JP7780071B2 - Catalyst for cyclic olefin copolymerization and method for producing cyclic olefin copolymer - Google Patents

Description

This disclosure relates to a catalyst for cyclic olefin copolymerization and a method for producing a cyclic olefin copolymer.

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).

Japanese Patent Application Laid-Open No. 2000-302811 JP 2007-063409 A

One aspect of the present disclosure aims to provide a catalyst for cyclic olefin copolymerization and a method for producing a cyclic olefin copolymer.

Specific means for solving the above problems are as follows, and the present invention encompasses the following aspects. The 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.

The 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 olefin selected from the group consisting of ethylene and an α-olefin.

One aspect of the present disclosure provides a catalyst for cyclic olefin copolymerization and a method for producing a cyclic olefin copolymer.

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, when multiple substances corresponding to each component are present in the composition, the content of each component refers to the total amount of those multiple substances present in the composition, unless otherwise specified. Furthermore, as used herein, "metallocene compounds" encompass organometallic complexes having two cyclopentadienyl anions and organometallic complexes having one cyclopentadienyl anion, so-called half-metallocene compounds. Embodiments of the present invention are described in detail below. 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 described below.

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

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

Metallocene Compound The cyclic olefin copolymerization catalyst includes at least one metallocene compound. The metallocene compound is an organometallic complex having one or two cyclopentadienyl anions as η ⁵ -ligands. Examples of 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 includes at least one of zirconium and titanium, and it is also preferable that the metallocene compound be zirconocene or titanocene. The η ⁵ -ligand is not limited to the cyclopentadienyl anion itself, but may also be a cyclopentadienyl anion having a substituent, such as an indenyl anion or a pentamethylcyclopentadienyl anion. Furthermore, the two η ⁵ -ligands may be linked by any linking group. The metallocene compound may have a hydrogen atom or a substituent in addition to the η ⁵ -ligand. Examples of the substituent include halogen atoms such as chlorine and bromine, alkyl groups such as methyl, ethyl and isopropyl, aryl groups such as phenyl, substituted silyl groups such as trimethylsilyl, and alkoxy groups such as methoxy, ethoxy and isopropoxy.

The metallocene compound may be, for example, a compound 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.

Examples of substituents on Cp include alkyl groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, aralkyl groups (arylalkyl groups) having 7 to 12 carbon atoms, alkylaryl groups having 7 to 12 carbon atoms, and alkylsilyl groups having 1 to 10 carbon atoms. Specific examples of Cp include methylcyclopentadienyl, ethylcyclopentadienyl, phenylcyclopentadienyl, benzylcyclopentadienyl, trimethylsilylcyclopentadienyl, 1,2-dimethylcyclopentadienyl, 1,3-dimethylcyclopentadienyl, 1,2,3-trimethylcyclopentadienyl, 1,2,4-trimethylcyclopentadienyl, pentamethylcyclodienyl, and indenyl. n is 1 or 2 and represents the coordination number of Cp. When n is 2, Cp may be the same or different.

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.

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 amide group, a diketonato group, a silyl group, and a silylalkyl group. When multiple Ls are present, they may be the same or different from each other.

Halogen atoms include fluorine, chlorine, bromine, and iodine. Alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and t-butyl groups. Alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, and t-butoxy groups. Aryl groups include phenyl and tolyl groups, aryloxy groups include phenoxy groups, and aralkyl groups include benzyl groups.

Examples of amide groups include amide, methylamide, ethylamide, butylamide, anilide, dimethylamide, diethylamide, trimethylsilylamide, trimethylsilylmethylamide, bis(trimethylsilyl)amide, and bis(diphenylsilyl)amide groups. Examples of silyl groups and silylalkyl groups include trimethylsilyl, triphenylsilyl, tris(trimethylsilyl)silyl, (trimethylsilyl)methyl, and bis(trimethylsilyl)methyl groups.

Diketonato groups are bidentate ligands because two carbonyl groups coordinate to the central metal M. 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.

Specific examples of metallocene compounds include those described in International Publication No. WO 2010/055652, International Publication No. WO 2004/081064, Japanese Patent Application Laid-Open No. H3-163088, and Japanese Patent Application Laid-Open No. 2000-302811. Metallocene compounds may be used alone or in combination of two or more.

Alkylmetalloxane Compound 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 has both an alkylaluminoxane structural unit and an 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.

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).

In the formula, ^R1 and ^R2 each independently represent an alkyl group having 1 to 6 carbon atoms. The alkyl group represented by ^R1 or ^R2 may be either linear or branched. The alkyl group may also have a ring structure. Specific examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a cyclobutyl group, a cyclopropylmethyl group, a pentyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 1,1-dimethylpropyl group, a 1,2-dimethylpropyl group, a 2,2-dimethylpropyl group, a cyclopentyl group, a cyclopropylethyl group, a hexyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, a 4-methylpentyl group, a 1,1-dimethylbutyl group, a 1,2-dimethylbutyl group, a 1,3-dimethylbutyl group, a 2,2-dimethylbutyl group, a 2,3-dimethylbutyl group, a 3,3-dimethylbutyl group, and a cyclohexyl group. The number of carbon atoms in the alkyl group of ^R1 or ^R2 is preferably 1 to 4, more preferably 1 to 3, from the viewpoint of polymerization activity.

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

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 selected appropriately depending on the purpose, etc.

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.

In addition to the alkylaluminoxane structural unit and the alkylgalloxane structural unit, the alkylmetalloxane compound may further contain other alkylmetalloxane structural units. Examples of other structural units include alkylboroxane structural units.

The presence of alkyl groups in alkylmetalloxane compounds can be confirmed, for example, by proton nuclear magnetic resonance (NMR) spectroscopy. The presence of aluminoxane and galloxane structures can be confirmed, for example, by infrared absorption (IR) spectroscopy, based on characteristic absorption around 600 cm ⁻¹ . Furthermore, the gallium and aluminum contents in alkylmetalloxane compounds can be measured, for example, by inductively coupled plasma (ICP) atomic emission spectroscopy, and the carbon and hydrogen contents can be measured using an elemental analyzer. Alkylmetalloxane compounds 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 compounds in the cyclic olefin copolymerization catalyst may be used alone or in combination of two or more.

The molar ratio of the alkylmetalloxane compound to the metallocene compound in the cyclic olefin copolymerization catalyst 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.

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.

Examples of co-catalysts that activate metallocene compounds other than alkylmetaloxane compounds include alkylmetal compounds containing a Group 13 element. Specific examples of alkylmetal compounds containing a Group 13 element 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.

When the cyclic olefin copolymerization catalyst 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, and more preferably 30% by weight or less, and for example, 0.01% by weight or more, preferably 1% by weight or more, and more preferably 5% by weight or more.

The cyclic olefin copolymerization catalyst is used to copolymerize 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.

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 α-olefins 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.

The copolymerization reaction of a cyclic olefin with at least one of ethylene and an α-olefin using a cyclic olefin copolymerization catalyst may also involve the presence of other polymerizable compounds. Examples of 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.

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 unsaturated glycidyls include glycidyl acrylate, glycidyl methacrylate, and monoglycidyl itaconic acid ester.

Examples of aromatic vinyl compounds include mono- or polyalkylstyrenes such as styrene, 3-phenylpropylene, α-methylstyrene, 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.

1. Method for Producing Cyclic Olefin Copolymer The method for producing a cyclic olefin copolymer comprises contacting the above-described 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.

Cyclic olefin copolymers can be produced by contacting a cyclic olefin copolymerization catalyst containing an alkylmetalloxane compound and a metallocene compound with an olefin mixture containing the desired cyclic olefin and at least one of ethylene and an α-olefin. Cyclic olefin copolymers can also be produced by adding a metallocene compound to a mixture containing an alkylmetalloxane compound and an olefin mixture.

In the method for producing a cyclic olefin copolymer, the amount of the alkylmetalloxane compound contained in the cyclic olefin copolymerization catalyst used is, for example, 10 ⁻⁷ mmol/L or more, preferably 10 ⁻⁵ mmol/L or more, as a concentration in a solvent, and for example, 10 ³ mmol/L or less, preferably 10 ² mmol/L or less. The pressure during production of the cyclic olefin copolymer may be atmospheric pressure or a pressure higher than atmospheric pressure. When production is performed at atmospheric pressure or a pressure higher than atmospheric pressure, the pressure is, for example, 20 MPa or less, preferably 10 MPa or less.

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.

The present invention will be explained in more detail below using examples, but the present invention is not limited to these examples.

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

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

Production Example 1
Synthesis of alkylmetalloxane compound (hereinafter sometimes abbreviated as MMGO) Equipped with a thermometer and a rotor, and the inside of a 300 mL four-necked flask was purged with nitrogen after drying under reduced pressure, 30 mL of a toluene solution of trimethylgallium (containing 121 mmol as trimethylgallium) and 90 mL of dehydrated toluene were added, cooled to -5 ° C, and stirred. Next, 2.28 g (127 mmol) of deoxygenated water degassed with nitrogen overnight was added dropwise using a syringe pump with a discharge rate adjusted to 5.0 μL / min, and stirring was continued for 15 hours under a nitrogen atmosphere at -5 ° C. Thereafter, the temperature was raised to 0 ° C, and 74 mL of a toluene solution of trimethylaluminum (manufactured by Sigma-Aldrich) (containing 148 mmol as trimethylaluminum) was slowly added dropwise over about 3 hours, and stirring was continued for another 2 hours while maintaining 0 ° C. The temperature was raised to 60 ° C, and the reaction was allowed to proceed for 10 hours. The precipitate was then filtered through a glass filter (G4), washed with dehydrated toluene and dehydrated hexane, and dried under reduced pressure for 5 hours to obtain 11.8 g of a white solid. The yield, calculated as aluminum, was 82%.

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%

Example 1
A 200 mL autoclave equipped with a thermometer and a rotor, whose interior had been purged with nitrogen after drying under reduced pressure, was charged with 0.281 g of MMGO obtained in Production Example 1 (total moles of Ga and Al: 3 mmol), 20 mL of dehydrated toluene, and 7.9 mL of cyclopentene, and heated 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 to replace the atmosphere inside the autoclave with ethylene, and the pressure was increased to 0.2 MPa (gauge pressure). After polymerization reaction at 30 ° C. for 30 minutes while maintaining a pressure of 0.2 MPa, the polymerization solution was added to a mixture of hydrochloric acid and methanol, and the resulting polymer was precipitated. After drying at 60 ° C. under reduced pressure, 0.268 g of polymer was obtained. The cyclopentene content (cyclopentene content: 0.40 mol%) of the resulting copolymer was calculated by NMR measurement. The results are shown in Table 1. In the table, "-" indicates that no additive was added.

Example 2
A 200 mL autoclave equipped with a thermometer and a rotor, the interior of which was replaced with nitrogen after drying under reduced pressure, was charged with 0.281 g of MMGO obtained in Production Example 1 (total moles of Ga and Al: 3 mmol), 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 as triethylgallium). After heating to 30 ° C., and after the internal temperature stabilized, 1.8 mL of a toluene solution of zirconocene dichloride (containing 0.5 μmol as zirconocene dichloride) was added. Ethylene was immediately introduced to replace the atmosphere inside the autoclave, and the gauge pressure was increased to 0.2 MPa. After performing a polymerization reaction at 30 ° C. for 10 minutes while maintaining a pressure of 0.2 MPa, the polymerization solution was added to a mixture of hydrochloric acid and methanol, and the resulting polymer was precipitated. After drying at 60 ° C. under reduced pressure, 1.01 g of polymer was obtained. The cyclopentene content of the resulting copolymer was calculated by NMR measurement (cyclopentene content: 1.2 mol %). The results are shown in Table 1.

Example 3
A 200 mL autoclave equipped with a thermometer and a rotor, whose interior had been purged with nitrogen after drying under reduced pressure, was charged with 0.281 g of MMGO obtained in Preparation Example 1 (total moles of Ga and Al: 3 mmol), 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 as trimethylaluminum). After heating to 30 ° C., and after the internal temperature stabilized, 1.8 mL of a toluene solution of zirconocene dichloride (containing 0.5 μmol as zirconocene dichloride) was added. Ethylene was immediately introduced to replace the atmosphere inside the autoclave, and the gauge pressure was increased to 0.2 MPa. After polymerization reaction at 30 ° C. for 10 minutes while maintaining a pressure of 0.2 MPa, the polymerization solution was added to a mixture of hydrochloric acid and methanol, and the resulting polymer was precipitated. After drying at 60 ° C. under reduced pressure, 1.05 g of polymer was obtained. The cyclopentene content of the resulting copolymer was calculated by NMR measurement (cyclopentene content: 0.96 mol%). The results are shown in Table 1.

Comparative Example 1
A 200 mL autoclave equipped with a thermometer and a rotor, which had been dried under reduced pressure and then purged with nitrogen, was charged with 3.8 mL (3 mmol based on Al atoms) of a toluene solution of methylaluminoxane (MAO: Tosoh Finechem Corporation, TMAO-212), 17 mL of dehydrated toluene, and 7.9 mL of cyclopentene, and 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 as zirconocene dichloride) was added. Ethylene was immediately introduced to replace the atmosphere inside the autoclave, and the gauge pressure was increased to 0.2 MPa. After polymerization reaction was carried out at 30°C for 10 minutes while maintaining the pressure at 0.2 MPa, the polymerization solution was poured into a mixed solution of hydrochloric acid and methanol, and the resulting polymer was precipitated. After drying at 60°C under reduced pressure, 0.366 g of polymer was obtained. The cyclopentene content of the resulting copolymer was calculated by NMR measurement (cyclopentene content: 3.4 mol%). The results are shown in Table 1.

Comparative Example 2
A 200 mL autoclave equipped with a thermometer and a rotor, which had been dried under reduced pressure and then purged with nitrogen, was charged with 3.8 mL (3 mmol based on Al atoms) of a toluene solution of methylaluminoxane (MAO: Tosoh Finechem Corporation, TMAO-212), 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 as 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 as zirconocene dichloride) was added. Ethylene was immediately introduced to replace the atmosphere inside the autoclave, and the gauge pressure was increased to 0.2 MPa. After carrying out a polymerization reaction at 30°C for 10 minutes while maintaining the pressure at 0.2 MPa, the polymerization solution was poured into a mixed solution of hydrochloric acid and methanol, and the resulting polymer was precipitated. The copolymer was dried at 60°C under reduced pressure to obtain 0.276 g of a polymer. The cyclopentene content of the copolymer was calculated by NMR measurement (cyclopentene content: 1.6 mol%). The results are shown in Table 1.

Table 1 confirms that Example 1, which contains an alkylmetalloxane compound as a cocatalyst, exhibits higher polymerization activity for cyclopentene copolymers than Comparative Examples 1 and 2, which contain methylaluminoxane as a cocatalyst. Furthermore, in Examples 2 and 3, it was confirmed that by further including a Group 13 alkylmetal compound as a cocatalyst compared to Example 1, the polymerization activity for cyclopentene copolymers was higher. On the other hand, in Comparative Example 2, it was confirmed that by further including a Group 13 alkylmetal compound as a cocatalyst compared to Comparative Example 1, the polymerization activity for cyclopentene copolymers was lower.

Example 4
A 200 mL autoclave equipped with a thermometer and a rotor, the interior of which was replaced with nitrogen after drying under reduced pressure, was charged with 0.281 g of MMGO obtained in Preparation Example 1 (total moles of Ga and Al: 3 mmol), 19 mL of dehydrated toluene, and 7.9 mL of cyclopentene, and the temperature was raised to 30 ° C. After the internal temperature stabilized, 3.2 mL of a toluene solution of pentamethylcyclopentadienyl titanium trichloride (containing 0.5 μmol of pentamethylcyclopentadienyl titanium trichloride) was added. Ethylene was immediately introduced to replace the atmosphere inside the autoclave, and the gauge pressure was increased to 0.2 MPa. After polymerization reaction at 30 ° C. for 30 minutes while maintaining a pressure of 0.2 MPa, the polymerization solution was added to a mixture of hydrochloric acid and methanol, and the resulting polymer was precipitated. After drying at 60 ° C. under reduced pressure, 0.335 g of polymer was obtained. 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 additive was added.

Example 5
A 200 mL autoclave equipped with a thermometer and a rotor, whose interior had been purged with nitrogen after drying under reduced pressure, was charged with 0.281 g of MMGO obtained in Production Example 1 (total moles of Ga and Al: 3 mmol), 17 mL of dehydrated toluene, and 7.9 mL of cyclopentene, and heated 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 replace the atmosphere inside the autoclave, and the pressure was increased to 0.2 MPa (gauge pressure). After polymerization reaction at 30 ° C. for 10 minutes while maintaining a pressure of 0.2 MPa, the polymerization solution was added to a mixture of hydrochloric acid and methanol, and the resulting polymer was precipitated. After drying at 60 ° C. under reduced pressure, 0.130 g of polymer was obtained. The cyclopentene content (cyclopentene content: 0.55 mol%) of the resulting copolymer was calculated by NMR measurement. The results are shown in Table 2.

Example 6
A 200 mL autoclave equipped with a thermometer and a rotor, and having its interior purged with nitrogen after drying under reduced pressure, was charged with 0.281 g of MMGO obtained in Preparation Example 1 (total moles of Ga and Al: 3 mmol), 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 as triethylgallium). After heating to 30 ° C., and after the internal temperature stabilized, 3.2 mL of a toluene solution of pentamethylcyclopentadienyltitanium trichloride (containing 0.5 μmol as pentamethylcyclopentadienyltitanium trichloride) was added. Ethylene was immediately introduced to replace the atmosphere in the autoclave, and the gauge pressure was increased to 0.2 MPa. After polymerization reaction for 10 minutes at 30 ° C. while maintaining a pressure of 0.2 MPa, the polymerization solution was added to a mixture of hydrochloric acid and methanol, and the resulting polymer was precipitated. The copolymer was dried under reduced pressure at 60° C. to obtain 0.206 g of a polymer. The cyclopentene content of the copolymer was calculated by NMR measurement (cyclopentene content: 20 mol%). The results are shown in Table 2.

Comparative Example 3
A 200 mL autoclave equipped with a thermometer and a rotor, which had been dried under reduced pressure and then purged with nitrogen, was charged with 4.0 mL (3 mmol based on Al atoms) of a toluene solution of methylaluminoxane (MAO: Tosoh Finechem Corporation, TMAO-212), 15 mL of dehydrated toluene, and 7.9 mL of cyclopentene, and 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 as pentamethylcyclopentadienyltitanium trichloride) was added. Ethylene was immediately introduced to replace the atmosphere inside the autoclave, and the gauge pressure was increased to 0.2 MPa. After carrying out a polymerization reaction at 30°C for 10 minutes while maintaining the pressure at 0.2 MPa, the polymerization solution was poured into a mixed solution of hydrochloric acid and methanol, and the resulting polymer was precipitated. After drying at 60°C under reduced pressure, 0.03 g of polymer was obtained. The copolymer thus obtained was found to contain no cyclopentene by NMR analysis, and the results are shown in Table 2.

Comparative Example 4
A 200 mL autoclave equipped with a thermometer and a rotor, which had been dried under reduced pressure and then purged with nitrogen, was charged with 4.8 mL (3.2 mmol based on Al atoms) of a toluene solution of methylaluminoxane (MAO: Tosoh Finechem Corporation, TMAO-212), 12 mL of dehydrated toluene, 7.9 mL of cyclopentene, and 2.5 mL of a toluene solution of triethylgallium (TEG) (containing 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 (containing 0.5 μmol as pentamethylcyclopentadienyltitanium trichloride) was added. Ethylene was immediately introduced to replace the atmosphere inside the autoclave, and the autoclave was pressurized to a gauge pressure of 0.2 MPa. 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 mixed solution of hydrochloric acid and methanol to precipitate the produced 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.

Table 2 confirms that Examples 4 and 5, which contain an alkylmetalloxane compound as a cocatalyst, have higher polymerization activity for cyclopentene copolymers than Comparative Examples 3 and 4, which contain methylaluminoxane as a cocatalyst. Furthermore, Example 6, which further contains a Group 13 alkylmetal compound as a cocatalyst compared to Examples 4 and 5, also confirmed that the polymerization activity for cyclopentene copolymers is higher. On the other hand, Comparative Example 4, which further contains a Group 13 alkylmetal compound as a cocatalyst compared to Comparative Example 3, also confirmed that the polymerization activity for cyclopentene copolymers is lower.

Production Example 2
Synthesis of alkylmetalloxane compound (catalyst component H) A 200 mL four-neck flask equipped with a thermometer and a rotor, and having its interior purged with nitrogen after drying under reduced pressure, was charged with 4.3 mL of trimethylgallium (containing 43 mmol as trimethylgallium), 22 mL of a toluene solution of trimethylaluminum (manufactured by Sigma-Aldrich) (containing 43 mmol as trimethylaluminum), and 60 mL of dehydrated toluene, 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 with a discharge rate adjusted to 5.0 μL / min, and stirring was continued for 15 hours under a nitrogen atmosphere at -5 ° C. The temperature was then raised to room temperature, further raised to 60 ° C, and the reaction was allowed to proceed 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%.

The main peaks in the infrared absorption (IR) spectrum and elemental analysis values of the resulting alkylmetalloxane compound 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%

Example 7
A 200 mL autoclave equipped with a thermometer and a rotor, the interior of which had been purged with nitrogen after drying under reduced pressure, was charged with 0.221 g of MMGO obtained in Production Example 2 (total moles of Ga and Al: 3 mmol), 35 mL of dehydrated toluene, and 12 mL of a solution of 2-norbornene and toluene (containing 49 mmol of 2-norbornene), and the temperature was raised to 70 ° C. After the internal temperature stabilized, 3.2 mL of a toluene solution of pentamethylcyclopentadienyl titanium trichloride (containing 0.5 μmol of pentamethylcyclopentadienyl titanium trichloride) was added. Ethylene was immediately introduced to replace the atmosphere inside the autoclave with ethylene, and the gauge pressure was increased to 0.2 MPa. After performing a polymerization reaction at 70 ° C. for 30 minutes while maintaining a pressure of 0.2 MPa, the polymerization solution was added to a mixture of hydrochloric acid and methanol, and the resulting polymer was precipitated. After drying at 60 ° C. under reduced pressure, 0.082 g of polymer was obtained. 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.

Comparative Example 5
A 200 mL autoclave equipped with a thermometer and a rotor, which had been dried under reduced pressure and then purged with nitrogen, was charged with 4.8 mL (3.0 mmol based on Al atoms) of a toluene solution of methylaluminoxane (MAO: Tosoh Finechem Corporation, TMAO-212), 30 mL of dehydrated toluene, and 12 mL of a solution of 2-norbornene and toluene (containing 49 mmol as 2-norbornene), and the temperature was raised to 70 ° C. After the internal temperature stabilized, 3.2 mL of a toluene solution of pentamethylcyclopentadienyl titanium trichloride (containing 0.5 μmol as pentamethylcyclopentadienyl titanium trichloride) was added. Ethylene was immediately introduced to replace the atmosphere inside the autoclave with ethylene, and the gauge pressure was increased to 0.2 MPa. After carrying out a polymerization reaction at 70 ° C. for 30 minutes while maintaining the pressure at 0.2 MPa, the polymerization solution was poured into a mixed solution of hydrochloric acid and methanol, and the resulting polymer was precipitated. Drying at 60°C under reduced pressure 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.

Table 3 confirms that Example 7, which contains an alkylmetalloxane compound as a cocatalyst, exhibits higher polymerization activity for the 2-norbornene copolymer than Comparative Example 5, which contains methylaluminoxane as a cocatalyst.

Claims (5)

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 copolymerization of a cyclic olefin, which is used for copolymerizing a cyclic olefin with at least one of ethylene and an α-olefin. 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.) The catalyst for cycloolefin copolymerization according to claim 1 or 2 , wherein the metallocene compound contains at least one of zirconium and titanium. 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. 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.