more, and even more preferably 0.005 or more, and for example, 1.7 or less, preferably 1.1 or less, more preferably 0.7 or less, and even more preferably 0.5 or less. The ratio of the number of alkylgalloxane structural units to the number of alkylaluminoxane structural units in the alkylmetalloxane compound is not limited to the above and may be appropriately selected depending on the purpose, etc.

[0027] From the viewpoint of polymerization activity, the gallium content in the alkylmetalloxane compound is, for example, 0.05% by weight or more, preferably 0.1% by weight or more, more preferably 0.2% by weight or more, and for example, 61% by weight or less, preferably 40% by weight or less, more preferably 30% by weight or less. From the viewpoint of polymerization activity, the aluminum content in the alkylmetalloxane compound is, for example, 14% by weight or more, preferably 18% by weight or more, more preferably 20% by weight or more, and for example, 43% by weight or less, preferably 40% by weight or less, more preferably 38% by weight or less.

[0028] The alkylmetalloxane compound may further contain other alkylmetalloxane structural units in addition to the alkylaluminoxane structural unit and the alkylgalloxane structural unit, such as an alkylboroxane structural unit.

[0029] The presence of alkyl groups in alkylmetalloxane compounds can be confirmed by, for example, proton nuclear magnetic resonance (NMR) spectroscopy. The presence of aluminoxane structures and galloxane structures can also be confirmed by, for example, infrared absorption (IR) spectroscopy at 600 cm -1This can be confirmed by characteristic absorption before and after the reaction. Furthermore, the gallium and aluminum contents in the alkylmetalloxane compound can be measured, for example, by inductively coupled plasma (ICP) emission spectroscopy, and the carbon and hydrogen contents can be measured using an elemental analyzer. The alkylmetalloxane compound can be synthesized by reacting trialkylgallium, trialkylaluminum, and water, but can also be efficiently produced by the production method described in JP 2019-059717 A, for example. The alkylmetalloxane compound in the cyclic olefin copolymerization catalyst may be used alone or in combination of two or more.

[0030] The molar ratio of the alkylmetalloxane compound to the metallocene compound in the catalyst for cyclic olefin copolymerization is, for example, 0.1 or more, preferably 10 or more, more preferably 100 or more, and is, for example, 100,000 or less, preferably 40,000 or less, more preferably 20,000 or less.

[0031] The catalyst for cyclic olefin copolymerization may further contain, as necessary, a compound other than the alkylmetalloxane compound that activates the metallocene compound as a co-catalyst. When the catalyst for cyclic olefin copolymerization contains compounds other than alkylmetalloxane compounds, the content of the compounds other than alkylmetalloxane compounds relative to the alkylmetalloxane compounds is, for example, 99% by weight or less, preferably 50% by weight or less, more preferably 30% by weight or less, and for example, 0.01% by weight or more, preferably 1% by weight or more, more preferably 5% by weight or more.

[0032] Examples of co-catalysts that activate metallocene compounds other than alkylmetaloxane compounds include alkylmetal compounds containing an element of Group 13. Specific examples of alkylmetal compounds containing an element of Group 13 include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisobutylaluminum, and tri-n-octylaluminum, alkylaluminum halides such as methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum chloride, and diethylaluminum chloride, trialkylgalliums such as trimethylgallium, triethylgallium, and triisobutylgallium, and boron compounds such as dimethylphenylammonium tetrakis(pentafluorophenyl)borate, trityltetrakis(pentafluorophenyl)borate, tris(pentafluorophenyl)boron, and tris(pentabromophenyl)boron.

[0033] When the catalyst for cyclic olefin copolymerization contains an alkylmetalloxane compound and an alkylmetal compound containing a Group 13 element, the content of the alkylmetalloxane compound containing a Group 13 element relative to the alkylmetalloxane compound is, for example, 99% by weight or less, preferably 50% by weight or less, more preferably 30% by weight or less, and for example, 0.01% by weight or more, preferably 1% by weight or more, more preferably 5% by weight or more.

[0034] The cyclic olefin copolymerization catalyst is used for copolymerizing a cyclic olefin with at least one olefin selected from the group consisting of ethylene and α-olefins. The cyclic olefin may be, for example, a cyclic olefin having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms. Specific examples of the cyclic olefin include cyclopentene, cyclohexene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, and 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene. The cyclic olefin may be used alone or in combination of two or more.

[0035] The α-olefin used in copolymerization with the cyclic olefin may be linear or branched. The α-olefin may be, for example, a linear or branched α-olefin having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms. Specific examples of the α-olefin include propylene, 1-butene, 2-butene, 1-pentene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 1-hexene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. The α-olefins may be used alone or in combination of two or more.

[0036] In the copolymerization reaction of a cyclic olefin with at least one of ethylene and an α-olefin using a cyclic olefin copolymerization catalyst, other polymerizable compounds may be present. Examples of the other polymerizable compounds include α,β-unsaturated carboxylic acids and their salts, α,β-unsaturated carboxylic acid esters, vinyl esters, unsaturated glycidyls, and aromatic vinyl compounds. These may be used alone or in combination of two or more.

[0037] Examples of α,β-unsaturated carboxylic acids include acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, and bicyclo[2.2.1]-5-heptene-2,3-dicarboxylic anhydride. Examples of their salts include metal salts such as lithium, sodium, potassium, zinc, magnesium, and calcium salts. Examples of α,β-unsaturated carboxylic acid esters include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, and isobutyl methacrylate. Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, and vinyl trifluoroacetate. Examples of the unsaturated glycidyl include glycidyl acrylate, glycidyl methacrylate, and monoglycidyl itaconic acid ester.

[0038] Examples of aromatic vinyl compounds include styrene, 3-phenylpropylene, α-methylstyrene, mono- or polyalkylstyrenes such as o-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, and p-ethylstyrene, and functional group-containing styrene derivatives such as methoxystyrene, ethoxystyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylbenzyl acetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene, and divinylbenzene.

[0039] Method for producing cyclic olefin copolymer The method for producing a cyclic olefin copolymer includes contacting the above-mentioned cyclic olefin copolymerization catalyst with a cyclic olefin and at least one of ethylene and an α-olefin. By using the cyclic olefin copolymerization catalyst, it is possible to efficiently produce a desired cyclic olefin copolymer. Here, the cyclic olefin copolymer refers to a copolymer containing structural units derived from a cyclic olefin and structural units derived from at least one of ethylene and an α-olefin.

[0040] The cyclic olefin copolymer can be produced by contacting a cyclic olefin copolymerization catalyst containing an alkylmetalloxane compound and a metallocene compound with an olefin mixture containing a desired cyclic olefin and at least one of ethylene and an α-olefin. Alternatively, the cyclic olefin copolymer may be produced by adding a metallocene compound to a mixture containing an alkylmetalloxane compound and an olefin mixture.

[0041] In the production of cyclic olefin copolymers, the amount of alkylmetalloxane compound contained in the catalyst for cyclic olefin copolymerization is, for example, 10 -7 mmol / L or more, preferably 10 -5 mmol / L or more, e.g., 10 3 mmol / L or less, preferably 10 2 The pressure during production of the cyclic olefin copolymer may be atmospheric pressure or a pressure higher than atmospheric pressure. When the copolymer is produced at atmospheric pressure or a pressure higher than atmospheric pressure, the pressure is, for example, 20 MPa or lower, preferably 10 MPa or lower.

[0042] The contact temperature between the cyclic olefin copolymerization catalyst and the olefin mixture is, for example, -50°C or higher and 200°C or lower, and preferably -20°C or higher and 100°C or lower. [Example]

[0043] The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

[0044] The analysis of alkylmetalloxane compounds was carried out by the following means. (1) Infrared absorption (IR) spectrum measurement Measurement of IR spectra by infrared spectroscopy was carried out using a Nicolet iS5 FT-IR manufactured by Thermo Fisher Scientific. (2) Gallium (Ga) and aluminum (Al) content analysis The Ga and Al contents in alkylmetalloxane compounds were determined by inductively coupled plasma (ICP) atomic emission spectroscopy. Specifically, the alkylmetalloxane compounds were hydrolyzed with hydrochloric acid, and the Ga and Al contents were measured at room temperature using an ICP atomic emission spectroscopy analyzer (SPS3100) manufactured by SII Nanotech Co., Ltd. using standard samples of Ga and Al. (3) Carbon (C) and hydrogen (H) content analysis Using an elemental analyzer (Perkin Elmer "2400II"), CH elemental analysis was carried out to calculate the contents of carbon atoms and hydrogen atoms.

[0045] The copolymers obtained in the following examples and comparative examples were analyzed by the following methods. (1)NMR measurement The NMR spectrum was measured using a Varian NMR (600 MHz) with deuterated 1,1,2,2-tetrachloroethane, with the solvent peak as the reference. 13 C-NMR spectra were measured using proton-gated decoupling to eliminate NOE. The comonomer content in the copolymer was determined based on the assignments in Macromolecules, Vol. 35, No. 26, 9640-9647 (2002) and Macromol. Chem. Phys., 203, 159-165 (2002). (2) Molecular weight measurement The molecular weight was determined by gel permeation chromatography (GPC) using a Tosoh HLC-8321GPC / HT column in o-dichlorobenzene as a solvent to determine the weight-average molecular weight and number-average molecular weight in terms of standard polystyrene.

[0046] Manufacturing Example 1 Synthesis of alkylmetalloxane compounds (hereinafter sometimes abbreviated as MMGO) A 300 mL four-neck flask equipped with a thermometer and a rotor, dried under reduced pressure, and purged with nitrogen, was charged with 30 mL of a toluene solution of trimethylgallium (containing 121 mmol of trimethylgallium) and 90 mL of dehydrated toluene, cooled to -5 °C, and stirred. Next, 2.28 g (127 mmol) of deoxygenated water, degassed overnight with nitrogen, was added dropwise using a syringe pump at a rate of 5.0 μL / min. Stirring was continued for 15 hours under a nitrogen atmosphere at -5 °C. The temperature was then raised to 0 °C, and 74 mL of a toluene solution of trimethylaluminum (Sigma-Aldrich) (containing 148 mmol of trimethylaluminum) was slowly added dropwise over approximately 3 hours. Stirring was continued for another 2 hours while maintaining the temperature at 0 °C. The temperature was then raised to 60 °C and the reaction was continued for 10 hours. The mixture was then filtered through a glass filter (G4), washed with dehydrated toluene and dehydrated hexane, and dried under reduced pressure for 5 hours, yielding 11.8 g of a white solid. The yield was 82% calculated as aluminum.

[0047] The obtained alkylmetalloxane compound was subjected to infrared absorption (IR) spectrum measurement. The main peaks are shown below. The elemental analysis values ​​(wt%) of the obtained alkylmetalloxane compound are also shown below. IR:2941cm -1 , 1214cm -1 , 651cm -1 Elemental analysis values: C: 31.0%, H: 6.81%, Ga: 2.4%, Al: 27.9%

[0048] Example 1 A 200 mL autoclave equipped with a thermometer and a rotor, dried under reduced pressure, and purged with nitrogen was charged with 0.281 g of MMGO (3 mmol of Ga and Al combined) obtained in Production Example 1, 20 mL of dehydrated toluene, and 7.9 mL of cyclopentene. The temperature was raised to 30 °C. After the internal temperature stabilized, 1.8 mL of a toluene solution of zirconocene dichloride (containing 0.5 μmol of zirconocene dichloride) was added. Ethylene was immediately introduced into the autoclave to purge the air with ethylene, and the pressure was increased to 0.2 MPa (gauge pressure). After polymerization for 30 minutes at 30 °C while maintaining the pressure at 0.2 MPa, the polymerization solution was poured into a mixture of hydrochloric acid and methanol, and the resulting polymer was precipitated. Drying at 60 °C under reduced pressure yielded 0.268 g of polymer. The cyclopentene content of the resulting copolymer (cyclopentene content: 0.40 mol%) was calculated by NMR analysis. The results are shown in Table 1. In the table, "-" indicates that no additive was added.

[0049] Example 2 A 200 mL autoclave equipped with a thermometer and a rotor, dried under reduced pressure, and purged with nitrogen was charged with 0.281 g of MMGO (3 mmol of Ga and Al total moles) obtained in Preparation Example 1, 18 mL of dehydrated toluene, 7.9 mL of cyclopentene, and 2.5 mL of a toluene solution of triethylgallium (TEG) (containing 0.232 mmol of triethylgallium). After heating to 30 °C and stabilizing the internal temperature, 1.8 mL of a toluene solution of zirconocene dichloride (containing 0.5 μmol of zirconocene dichloride) was added. Ethylene was immediately introduced to purify the autoclave, and the gauge pressure was increased to 0.2 MPa. After polymerization at 30 °C for 10 minutes while maintaining the pressure at 0.2 MPa, the polymerization solution was poured into a mixture of hydrochloric acid and methanol, and the resulting polymer was precipitated. Drying at 60 °C under reduced pressure yielded 1.01 g of polymer. The cyclopentene content of the resulting copolymer was calculated by NMR measurement (cyclopentene content: 1.2 mol%). The results are shown in Table 1.

[0050] Example 3 A 200 mL autoclave equipped with a thermometer and a rotor, dried under reduced pressure, and purged with nitrogen was charged with 0.281 g of MMGO (3 mmol of Ga and Al total moles) obtained in Production Example 1, 20 mL of dehydrated toluene, 7.9 mL of cyclopentene, and 0.11 mL of a toluene solution of trimethylaluminum (TMA) (containing 0.22 mmol of trimethylaluminum). After heating to 30°C and stabilizing the internal temperature, 1.8 mL of a toluene solution of zirconocene dichloride (containing 0.5 μmol of zirconocene dichloride) was added. Ethylene was immediately introduced to purify the autoclave, and the gauge pressure was increased to 0.2 MPa. After polymerization at 30°C for 10 minutes while maintaining the pressure at 0.2 MPa, the polymerization solution was poured into a mixture of hydrochloric acid and methanol, and the resulting polymer was precipitated. Drying at 60°C under reduced pressure yielded 1.05 g of polymer. The cyclopentene content of the resulting copolymer was calculated by NMR measurement (cyclopentene content: 0.96 mol%). The results are shown in Table 1.

[0051] Comparative Example 1 A 200 mL autoclave equipped with a thermometer and rotor, dried under reduced pressure, and purged with nitrogen was charged with 3.8 mL of a toluene solution of methylaluminoxane (MAO: Tosoh Finechem Corporation, TMAO-212) (3 mmol based on Al atoms), 17 mL of dehydrated toluene, and 7.9 mL of cyclopentene. The temperature was raised to 30 °C. After the internal temperature stabilized, 1.8 mL of a toluene solution of zirconocene dichloride (containing 0.5 μmol of zirconocene dichloride) was added. Ethylene was immediately introduced into the autoclave to purify the atmosphere, and the pressure was increased to 0.2 MPa (gauge pressure). After polymerization at 30 °C for 10 minutes while maintaining the pressure at 0.2 MPa, the polymerization solution was poured into a mixture of hydrochloric acid and methanol, and the resulting polymer was precipitated. Drying at 60 °C under reduced pressure yielded 0.366 g of polymer. The cyclopentene content of the resulting copolymer was calculated by NMR measurement (cyclopentene content: 3.4 mol%). The results are shown in Table 1.

[0052] Comparative Example 2 A 200 mL autoclave equipped with a thermometer and rotor, dried under reduced pressure, and purged with nitrogen was charged with 3.8 mL of a toluene solution of methylaluminoxane (MAO: Tosoh Finechem Corporation, TMAO-212) (3 mmol based on Al atoms), 13 mL of dehydrated toluene, 7.9 mL of cyclopentene, and 2.5 mL of a toluene solution of triethylgallium (TEG) (containing 0.232 mmol of triethylgallium). After heating to 30 °C and stabilizing the internal temperature, 1.8 mL of a toluene solution of zirconocene dichloride (containing 0.5 μmol of zirconocene dichloride) was added. Ethylene was immediately introduced into the autoclave to purge the interior air, and the pressure was increased to 0.2 MPa (gauge pressure). After polymerization at 30 °C for 10 minutes while maintaining the pressure at 0.2 MPa, the polymerization solution was poured into a mixture of hydrochloric acid and methanol to precipitate the resulting polymer. Drying under reduced pressure at 60°C yielded 0.276g of polymer. The cyclopentene content of the resulting copolymer was calculated by NMR measurement (cyclopentene content: 1.6 mol%). The results are shown in Table 1.

[0053] [Table 1]

[0054] From Table 1, it was confirmed that Example 1, which contained an alkylmetalloxane compound as a co-catalyst, had a higher polymerization activity for the cyclopentene copolymer than Comparative Examples 1 and 2, which contained methylaluminoxane as a co-catalyst. Furthermore, it was confirmed that Examples 2 and 3, which contained a Group 13 alkylmetal compound as a co-catalyst in addition to Example 1, further increased the polymerization activity for the cyclopentene copolymer. On the other hand, it was confirmed that Comparative Example 2, which contained a Group 13 alkylmetal compound as a co-catalyst in addition to Comparative Example 1, decreased the polymerization activity for the cyclopentene copolymer.

[0055] Example 4 A 200 mL autoclave equipped with a thermometer and a rotor, dried under reduced pressure, and purged with nitrogen was charged with 0.281 g of MMGO (3 mmol total moles of Ga and Al) obtained in Production Example 1, 19 mL of dehydrated toluene, and 7.9 mL of cyclopentene. The temperature was raised to 30 °C. After the internal temperature stabilized, 3.2 mL of a toluene solution of pentamethylcyclopentadienyltitanium trichloride (containing 0.5 μmol of pentamethylcyclopentadienyltitanium trichloride) was added. Ethylene was immediately introduced to purify the autoclave, and the gauge pressure was increased to 0.2 MPa. After polymerization at 30 °C for 30 minutes while maintaining the pressure at 0.2 MPa, the polymerization solution was poured into a mixture of hydrochloric acid and methanol, and the resulting polymer was precipitated. Drying at 60 °C under reduced pressure yielded 0.335 g of polymer. The cyclopentene content of the resulting copolymer (cyclopentene content: 22 mol%) was calculated by NMR measurement. The results are shown in Table 2. In the table, "-" indicates that no compound was added.

[0056] Example 5 A 200 mL autoclave equipped with a thermometer and a rotor, dried under reduced pressure, and purged with nitrogen was charged with 0.281 g of MMGO (3 mmol of Ga and Al combined) obtained in Production Example 1, 17 mL of dehydrated toluene, and 7.9 mL of cyclopentene. The temperature was raised to 30 °C. After the internal temperature stabilized, 4.6 mL of a toluene solution of titanocene dichloride (containing 0.5 μmol of titanocene dichloride) was added. Ethylene was immediately introduced to purify the autoclave, and the pressure was increased to 0.2 MPa (gauge pressure). After polymerization was carried out at 30 °C for 10 minutes while maintaining the pressure at 0.2 MPa, the polymerization solution was poured into a mixture of hydrochloric acid and methanol, and the resulting polymer was precipitated. Drying at 60 °C under reduced pressure yielded 0.130 g of polymer. The cyclopentene content of the resulting copolymer (0.55 mol%) was calculated by NMR analysis. The results are shown in Table 2.

[0057] Example 6 A 200 mL autoclave equipped with a thermometer and a rotor, dried under reduced pressure, and purged with nitrogen was charged with 0.281 g of MMGO (3 mmol of Ga and Al total moles) obtained in Production Example 1, 16 mL of dehydrated toluene, 7.9 mL of cyclopentene, and 2.5 mL of a toluene solution of triethylgallium (TEG) (containing 0.232 mmol of triethylgallium). After heating to 30 °C and stabilizing the internal temperature, 3.2 mL of a toluene solution of pentamethylcyclopentadienyltitanium trichloride (containing 0.5 μmol of pentamethylcyclopentadienyltitanium trichloride) was added. Ethylene was immediately introduced to purify the autoclave, and the gauge pressure was increased to 0.2 MPa. After polymerization at 30 °C for 10 minutes while maintaining the pressure at 0.2 MPa, the polymerization solution was poured into a mixture of hydrochloric acid and methanol, and the resulting polymer was precipitated. Drying under reduced pressure at 60°C yielded 0.206g of polymer. The cyclopentene content of the resulting copolymer was calculated by NMR measurement (cyclopentene content: 20 mol%). The results are shown in Table 2.

[0058] Comparative Example 3 A 200 mL autoclave equipped with a thermometer and rotor, dried under reduced pressure, and purged with nitrogen was charged with 4.0 mL of a toluene solution of methylaluminoxane (MAO: Tosoh Finechem Corporation, TMAO-212) (3 mmol based on Al atoms), 15 mL of dehydrated toluene, and 7.9 mL of cyclopentene. The temperature was raised to 30 °C. After the internal temperature stabilized, 3.2 mL of a toluene solution of pentamethylcyclopentadienyltitanium trichloride (containing 0.5 μmol of pentamethylcyclopentadienyltitanium trichloride) was added. Ethylene was immediately introduced into the autoclave to purify the atmosphere, and the pressure was increased to 0.2 MPa (gauge pressure). After polymerization at 30 °C for 10 minutes while maintaining the pressure at 0.2 MPa, the polymerization solution was poured into a mixture of hydrochloric acid and methanol, and the resulting polymer was precipitated. Drying at 60 °C under reduced pressure yielded 0.03 g of polymer. NMR analysis of the resulting copolymer revealed that it contained no cyclopentene. The results are shown in Table 2.

[0059] Comparative Example 4 A 200 mL autoclave equipped with a thermometer and rotor, dried under reduced pressure, and purged with nitrogen was charged with 4.8 mL of a toluene solution of methylaluminoxane (MAO: Tosoh Finechem Corporation, TMAO-212) (3.2 mmol based on Al atoms), 12 mL of dehydrated toluene, 7.9 mL of cyclopentene, and 2.5 mL of a toluene solution of triethylgallium (TEG) (0.232 mmol as triethylgallium). After heating to 30 °C and stabilizing the internal temperature, 3.2 mL of a toluene solution of pentamethylcyclopentadienyltitanium trichloride (0.5 μmol as pentamethylcyclopentadienyltitanium trichloride) was added. Ethylene was immediately introduced into the autoclave to purify the air inside, and the autoclave was pressurized to 0.2 MPa (gauge pressure). After carrying out the polymerization reaction at 30°C for 10 minutes while maintaining a pressure of 0.2 MPa, the polymerization solution was poured into a mixture of hydrochloric acid and methanol to precipitate the resulting polymer. Drying at 60°C under reduced pressure yielded 0.022 g of polymer. The cyclopentene content of the resulting copolymer (cyclopentene content: 0.34 mol%) was calculated by NMR measurement. The results are shown in Table 2.

[0060] [Table 2]

[0061] From Table 2, it was confirmed that in Examples 4 and 5, which contained an alkylmetalloxane compound as a co-catalyst, the polymerization activity of the cyclopentene copolymer was higher than in Comparative Examples 3 and 4, which contained methylaluminoxane as a co-catalyst. Furthermore, it was confirmed that in Example 6, by further including a Group 13 alkylmetal compound as a co-catalyst compared to Examples 4 and 5, the polymerization activity of the cyclopentene copolymer was higher. On the other hand, it was confirmed that in Comparative Example 4, by further including a Group 13 alkylmetal compound as a co-catalyst compared to Comparative Example 3, the polymerization activity of the cyclopentene copolymer was lower.

[0062] Manufacturing Example 2 Synthesis of alkylmetalloxane compounds (catalyst component H) A 200 mL four-neck flask equipped with a thermometer and a rotor, dried under reduced pressure, and purged with nitrogen, was charged with 4.3 mL of trimethylgallium (containing 43 mmol as trimethylgallium), 22 mL of a toluene solution of trimethylaluminum (Sigma-Aldrich) (containing 43 mmol as trimethylaluminum), and 60 mL of dehydrated toluene. The flask was then cooled to -5°C and stirred. Next, 0.790 g (43.9 mmol) of deoxygenated water, degassed overnight with nitrogen, was added dropwise using a syringe pump at a discharge rate of 5.0 μL / min. The mixture was stirred for 15 hours under a nitrogen atmosphere at -5°C. The temperature was then raised to room temperature and further raised to 60°C, where the mixture was reacted for 10 hours. The resulting slurry was filtered through a glass filter and dried to obtain 3.2 g of a white powder. The yield, calculated as Al, was 97%.

[0063] The main peaks in the infrared absorption (IR) spectrum of the resulting alkylmetalloxane compound and the elemental analysis data are shown below. IR:2944cm -1 , 1215cm -1 , 643cm -1 Elemental analysis values: C: 26.1%, H: 6.81%, Ga: 5.1%, Al: 34.7%

[0064] Example 7 A 200 mL autoclave equipped with a thermometer and a rotor, dried under reduced pressure, and purged with nitrogen was charged with 0.221 g of MMGO (3 mmol of Ga and Al total moles) obtained in Production Example 2, 35 mL of dehydrated toluene, and 12 mL of a solution of 2-norbornene and toluene (containing 49 mmol of 2-norbornene). The autoclave was heated to 70 °C. After the internal temperature stabilized, 3.2 mL of a toluene solution of pentamethylcyclopentadienyltitanium trichloride (containing 0.5 μmol of pentamethylcyclopentadienyltitanium trichloride) was added. Ethylene was immediately introduced to purify the autoclave with ethylene, and the gauge pressure was increased to 0.2 MPa. After polymerization at 70 °C for 30 minutes while maintaining the pressure at 0.2 MPa, the polymerization solution was poured into a mixture of hydrochloric acid and methanol, and the resulting polymer was precipitated. Drying at 60 °C under reduced pressure yielded 0.082 g of polymer. The 2-norbornene content of the resulting copolymer (2-norbornene: 11.3 mol%) was calculated by NMR measurement. The results are shown in Table 3.

[0065] Comparative Example 5 A 200 mL autoclave equipped with a thermometer and rotor, dried under reduced pressure, and purged with nitrogen was charged with 4.8 mL of a toluene solution of methylaluminoxane (MAO: Tosoh Finechem Corporation, TMAO-212) (3.0 mmol based on Al atoms), 30 mL of dehydrated toluene, and 12 mL of a 2-norbornene and toluene solution (containing 49 mmol of 2-norbornene). The temperature was raised to 70 °C. After the internal temperature stabilized, 3.2 mL of a toluene solution of pentamethylcyclopentadienyltitanium trichloride (containing 0.5 μmol of pentamethylcyclopentadienyltitanium trichloride) was added. Ethylene was immediately introduced to purge the autoclave with ethylene, and the pressure was increased to 0.2 MPa (gauge pressure). After polymerization for 30 minutes at 70 °C while maintaining the pressure at 0.2 MPa, the polymerization solution was poured into a mixture of hydrochloric acid and methanol to precipitate the resulting polymer. Drying under reduced pressure at 60°C yielded 0.020g of polymer. The 2-norbornene content of the resulting copolymer (2-norbornene; 11.4 mol%) was calculated by NMR measurement. The results are shown in Table 3.

[0066] [Table 3]

[0067] From Table 3, it was confirmed that Example 7, which contained an alkylmetalloxane compound as a co-catalyst, had a higher polymerization activity for the 2-norbornene copolymer than Comparative Example 5, which contained methylaluminoxane as a co-catalyst.

Claims

1. a metallocene compound, an alkylmetalloxane compound containing an alkylaluminoxane structural unit and an alkylgalloxane structural unit, and an alkylmetal compound containing a Group 13 element; A catalyst for cyclic olefin copolymerization used in copolymerizing a cyclic olefin with at least one of ethylene and an α-olefin.

2. The catalyst for cycloolefin copolymerization according to claim 1, wherein the metallocene compound is represented by the following formula (1): Cp ｎ ML （ｍ－ｎ） ((1) (In the formula, Cp represents a cyclopentadienyl group which may have a substituent; M represents a transition metal atom of Group 4 or Group 5; L represents at least one selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, an amide group, a diketonato group, a silyl group, and a silylalkyl group; m represents the valence of the transition metal M; and n represents 1 or 2.)

3. The catalyst for cycloolefin copolymerization according to claim 1 or 2, wherein the metallocene compound contains at least one of zirconium and titanium.

4. 4. The catalyst for cyclic olefin copolymerization according to claim 1, wherein the alkylmetalloxane compound has a ratio of the number of alkylgalloxane structural units to the number of alkylaluminoxane structural units of 0.001 or more and 1.7 or less.

5. A method for producing a cyclic olefin copolymer, comprising contacting the cyclic olefin copolymerization catalyst according to any one of claims 1 to 4 with a cyclic olefin and at least one of ethylene and an α-olefin.

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