WO2024084974A1 - Procédé de production d'un copolymère d'oléfine cyclique - Google Patents

Procédé de production d'un copolymère d'oléfine cyclique Download PDF

Info

Publication number
WO2024084974A1
WO2024084974A1 PCT/JP2023/036279 JP2023036279W WO2024084974A1 WO 2024084974 A1 WO2024084974 A1 WO 2024084974A1 JP 2023036279 W JP2023036279 W JP 2023036279W WO 2024084974 A1 WO2024084974 A1 WO 2024084974A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
atom
cyclic olefin
olefin copolymer
producing
Prior art date
Application number
PCT/JP2023/036279
Other languages
English (en)
Japanese (ja)
Inventor
健 鈴木
智之 多田
琴広 野村
Original Assignee
ポリプラスチックス株式会社
東京都公立大学法人
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ポリプラスチックス株式会社, 東京都公立大学法人 filed Critical ポリプラスチックス株式会社
Publication of WO2024084974A1 publication Critical patent/WO2024084974A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring

Definitions

  • the present invention relates to a method for producing a cyclic olefin copolymer containing structural units derived from norbornene monomers and structural units derived from ethylene.
  • Cyclic olefin homopolymers and cyclic olefin copolymers have low moisture absorption and high transparency and are used in a variety of applications including optical materials such as optical disk substrates, optical films, and optical fibers.
  • a representative cyclic olefin copolymer is a copolymer of cyclic olefin and ethylene, which is widely used as a transparent resin.
  • the glass transition temperature (Tg) of the copolymer of cyclic olefin and ethylene can be changed depending on the copolymerization composition of the cyclic olefin and ethylene, so that a copolymer having a glass transition temperature adjusted in a wide temperature range can be produced (see, for example, Non-Patent Document 1).
  • Non-Patent Document 1 there is a problem that a copolymer of a cyclic olefin and ethylene cannot be produced in high yield by the method described in Non-Patent Document 1. As a countermeasure to this problem, it is considered to carry out polymerization using a highly active catalyst. However, when a highly active catalyst is used for polymerization in order to improve the production efficiency of the cyclic olefin copolymer, polyethylene-like impurities may be easily generated. If the cyclic olefin copolymer contains polyethylene-like impurities, the cyclic olefin copolymer becomes turbid when dissolved in a solvent.
  • the cyclic olefin copolymer contains polyethylene-like impurities, there is a concern that the transparency of the cyclic olefin copolymer may decrease. Furthermore, if polyethylene-like impurities are generated, a process that increases production costs is required to filter and remove insoluble polyethylene-like impurities in the general production process for producing the cyclic olefin copolymer.
  • the present invention has been made in consideration of the above problems, and aims to provide a method for producing a cyclic olefin copolymer that can efficiently produce a cyclic olefin copolymer by copolymerizing a norbornene monomer and a monomer containing ethylene while suppressing the generation of polyethylene-like impurities.
  • the present invention provides the following:
  • a method for producing a cyclic olefin copolymer containing a constituent unit derived from a norbornene monomer and a constituent unit derived from ethylene comprising the steps of: charging at least norbornene monomer and ethylene as monomers into a polymerization vessel; polymerizing the monomers in a polymerization vessel in the presence of a metal-containing catalyst;
  • the metal-containing catalyst has a bond represented by M-A-Z, M is an atom of a transition metal of Group 4 of the periodic table;
  • A is an oxygen atom, a sulfur atom, a selenium atom, or a tellurium atom;
  • Z is a phenyl group having a substituent;
  • a production method in which a hydrocarbon group which may contain a silicon atom or a germanium atom is bonded to the phenyl group at the para position relative to the position to which A is bonded.
  • the metal-containing catalyst is represented by the following formula (a1):
  • M is Ti, Zr, or Hf
  • X is an organic substituent having 1 to 20 carbon atoms which may contain a heteroatom, or a halogen atom
  • L1 is represented by the following formula (a1a): is a group represented by L2 is represented by the following formula (a1b): is a group represented by In formula (a1a), R a1 to R a5 each independently represent the same or different and a hydrogen atom, an organic substituent having 1 to 20 carbon atoms which may contain a heteroatom, or an inorganic substituent, and two adjacent groups among R a1 to R a5 on the 5-membered ring may be bonded to each other to form a ring;
  • R a6 and R a7 may be the same or different and each independently represent a hydrogen atom, an organic substituent having 1 to 20 carbon atoms which may contain a heteroatom, or an inorganic substituent, and two adjacent
  • the present invention provides a method for producing a cyclic olefin copolymer that can efficiently produce a cyclic olefin copolymer by copolymerizing a norbornene monomer and a monomer containing ethylene while suppressing the generation of polyethylene-like impurities.
  • a cyclic olefin copolymer containing constituent units derived from a norbornene monomer and constituent units derived from ethylene is produced.
  • the manufacturing method includes: charging at least norbornene monomer and ethylene as monomers into a polymerization vessel; and polymerizing the monomers in a polymerization vessel in the presence of a metal-containing catalyst.
  • charging norbornene monomer and ethylene as monomers into a polymerization vessel is also referred to as a charging step
  • polymerizing the monomers in the polymerization vessel in the presence of a metal-containing catalyst is also referred to as a polymerization step.
  • the monomers in the polymerization vessel are polymerized in the presence of a metal-containing catalyst having a specific structure, which will be described later.
  • a metal-containing catalyst having a specific structure which will be described later, in the copolymerization of norbornene monomer and ethylene, the yield of cyclic olefin copolymer per unit weight of catalyst can be increased.
  • ⁇ Preparation process> In the charging step, norbornene monomer and ethylene are charged as monomers into a polymerization vessel. Norbornene monomer and other monomers other than ethylene may be charged into the polymerization vessel within a range that does not impair the object of the present invention.
  • the total ratio of the constituent units derived from norbornene monomer and the constituent units derived from ethylene is typically preferably 80% by mass or more, more preferably 95% by mass or more, and even more preferably 98% by mass or more, based on the total constituent units.
  • the norbornene monomer and the other monomer other than ethylene are not particularly limited as long as they are copolymerizable with the norbornene monomer and ethylene.
  • a typical example of such other monomer is an ⁇ -olefin.
  • the ⁇ -olefin may be substituted with at least one type of substituent such as a halogen atom.
  • C3 to C12 ⁇ -olefins are preferred.
  • the C3 to C12 ⁇ -olefins include propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 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, and 1-dodecene. Of these, 1-hexene, 1-octene, and 1-decene are preferred.
  • the method of feeding ethylene into the polymerization solution is not particularly limited as long as the desired amount of ethylene can be charged into the polymerization vessel.
  • ethylene is preferably charged into the polymerization vessel so that the charging pressure of ethylene in the polymerization vessel is 0.5 MPa or more.
  • the charging pressure of ethylene is more preferably 0.55 MPa or more, and even more preferably 0.6 MPa or more.
  • the charging pressure of ethylene is, for example, preferably 10 MPa or less, more preferably 5 MPa or less, and even more preferably 3 MPa or less.
  • the feeding pressure of ethylene is preferably from 0.5 to 10 MPa, more preferably from 0.55 to 5 MPa, and even more preferably from 0.6 to 3 MPa.
  • the ethylene charging pressure is a gauge pressure.
  • a solvent may be charged into the polymerization vessel together with the norbornene monomer and ethylene.
  • the solvent is not particularly limited as long as it does not inhibit the polymerization reaction.
  • Preferred solvents include, for example, hydrocarbon solvents such as aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents, and halogenated hydrocarbon solvents. Hydrocarbon solvents are preferred because of their ease of handling, thermal stability, and chemical stability, and aliphatic hydrocarbon solvents are more preferred.
  • preferred solvents include aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, isooctane, isododecane, mineral oil, cyclohexane, methylcyclohexane, and decahydronaphthalene (decalin), aromatic hydrocarbon solvents such as benzene, toluene, and xylene, and halogenated hydrocarbon solvents such as chloroform, methylene chloride, dichloromethane, dichloroethane, and chlorobenzene.
  • aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, isooctane, isododecane, mineral oil, cyclohexane, methylcyclohexane, and decahydronaphthalene (decalin)
  • aromatic hydrocarbon solvents such as benzene, to
  • the concentration of the norbornene monomer is preferably, for example, 0.5% by mass or more as a lower limit, and more preferably 10% by mass or more as an upper limit, and is preferably, for example, 50% by mass or less, and more preferably 35% by mass or less as an upper limit.
  • the concentration of the norbornene monomer is preferably 0.5 to 50% by mass, and more preferably 10 to 35% by mass.
  • the norbornene monomer may be, for example, norbornene or a substituted norbornene, and is preferably norbornene.
  • the norbornene monomer may be used alone or in combination of two or more.
  • substituted norbornene is not particularly limited, and examples of the substituents that the substituted norbornene has include halogen atoms and monovalent or divalent hydrocarbon groups.
  • Specific examples of substituted norbornenes include compounds represented by the following general formula (I).
  • R 1 to R 12 may be the same or different and each represents an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group; R 9 and R 10 , and R 11 and R 12 may combine together to form a divalent hydrocarbon group; R 9 or R 10 and R 11 or R 12 may be joined to form a ring.
  • R 1 to R 12 in the general formula (I) may be the same or different, and each is an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group.
  • R 1 to R 8 include a hydrogen atom; a halogen atom such as fluorine, chlorine, or bromine; and an alkyl group having 1 to 20 carbon atoms, and these may be different from each other, may be partially different, or may all be the same.
  • R 9 to R 12 include a hydrogen atom; a halogen atom such as fluorine, chlorine, or bromine; an alkyl group having 1 to 20 carbon atoms; a cycloalkyl group such as a cyclohexyl group; a substituted or unsubstituted aromatic hydrocarbon group such as a phenyl group, a tolyl group, an ethylphenyl group, an isopropylphenyl group, a naphthyl group, or an anthryl group; a benzyl group, a phenethyl group, or an aralkyl group in which an aryl group is substituted on an alkyl group; and the like. These may be different from each other, may be partially different, or may all be the same.
  • divalent hydrocarbon group formed by combining R 9 and R 10 , or R 11 and R 12 together include alkylidene groups such as an ethylidene group, a propylidene group, and an isopropylidene group.
  • the ring formed may be a monocyclic or polycyclic ring, a polycyclic ring having a bridge, a ring having a double bond, or a ring consisting of a combination of these rings. These rings may have a substituent such as a methyl group.
  • substituted norbornene represented by the general formula (I) include 5-methyl-bicyclo[2.2.1]hept-2-ene, 5,5-dimethyl-bicyclo[2.2.1]hept-2-ene, 5-ethyl-bicyclo[2.2.1]hept-2-ene, 5-butyl-bicyclo[2.2.1]hept-2-ene, 5-ethylidene-bicyclo[2.2.1]hept-2-ene, 5-hexyl- Bicyclic olefins such as bicyclo[2.2.1]hept-2-ene, 5-octyl-bicyclo[2.2.1]hept-2-ene, 5-octadecyl-bicyclo[2.2.1]hept-2-ene, 5-methylidene-bicyclo[2.2.1]hept-2-ene, 5-vinyl-bicyclo[2.2.1]hept-2-ene, and 5-propenyl-bicyclo[2.2.1]hept-2-ene; Tri
  • alkyl-substituted norbornenes e.g., bicyclo[2.2.1]hept-2-ene substituted with one or more alkyl groups
  • alkylidene-substituted norbornenes e.g., bicyclo[2.2.1]hept-2-ene substituted with one or more alkylidene groups
  • 5-ethylidene-bicyclo[2.2.1]hept-2-ene common name: 5-ethylidene-2-norbornene, or simply ethylidenenorbornene
  • the monomers in a polymerization vessel are polymerized in the presence of the metal-containing catalyst described below.
  • the temperature during polymerization is not particularly limited. In view of good yield of the cyclic olefin copolymer, the temperature during polymerization is preferably 20° C. or higher, more preferably 30° C. or higher, even more preferably 50° C. or higher, even more preferably 60° C. or higher, and particularly preferably 70° C. or higher. The temperature during polymerization may be 80° C. or higher.
  • the upper limit of the temperature during polymerization is not particularly limited, and the upper limit of the temperature during polymerization may be, for example, 200° C. or less, 140° C.
  • the temperature during polymerization is preferably 20 to 200°C, more preferably 30 to 200°C, even more preferably 50 to 200°C, even more preferably 60 to 140°C, and particularly preferably 70 to 120°C.
  • M is an atom of a transition metal of Group 4 of the periodic table.
  • A is an oxygen atom, a sulfur atom, a selenium atom, or a tellurium atom.
  • Z is a phenyl group having a substituent. In the phenyl group, a hydrocarbon group which may contain a silicon atom or a germanium atom is bonded at the para position relative to the position to which A is bonded.
  • Ti, Zr, and Hf are preferred, and Ti and Zr are more preferred.
  • A is an oxygen atom, a sulfur atom, a selenium atom, or a tellurium atom. Of these, A is preferably an oxygen atom or a sulfur atom, and more preferably an oxygen atom.
  • Z is a phenyl group having a substituent.
  • a hydrocarbon group which may contain a silicon atom or a germanium atom is bonded at the para position relative to the position to which A is bonded.
  • Such a hydrocarbon group may contain two or more atoms selected from silicon atoms and germanium atoms.
  • the number of atoms selected from silicon atoms and germanium atoms in such a hydrocarbon group is preferably 0 to 2, and more preferably 0 or 1.
  • the total number of carbon atoms, silicon atoms, and germanium atoms contained in the hydrocarbon group which may contain a silicon atom or a germanium atom is not particularly limited as long as the desired effect is not impaired.
  • the total number of carbon atoms, silicon atoms, and germanium atoms contained in the hydrocarbon group which may contain a silicon atom or a germanium atom is preferably 3 or more, more preferably 3 to 20, even more preferably 3 to 12, and particularly preferably 3 to 8.
  • Suitable examples of the branched hydrocarbon group which may contain a silicon atom or a germanium atom include a branched alkyl group, a dialkylsilyl group, a trialkylsilyl group, a diarylsilyl group, a triarylsilyl group, a dialkylgermyl group, a trialkylgermyl group, a diarylgermyl group, and a triarylgermyl group. Of these, branched alkyl groups, dialkylsilyl groups, trialkylsilyl groups, diarylsilyl groups, and triarylsilyl groups are preferred.
  • branched alkyl groups include isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, sec-pentyl, and tert-pentyl groups.
  • Specific examples of the dialkylsilyl group include a dimethylsilyl group, a diethylsilyl group, a methylethylsilyl group, a di-n-propylsilyl group, and a diisopropylsilyl group.
  • trialkylsilyl group examples include a trimethylsilyl group, a triethylsilyl group, a methyldiethylsilyl group, and a dimethylethylsilyl group.
  • a specific example of the diarylsilyl group is a diphenylsilyl group.
  • a specific example of the triarylsilyl group is a triphenylsilyl group.
  • the phenyl group represented by Z preferably has substituents at the 2- and 6-positions when the position to which A is bonded is the 1-position.
  • substituents bonded to the 2- and 6-positions are preferably organic substituents having 1 to 20 carbon atoms.
  • the organic substituent having 1 to 20 carbon atoms when the organic substituent contains a heteroatom, the type of the heteroatom is not particularly limited as long as it does not impair the object of the present invention.
  • the heteroatom include an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom, a selenium atom, and a halogen atom.
  • organic substituents include alkyl groups having 1 to 20 carbon atoms; alkoxy groups having 1 to 20 carbon atoms; cycloalkyl groups having 3 to 20 carbon atoms; aliphatic acyl groups having 2 to 20 carbon atoms; benzoyl groups; ⁇ -naphthylcarbonyl groups; ⁇ -naphthylcarbonyl groups; aromatic hydrocarbon groups having 6 to 20 carbon atoms; aralkyl groups having 7 to 20 carbon atoms; monoalkylsilyl groups, dialkylsilyl groups, and trialkylsilyl groups having 1 to 20 carbon atoms; monosubstituted amino groups substituted with a hydrocarbon group having 1 to 20 carbon atoms; and disubstituted amino groups substituted with a hydrocarbon group having 1 to 20 carbon atoms.
  • alkyl groups having 1 to 20 carbon atoms are preferred, alkyl groups having 3 to 12 carbon atoms are more preferred, and alkyl groups having 3 to 8 carbon atoms are even more preferred.
  • the organic substituents bonded to the 2- and 6-positions of the phenyl group represented by Z are preferably branched chain alkyl groups having 3 to 20 carbon atoms, more preferably branched chain alkyl groups having 3 to 12 carbon atoms, and even more preferably branched chain alkyl groups having 3 to 8 carbon atoms.
  • the substituents bonded to the 2- and 6-positions as Z are preferably an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a sec-pentyl group, and a tert-pentyl group, and more preferably an isopropyl group and a tert-butyl group.
  • phenyl groups having a substituent as Z include 4-substituted phenyl groups such as 4-methylphenyl group, 4-ethylphenyl group, 4-n-propylphenyl group, 4-isopropylphenyl group, 4-n-butylphenyl group, 4-isobutylphenyl group, 4-sec-butylphenyl group, 4-tert-butylphenyl group, 4-n-pentylphenyl group, 4-isopentylphenyl group, 4-neopentylphenyl group, 4-sec-pentylphenyl group, tert-pentylphenyl group, 4-trimethylsilylphenyl group, and 4-triethylsilylphenyl group; 2,6-diisopropyl-4-methylphenyl group, ...
  • 4-substituted phenyl groups such as 4-methylphenyl group, 4-ethylphenyl group, 4-n-propyl
  • the metal-containing catalyst is preferably a compound represented by the following formula (a1).
  • M is Ti, Zr, or Hf
  • X is an organic substituent having 1 to 20 carbon atoms which may contain a heteroatom, or a halogen atom
  • L1 is represented by the following formula (a1a): is a group represented by L2 is represented by the following formula (a1b): is a group represented by In formula (a1a), R a1 to R a5 may be the same or different and each independently represents a hydrogen atom, an organic substituent having 1 to 20 carbon atoms which may contain a heteroatom, or an inorganic substituent.
  • R a6 and R a7 may be the same or different and each independently represent a hydrogen atom, an organic substituent having 1 to 20 carbon atoms which may contain a heteroatom, or an inorganic substituent, and R a8 represents a hydrocarbon group which may contain a silicon atom or a germanium atom.
  • M is Ti, Zr, or Hf, with Ti being particularly preferred in terms of the ease of obtaining and producing metal-containing catalysts and the activity of the catalyst.
  • X is an organic substituent having 1 to 20 carbon atoms which may contain a heteroatom, or a halogen atom.
  • the organic substituent having 1 to 20 carbon atoms which may contain a heteroatom when the organic substituent contains a heteroatom, the type of the heteroatom is not particularly limited as long as it does not impair the object of the present invention.
  • the heteroatom include an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a silicon atom, a selenium atom, and a halogen atom.
  • the organic substituent is not particularly limited as long as it does not inhibit the reaction for producing the metal-containing compound represented by the above formula (a1).
  • alkyl groups having 1 to 6 carbon atoms alkoxy groups having 1 to 6 carbon atoms; cycloalkyl groups having 3 to 8 carbon atoms; aliphatic acyl groups having 2 to 6 carbon atoms; benzoyl groups; phenyl groups; benzyl groups; phenethyl groups; monoarylsilyl groups, diarylsilyl groups, and triarylsilyl groups having 6 to 20 carbon atoms; and monoalkylsilyl groups, dialkylsilyl groups, and trialkylsilyl groups having 1 to 20 carbon atoms are preferred.
  • methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, tert-butyloxy, acetyl, propionyl, butanoyl, phenyl, triphenylsilyl, trimethylsilyl, triethylsilyl, and tert-butyldimethylsilyl are more preferred.
  • X is preferably a halogen atom, more preferably a chlorine atom or a bromine atom, and particularly preferably a chlorine atom.
  • R a1 to R a5 are each independently the same or different and are an organic or inorganic substituent having 1 to 20 carbon atoms which may contain a hydrogen atom or a heteroatom. In addition, two adjacent groups among R a1 to R a5 on the five-membered ring may be bonded to each other to form a ring. In formula (a1a), it is preferable that at least one of R a1 to R a5 is an organic substituent having 3 to 20 carbon atoms. It is more preferable that one of R a1 to R a5 is an organic substituent having 3 to 20 carbon atoms, and four of R a1 to R a5 are hydrogen atoms.
  • the organic substituents represented by R a1 to R a5 are preferably branched groups.
  • organic substituent having 1 to 20 carbon atoms which may contain a heteroatom as R a1 to R a5 are the same as the specific examples and preferred examples of the organic substituent having 1 to 20 carbon atoms which may contain a heteroatom as X.
  • an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a trimethylsilyl group, and a triethylsilyl group are preferred, and an isopropyl group, a tert-butyl group, a trimethylsilyl group, and a triethylsilyl group are more preferred.
  • the inorganic substituent is not particularly limited as long as it is a group that does not inhibit the reaction for producing the metal-containing compound represented by the above formula (a1).
  • Specific examples of the inorganic substituent include a halogen atom, a nitro group, an unsubstituted amino group, and a cyano group.
  • R a6 and R a7 may be the same or different and each independently represent a hydrogen atom, an organic substituent having 1 to 20 carbon atoms which may contain a heteroatom, or an inorganic substituent.
  • Specific examples and preferred examples of the organic substituents as R a6 and R a7 in formula (a1b) are the same as the specific examples and preferred examples of the organic substituents bonded to the 2- and 6-positions of the phenyl group as Z, respectively.
  • Specific examples and preferred examples of the inorganic substituents as R a6 and R a7 in formula (a1b) are the same as the specific examples and preferred examples of the inorganic substituents as R a1 to R a5 , respectively.
  • R a8 is a hydrocarbon group which may contain a silicon atom or a germanium atom.
  • the hydrocarbon group which may contain a silicon atom or a germanium atom as R a8 is the same as the hydrocarbon group which may contain a silicon atom or a germanium atom in the phenyl group represented by Z.
  • Preferred examples of the group represented by formula (a1b) include 4-substituted phenoxy groups such as 4-methylphenoxy group, 4-ethylphenoxy group, 4-n-propylphenoxy group, 4-isopropylphenoxy group, 4-n-butylphenoxy group, 4-isobutylphenoxy group, 4-sec-butylphenoxy group, 4-tert-butylphenoxy group, 4-n-pentylphenoxy group, 4-isopentylphenoxy group, 4-neopentylphenoxy group, 4-sec-pentylphenoxy group, tert-pentylphenoxy group, 4-trimethylsilylphenoxy group, and 4-triethylsilylphenoxy group; 2,6-diisopropyl-4-methylphenoxy group, 2,6 -diisopropyl-4-ethylphenoxy group, 2,6-diisopropyl-4-n-dipropylphenoxy group, 2,4,6-triisopropylphen
  • metal-containing compound represented by formula (a1) explained above include the following metal-containing compounds.
  • M in the following formula is the same as M in formula (a1).
  • Si(Me) 3 is a trimethylsilyl group
  • Si(Et) 3 is a triethylsilyl group
  • i-Pr is an isopropyl group
  • n-Bu is an n-butyl group
  • t-Bu is a tert-butyl group.
  • the polymerization of the monomer is preferably carried out in the presence of the above-mentioned metal-containing catalyst and a co-catalyst.
  • a co-catalyst any compound generally used as a co-catalyst in the polymerization of olefins can be used without any particular limitation.
  • Suitable examples of the co-catalyst include aluminoxane and ionic compounds.
  • the polymerization of the monomer is preferably carried out using at least one of aluminoxane and a borate compound as an ionic compound as a co-catalyst, and more preferably using aluminoxane as a co-catalyst.
  • the above metal-containing catalyst is preferably mixed with an aluminoxane and/or an ionic compound to form a catalyst composition.
  • the ionic compound is a compound that generates a cationic transition metal compound by reacting with a metal-containing catalyst.
  • the catalyst composition is preferably prepared using a solution of a metal-containing catalyst.
  • the solvent contained in the solution of the metal-containing catalyst is not particularly limited.
  • Preferred solvents include aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, isooctane, isododecane, mineral oil, cyclohexane, methylcyclohexane, decahydronaphthalene (decalin), and mineral oil, aromatic hydrocarbon solvents such as benzene, toluene, and xylene, and halogenated hydrocarbon solvents such as chloroform, methylene chloride, dichloromethane, dichloroethane, and chlorobenzene.
  • the amount of solvent used is not particularly limited as long as it is possible to produce a catalyst composition with the desired performance.
  • an amount of solvent is used such that the concentrations of the metal-containing catalyst, aluminoxane, and ionic compound are preferably 0.00000001 to 100 mol/L, more preferably 0.00000005 to 50 mol/L, and particularly preferably 0.0000001 to 20 mol/L.
  • the value of (M b1 +M b2 )/M a is preferably 1 to 200,000, more preferably 5 to 100,000, and particularly preferably 10 to 80,000, where M a is the number of moles of the transition metal element in the metal-containing catalyst, M b1 is the number of moles of aluminum in the aluminoxane, and M b2 is the number of moles of the ionic compound.
  • the temperature at which the liquid containing the raw materials for the catalyst composition is mixed is not particularly limited, but is preferably -100 to 100°C, and more preferably -50 to 50°C.
  • the mixing of the metal-containing catalyst solution with the aluminoxane and/or ionic compound to prepare the catalyst composition may be carried out in an apparatus separate from the polymerization vessel prior to polymerization, or may be carried out in the polymerization vessel prior to or during polymerization.
  • aluminoxane As the aluminoxane, various aluminoxanes that have been conventionally used as cocatalysts in the polymerization of various olefins can be used without any particular limitation. Typically, the aluminoxane is an organic aluminoxane. In producing the catalyst composition, the aluminoxane may be used alone or in combination of two or more kinds.
  • alkylaluminoxanes are preferably used.
  • alkylaluminoxanes include compounds represented by the following formula (b1-1) or (b1-2).
  • the alkylaluminoxanes represented by the following formula (b1-1) or (b1-2) are products obtained by reacting trialkylaluminum with water.
  • R represents an alkyl group having 1 to 4 carbon atoms
  • n represents an integer of 0 to 40, preferably 2 to 30.
  • alkylaluminoxanes examples include methylaluminoxane and modified methylaluminoxanes in which some of the methyl groups of methylaluminoxane have been replaced with other alkyl groups.
  • modified methylaluminoxanes having an alkyl group with 2 to 4 carbon atoms such as an ethyl group, propyl group, isopropyl group, butyl group, or isobutyl group as the alkyl group after substitution are preferred, and modified methylaluminoxanes in which some of the methyl groups have been replaced with isobutyl groups are more preferred.
  • alkylaluminoxanes include methylaluminoxane, ethylaluminoxane, propylaluminoxane, butylaluminoxane, isobutylaluminoxane, methylethylaluminoxane, methylbutylaluminoxane, and methylisobutylaluminoxane, with methylaluminoxane and methylisobutylaluminoxane being preferred among them.
  • Alkyl aluminoxanes can be prepared by known methods. Commercially available alkyl aluminoxanes may also be used. Commercially available alkyl aluminoxanes include, for example, MMAO-3A, TMAO-200 series, TMAO-340 series, solid MAO (all manufactured by Tosoh Finechem Co., Ltd.), and methylaluminoxane solution (manufactured by Albemarle Corporation). It is more preferable to use alkyl aluminoxanes other than solid MAO, as this makes it easier to suppress the generation of polyethylene-like impurities.
  • An ionic compound is a compound that produces a cationic transition metal compound upon reaction with a metal-containing catalyst.
  • ionic compounds that can be used include ionic compounds containing ions such as an anion of tetrakis(pentafluorophenyl)borate, an amine cation having an active proton such as the dimethylphenylammonium cation (( CH3 ) 2N ( C6H5 )H + ), a tri-substituted carbonium cation such as ( C6H5 ) 3C + , a carborane cation, a metal carborane cation, and a ferrocenium cation having a transition metal.
  • a suitable example of an ionic compound is a borate.
  • Preferred specific examples of borates include tetrakis(pentafluorophenyl)tritylborate, dimethylphenylammonium tetrakis(pentafluorophenyl)borate, and N-methyldialkylammonium tetrakis(pentafluorophenyl)borate such as N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate and N-methyldinormaldecylammonium tetrakis(pentafluorophenyl)borate.
  • the phenolic hydroxyl group and the halogen atom are bonded to the same aromatic ring, which may be a single ring or a condensed ring.
  • Hindered phenols are phenols having a bulky substituent at least on one of the two adjacent positions to the phenolic hydroxyl group.
  • the bulky substituent include alkyl groups other than methyl groups such as isopropyl, isobutyl, sec-butyl, and tert-butyl, alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, alkoxy groups, aryloxy groups, substituted amino groups, alkylthio groups, and arylthio groups.
  • hindered phenols include 2,6-di-tert-butyl-p-cresol (BHT), 2,6-di-tert-butylphenol, 2-tert-butylphenol, 2-tert-butyl-p-cresol, 3,3',5,5'-tetra-tert-butyl-4,4'-dihydroxybiphenyl, 3,3',5,5'-tetra-tert-butyl-2,2'-dihydroxybiphenyl, 4,4'-butylidenebis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 4,4',4"-(1-methylpropanylidene)tris(6-tert-butyl-m-cresol), and 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylmethyl)2,4,6-trimethylbenzene.
  • BHT 2,6-di-
  • 2,6-di-tert-butyl-p-cresol (BHT) and 2,6-di-tert-butylphenol are preferred because they have a small molecular weight and the desired effect of using the hindered phenol can be easily obtained by using a small amount of the hindered phenol.
  • the hindered phenol reacts with the alkylaluminum compound in the polymerization system, thereby contributing to an increase in the yield of the cyclic olefin copolymer. For this reason, it is preferable to use the hindered phenol together with the alkylaluminum.
  • the hindered phenol may be mixed with the alkylaluminum in the polymerization machine before use. The mixture obtained by mixing the alkylaluminum and the hindered phenol before polymerization may be introduced into the polymerization machine.
  • Aluminoxane is as explained in the manufacturing method of the catalyst composition.
  • the amount used is preferably 1 to 1,000,000 moles, and more preferably 10 to 100,000 moles, in terms of the number of moles of aluminum in the aluminoxane per mole of metal-containing catalyst.
  • the polymerization is also preferably carried out in the presence of a metal-containing catalyst, an aluminoxane, and a hindered phenol, or in the presence of a metal-containing catalyst, an ionic compound, and a hindered phenol.
  • the monomers in the polymerization vessel are polymerized in the presence of a metal-containing catalyst and an alkyl metal compound.
  • the alkyl metal compound is not particularly limited as long as it is a compound that has been conventionally applied to the polymerization reaction of olefins such as cyclic olefins.
  • Suitable alkyl metal compounds include alkyl aluminum compounds having at least one alkyl group bonded to an Al atom, and alkyl zinc compounds having at least one alkyl group bonded to a Zn atom.
  • the alkyl metal compounds may be used alone or in combination of two or more.
  • alkylaluminum compound any compound that has been conventionally used for the polymerization of olefins, etc., can be used without any particular limitation.
  • alkylaluminum compound for example, a compound represented by the following general formula (II) can be mentioned.
  • R 01 is an alkyl group having 1 to 15 carbon atoms
  • X is a halogen atom or a hydrogen atom
  • z1 is an integer of 1 to 3.
  • the number of carbon atoms in the alkyl group represented by R 01 is 1 to 15, and from the viewpoint of ease of obtaining the desired effect, is preferably 1 to 8, and is further preferably 2 to 8.
  • Specific preferred examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, and an n-octyl group.
  • alkylaluminum compounds include trialkylaluminums such as trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, trisec-butylaluminum, tri-n-pentylaluminum, tri-n-hexylaluminum, tri-n-heptylaluminum, and tri-n-octylaluminum; dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, and diisobutylaluminum chloride; dialkylaluminum hydrides such as dimethylaluminum hydride, diethylaluminum hydride, di-n-propyldimethylaluminum hydride, diisopropyldimethylaluminum hydride, di-n-butyla
  • alkylzinc compound any compound that has been conventionally used for the polymerization of olefins, etc., can be used without any particular limitation.
  • alkylzinc compound for example, a compound represented by the following general formula (III) can be mentioned.
  • R 02 z2 ZnX 2-z2 (III)
  • R02 is an alkyl group having 1 to 15, preferably 1 to 8, carbon atoms
  • X is a halogen atom or a hydrogen atom
  • z2 is an integer of 1 to 3.
  • the number of carbon atoms in the alkyl group represented by R 02 is 1 to 15, and from the viewpoint of easily obtaining the desired effect, 1 to 8 is more preferable, and 2 to 8 is even more preferable.
  • Specific preferred examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, and an n-octyl group.
  • alkyl zinc compounds include dialkyl zincs such as dimethyl zinc, diethyl zinc, di-n-propyl zinc, diisopropyl zinc, di-n-butyl zinc, diisobutyl zinc, di-sec-butyl zinc, di-n-pentyl zinc, di-n-hexyl zinc, di-n-heptyl zinc, and di-n-octyl zinc; alkyl zinc halides such as methyl zinc chloride, ethyl zinc chloride, and isobutyl zinc chloride; and alkyl zinc hydrides such as methyl zinc hydride, ethyl zinc hydride, and isobutyl zinc hydride.
  • dialkyl zincs such as dimethyl zinc, diethyl zinc, di-n-propyl zinc, diisopropyl zinc, di-n-butyl zinc, diisobutyl zinc, di-sec-butyl zinc, di-n-pentyl zinc, di-
  • alkyl metal compounds one or more selected from the group consisting of trialkylaluminum, dialkylaluminum hydride, and dialkylzinc are preferred, with trialkylaluminum and/or dialkylaluminum hydride being more preferred.
  • the amount of alkyl metal compound used together with the metal-containing catalyst is preferably 1 to 500,000 moles, and more preferably 10 to 50,000 moles, in terms of the number of moles of alkyl metal compound per mole of metal-containing catalyst.
  • the polymerization conditions are not particularly limited as long as a cyclic olefin copolymer having desired physical properties can be obtained, and known conditions can be used.
  • the amount of the catalyst composition used is derived from the amount of the metal-containing compound used in the preparation thereof.
  • the amount of the catalyst composition used is preferably 0.000000001 to 0.005 mol, more preferably 0.00000001 to 0.0005 mol, in terms of the mass of the metal-containing compound used in the preparation thereof, per mol of the norbornene monomer.
  • the polymerization time is not particularly limited, and the polymerization is carried out until a desired yield is reached or the molecular weight of the polymer increases to a desired level.
  • the polymerization time varies depending on the temperature, the catalyst composition, and the monomer composition, but is typically 0.01 to 120 hours, preferably 0.1 to 80 hours, and more preferably 0.2 to 10 hours.
  • the catalyst composition is added continuously to the polymerization vessel.
  • the cyclic olefin copolymer can be continuously produced, and the production cost of the cyclic olefin copolymer can be reduced.
  • a norbornene monomer and a monomer containing ethylene are copolymerized to efficiently produce a cyclic olefin copolymer while suppressing the production of polyethylene-like impurities.
  • the suppression of the formation of polyethylene-like impurities can be confirmed, for example, by visually observing a solution in which 0.1 g of a cyclic olefin copolymer sample is dissolved in 10 g of toluene. If no turbidity is observed when the toluene solution is visually observed, the formation of polyethylene-like impurities is suppressed.
  • the glass transition temperature of the resulting cyclic olefin copolymer is not particularly limited, but from the viewpoint of processability, it is, for example, preferably 185°C or less, more preferably 160°C or less, even more preferably 130°C or less, even more preferably 120°C or less, and particularly preferably 100°C or less.
  • a sample of a cyclic olefin copolymer is subjected to measurement by a differential scanning calorimeter under conditions of a nitrogen atmosphere and a temperature increase rate of 20° C./min according to the method described in JIS K7121, a glass transition temperature derived from the cyclic olefin copolymer is observed in the range of 50 to 250° C.
  • the obtained DSC curve does not have a peak of melting point (melting enthalpy) derived from polyethylene-like impurities. This means that there is no polyethylene-like impurity in the cyclic olefin copolymer or the amount of polyethylene-like impurities is extremely small. Note that, when the cyclic olefin copolymer contains polyethylene-like impurities, the melting point peak derived from the polyethylene-like impurities on the DSC curve is generally detected within the range of 90°C to 140°C.
  • the cyclic olefin copolymer produced by the above method has a low content of polyethylene-like impurities and is highly transparent. For this reason, the cyclic olefin copolymer produced by the above method is particularly suitable for use in optical films or sheets, and film or sheet materials for packaging materials, which require a high level of transparency from the standpoint of optical functionality and aesthetics.
  • Examples 1 to 16 and Comparative Examples 1 to 4 In producing the cyclic olefin resin composition, the following Cat. 1 to Cat. 9 were used as the metal-containing catalyst in the examples and comparative examples.
  • CC1 N-methyldialkylammonium tetrakis(pentafluorophenyl)borate (alkyl: C14 to C18 (average: C17.5) (manufactured by Tosoh Finechem Co., Ltd.)
  • CC2 6.5 mass % (as the content of Al atoms)
  • MMAO-3A toluene solution a solution of methylisobutylaluminoxane represented by [(CH 3 ) 0.7 (iso-C 4 H 9 ) 0.3 AlO] n , manufactured by Tosoh Finechem Co., Ltd., containing 6 mol % of trimethylaluminum based on the total Al).
  • Example 1 (Examples 1 to 8, Examples 10 to 16, and Comparative Examples 1 to 4)
  • Decalin as a polymerization solvent and 2-norbornene in the amount shown in Table 1 were added to a thoroughly dried 150 mL stainless steel autoclave containing a stirrer. After heating the autoclave to a polymerization temperature of 90° C., a metal-containing catalyst solution was added so that the amount of the metal-containing catalyst was 0.5 ⁇ mol. The metal-containing catalyst solution was prepared using decalin. Then, 0.93 ⁇ mol of the cocatalyst CC1 was added. Then, ethylene pressure of 0.9 MPa was applied, and the polymerization initiation point was 30 seconds later.
  • the total amount of the monomer solution immediately before the application of ethylene pressure was 80 mL. 15 minutes after the start of polymerization, the supply of ethylene was stopped, and the pressure was carefully returned to normal pressure, and then isopropyl alcohol was added to the reaction solution to stop the reaction.Then, the polymerization solution was poured into a mixed solvent of 300 mL of acetone, 200 mL of methanol or isopropyl alcohol, and 5 mL of hydrochloric acid to precipitate the copolymer. The copolymer was recovered by suction filtration, washed with acetone and methanol, and then vacuum dried at 110°C for 12 hours to obtain a copolymer of norbornene and ethylene. The copolymer yield (kg) per gram of catalyst, calculated from the amount of catalyst used and the amount of copolymer obtained, is shown in Table 1.
  • Example 9 To a thoroughly dried 150 mL stainless steel autoclave containing a stirrer, decalin as a polymerization solvent and 2-norbornene in the amount shown in Table 1 were added. Then, 5000 ⁇ mol of the cocatalyst CC2 was added. After heating the autoclave to a polymerization temperature of 90° C., a metal-containing catalyst solution was added so that the amount of the metal-containing catalyst was 0.5 ⁇ mol. The metal-containing catalyst solution was prepared using decalin. Then, ethylene pressure of 0.9 MPa was applied, and the polymerization initiation point was 30 seconds later. The total amount of the monomer solution immediately before the application of ethylene pressure was 80 mL.
  • the glass transition temperature was measured and a turbidity test was performed according to the following methods.
  • the results of the glass transition temperature measurement and the turbidity test are shown in Table 1.
  • Tg Glass transition temperature
  • DSC device Differential scanning calorimeter (PerkinElmer, DSC-8500) Measurement atmosphere: Nitrogen Measurement temperature range: 50-250°C Heating condition: 20° C./min.
  • N.D. indicates that no peak of the glass transition temperature derived from the cyclic olefin copolymer is detected in the above measurement temperature range on the DSC curve.
  • Examples 1 to 16 it is understood that by polymerizing norbornene monomer and ethylene in the presence of a metal-containing catalyst having a predetermined structure, it is possible to efficiently obtain a copolymer of norbornene and ethylene while suppressing the production of polyethylene-like impurities.
  • Comparative Examples 1 to 4 it is found that when a metal-containing catalyst having a structure other than the predetermined structure is used, it is difficult to efficiently obtain a copolymer of norbornene and ethylene, and further, ethylene-like impurities are likely to be produced. In addition, no peak corresponding to the melting point was observed on the DSC curve obtained when Tg was measured in Examples 1 to 16. On the other hand, in Comparative Examples 1 to 4, a peak corresponding to the melting point of the polyethylene-like impurity was observed on the DSC curve obtained when Tg was measured.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

La présente invention concerne un procédé de production d'un copolymère d'oléfine cyclique, le procédé permettant une production efficace d'un copolymère d'oléfine cyclique par copolymérisation de monomères comprenant de l'éthylène et un monomère de norbornène, tout en supprimant la génération d'impuretés de type polyéthylène.　Des monomères comprenant un monomère norbornène et de l'éthylène sont polymérisés en présence d'un catalyseur contenant un métal qui a une structure spécifique. Un composé qui a une liaison représentée par M-A-Z est utilisé en tant que catalyseur contenant du métal. M représente un atome de métal de transition du groupe 4 du tableau périodique. A représente un atome d'oxygène, un atome de soufre, un atome de sélénium ou un atome de tellure ; et Z représente un groupe phényle ayant un substituant. Par rapport au groupe phényle représenté par Z, un groupe hydrocarboné qui peut contenir un atome de silicium ou un atome de germanium est lié à la position para de la position à laquelle A est lié.
PCT/JP2023/036279 2022-10-18 2023-10-04 Procédé de production d'un copolymère d'oléfine cyclique WO2024084974A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2022167028 2022-10-18
JP2022-167028 2022-10-18

Publications (1)

Publication Number Publication Date
WO2024084974A1 true WO2024084974A1 (fr) 2024-04-25

Family

ID=90737366

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2023/036279 WO2024084974A1 (fr) 2022-10-18 2023-10-04 Procédé de production d'un copolymère d'oléfine cyclique

Country Status (1)

Country Link
WO (1) WO2024084974A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10279630A (ja) * 1997-04-04 1998-10-20 Sumitomo Chem Co Ltd オレフィン系重合体の製造方法
US20030065118A1 (en) * 1999-12-14 2003-04-03 Phillips Petroleum Company Dialkenyl-tricyclic-nonaromatic/olefin polymers

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10279630A (ja) * 1997-04-04 1998-10-20 Sumitomo Chem Co Ltd オレフィン系重合体の製造方法
US20030065118A1 (en) * 1999-12-14 2003-04-03 Phillips Petroleum Company Dialkenyl-tricyclic-nonaromatic/olefin polymers

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
TSUBOTA, MIKI: "Copolymerization of Ethylene and Cyclic Olefin Using Various Group 4 Transition Metal Complex Catalysts", ABSTRACTS OF THE SYMPOSIUM ON PETROLEUM AND PETROCHEMISTRY, vol. 32, 2002, pages 284 - 285 *

Similar Documents

Publication Publication Date Title
WO2020204188A1 (fr) Procede de production de polymere de cycloolefine
JP2018145425A (ja) 環状オレフィン樹脂組成物、その製造方法、及び成形品
JP6491804B1 (ja) 共重合体及び共重合体の製造方法
WO2020204187A1 (fr) Procede de production de polymere de cycloolefine
CN106232641B (zh) 环状烯烃共聚物的制造方法
US11795256B2 (en) Production method for cyclic olefin copolymer and catalyst composition for copolymerization of norbornene monomer and ethylene
WO2024084974A1 (fr) Procédé de production d'un copolymère d'oléfine cyclique
JP7175426B2 (ja) 環状オレフィン共重合体の製造方法
JP7073467B2 (ja) 環状オレフィン共重合体の製造方法
JP7257595B2 (ja) 環状オレフィン共重合体の製造方法
JP7329720B1 (ja) 環状オレフィン共重合体の製造方法及び触媒組成物
JP7361239B1 (ja) 環状オレフィン共重合体の製造方法
JP2022060007A (ja) 環状オレフィン共重合体、成形品、及び環状オレフィン共重合体の製造方法
JP7101063B2 (ja) メタロセン触媒の触媒活性の検定方法、オレフィンモノマー重合用の触媒組成物の製造方法、及びポリマーの製造方法
JP7127231B1 (ja) 透明物品
JP7383852B1 (ja) 環状オレフィン共重合体、及び環状オレフィン共重合体の製造方法
JP7426543B2 (ja) 環状オレフィン共重合体、樹脂組成物及びフィルム状又はシート状の成形品
JP7383853B1 (ja) 環状オレフィン共重合体、及び環状オレフィン共重合体の製造方法
JP2023042441A (ja) ノルボルナン骨格含有重合体の製造方法、及びノルボルナン骨格含有重合体
JP2022030194A (ja) 環状オレフィン共重合体、及び環状オレフィン共重合体の製造方法
JP2023112594A (ja) 樹脂組成物、及びフィルム
JPS63308010A (ja) 分枝α−オレフィン共重合体およびその製造方法