Process for the production of cyclic olefin copolymers and catalyst composition

Abstract

A method for producing a cyclic olefin copolymer containing a structural unit derived from a norbornene monomer and a structural unit derived from ethylene, the method comprising: a step of charging at least the norbornene monomer and ethylene as monomers into a polymerization vessel; and a step of causing the monomers in the polymerization vessel to undergo polymerization in the presence of a catalyst having a phosphinimide group, wherein the catalyst having the phosphinimide group is composed of a compound having a specific structure.

Description

Technical Field

[0001] This invention relates to a method for manufacturing cyclic olefin copolymers and a catalyst composition. Background Technology

[0002] Cyclic olefin homopolymers and copolymers possess low hygroscopicity and high transparency, making them suitable for a wide range of applications, primarily in optical materials such as optical disc substrates, optical films, and optical fibers. A representative example of a cyclic olefin copolymer is the copolymer of cyclic olefins and ethylene, which is widely used as a transparent resin. Because the glass transition temperature (Tg) of cyclic olefin-ethylene copolymers can be varied depending on the copolymer composition of the cyclic olefins and ethylene, copolymers with adjustable glass transition temperatures over a wide temperature range can be manufactured (see, for example, Non-Patent Literature 1).

[0003] Existing technical documents

[0004] Non-patent literature

[0005] Non-patent literature 1: Incoronata, Tritto et al., Coordination Chemistry Reviews, 2006, Vol. 250, pp. 212-241 Summary of the Invention

[0006] The problem that the invention aims to solve

[0007] However, the method described in Non-Patent Literature 1 has the problem of not being able to produce copolymers of cyclic olefins and ethylene in high yield. As a solution to this problem, using a highly active catalyst for polymerization can be considered. However, when using a highly active catalyst for polymerization, there is a tendency to generate polyethylene-like impurities. When the cyclic olefin copolymer contains polyethylene-like impurities, turbidity occurs when the cyclic olefin copolymer is dissolved in a solvent. Therefore, there is a concern about a decrease in the transparency of the cyclic olefin copolymer. Moreover, when polyethylene-like impurities are generated, the general manufacturing process for producing cyclic olefin copolymers requires processes such as filtration and removal of insoluble polyethylene-like impurities, which increases manufacturing costs.

[0008] The present invention was made in view of the above-mentioned problems, and its objective is to provide a method for manufacturing cyclic olefin copolymers that can obtain cyclic olefin copolymers in high yield and with less formation of polyethylene-like impurities.

[0009] Furthermore, another objective of the present invention is to provide a catalyst composition that exhibits high activity relative to the copolymerization of cyclic olefins and ethylene and can suppress the formation of polyethylene-like impurities.

[0010] Technical solutions for solving the problem

[0011] In order to solve the aforementioned problems, the inventors conducted in-depth research and found that the above problems can be solved by using a catalyst with a specific structure having a phosphonium imide group in the copolymer of cyclic olefins and ethylene, thereby achieving the present invention.

[0012] One aspect of the present invention that solves the aforementioned problem is as follows.

[0013] (1) A method for manufacturing a cyclic olefin copolymer, wherein the cyclic olefin copolymer contains structural units derived from norbornene monomer and structural units derived from ethylene.

[0014] The method for manufacturing the cyclic olefin copolymer includes:

[0015] At least the process of loading norbornene monomer and ethylene as monomers into the polymerization container; and

[0016] The process of polymerizing the monomer within the polymerization vessel in the presence of a catalyst having phosphonium imide groups.

[0017] The catalyst having the phosphonium imide group is a compound represented by the following general formula (A), wherein the group in general formula (A) is composed of -(CH2). n R represents a substituent that satisfies condition A.

[0018] Condition A: In the case of -(CH2) n R represents compounds in which a substituent is bonded to a benzene ring (C6H5-(CH2)). n In R), the -(CH2) n The charge of the carbon atom in the substituent represented by R that is directly bonded to the benzene ring is less than -0.46.

[0019] [Chemical Formula 1]

[0020]

[0021] In general formula (A), M represents a transition metal of group 4 in the periodic table, X represents an organic substituent or halogen atom containing 1 to 20 carbon atoms (which may contain heteroatoms), and R... a1 ~R a3 Each can independently represent a hydrogen atom, which may be the same or different, and an organic or inorganic substituent containing 1 to 20 carbon atoms, which may contain heteroatoms. R represents one or more selected from hydrogen atoms, alkyl, cycloalkyl, haloalkyl, aryl, haloaryl, alkylsilyl, and arylsilyl, and n represents an integer from 1 to 5.

[0022] (2) According to the method for manufacturing the cyclic olefin copolymer described in (1) above, the insertion activation energy of the catalyst relative to titanium-ethylene-ethylene is less than 7 kcal / mol.

[0023] (3) In the method for manufacturing the cyclic olefin copolymer according to (1) or (2) above, the insertion activation energy of norbornene relative to titanium-norbornene-ethylene in the catalyst is less than 31 kcal / mol.

[0024] (4) According to any one of the methods for manufacturing the cyclic olefin copolymer described in (1) to (3) above, R in the general formula (A) a1 ~R a3 It is a cyclic or acyclic tertiary alkyl group or an aromatic cyclic group having at least one alkyl group in the ortho position.

[0025] (5) In the method for manufacturing the cyclic olefin copolymer according to any one of (1) to (4) above, R in the general formula (A) is a perfluorophenyl.

[0026] (6) A catalyst composition comprising a catalyst composition having a phosphonium imide group for copolymerizing norbornene monomer with ethylene, wherein,

[0027] The catalyst having the phosphonium imide group is a compound represented by the following general formula (A), wherein the group in general formula (A) is composed of -(CH2). n R represents a substituent that satisfies condition A.

[0028] Condition A: In the case of -(CH2) n R represents compounds in which a substituent is bonded to a benzene ring (C6H5-(CH2)). n In R), the -(CH2) n The charge of the carbon atom in the substituent represented by R that is directly bonded to the benzene ring is less than -0.46.

[0029] [Chemical Formula 2]

[0030]

[0031] In general formula (A), M represents a transition metal of group 4 in the periodic table, X represents an organic substituent or halogen atom containing 1 to 20 carbon atoms (which may contain heteroatoms), and R... a1 ~R a3 Each can independently represent a hydrogen atom, which may be the same or different, and an organic or inorganic substituent containing 1 to 20 carbon atoms, which may contain heteroatoms. R represents one or more selected from hydrogen atoms, alkyl, cycloalkyl, haloalkyl, aryl, haloaryl, alkylsilyl, and arylsilyl, and n represents an integer from 1 to 5.

[0032] (7) According to the catalyst composition described in (6) above, R in the general formula (A) a1~R a3 It is a cyclic or acyclic tertiary alkyl group or an aromatic cyclic group having at least one alkyl group in the ortho position.

[0033] (8) In the catalyst composition according to (6) or (7) above, R in the general formula (A) is a perfluorophenyl.

[0034] Invention Effects

[0035] According to the present invention, a method for manufacturing a cyclic olefin copolymer that can be obtained in high yield and with less formation of polyethylene-like impurities can be provided.

[0036] Furthermore, according to the present invention, a catalyst composition that exhibits high activity relative to the copolymerization of cyclic olefins and ethylene and can suppress the formation of polyethylene-like impurities can be provided. Detailed Implementation

[0037] <Method for manufacturing cyclic olefin copolymers>

[0038] The method for manufacturing the cyclic olefin copolymer of this embodiment is a method for manufacturing a cyclic olefin copolymer containing structural units derived from norbornene monomer and structural units derived from ethylene. The method includes: a step of loading at least norbornene monomer and ethylene as monomers into a polymerization container (hereinafter also referred to as the "loading step"); and a step of polymerizing the monomers in the polymerization container in the presence of a catalyst having a phosphonium imide group (hereinafter also referred to as the "polymerization step"). Furthermore, the catalyst having a phosphonium imide group is a compound represented by the following general formula (A), and the phosphonium imide group in the following general formula (A) is represented by -(CH2). n R represents a substituent that satisfies condition A.

[0039] Condition A: In the case of -(CH2) n R represents compounds in which a substituent is bonded to a benzene ring (C6H5-(CH2)). n In R), -(CH2) n The charge of the carbon atom in the substituent represented by R that is directly bonded to the benzene ring is less than -0.46.

[0040] [Chemical Formula 3]

[0041]

[0042] In general formula (A), M represents a transition metal of group 4 in the periodic table, X represents an organic substituent or halogen atom containing 1 to 20 carbon atoms (which may contain heteroatoms), and R... a1 ~R a3Each can independently represent a hydrogen atom, which may be the same or different, and an organic or inorganic substituent containing 1 to 20 carbon atoms, which may contain heteroatoms. R represents one or more selected from hydrogen atoms, alkyl, cycloalkyl, haloalkyl, aryl, haloaryl, alkylsilyl, and arylsilyl, and n represents an integer from 1 to 5.

[0043] The method for manufacturing cyclic olefin copolymers in this embodiment is characterized by a catalyst used for the copolymerization of norbornene and ethylene. This catalyst has high activity, thus allowing for the production of large quantities of cyclic olefin copolymers with a smaller amount of material. Furthermore, despite its high activity, this catalyst is less prone to generating polyethylene-like impurities, resulting in cyclic olefin copolymers with excellent transparency.

[0044] The following is a detailed description of each process.

[0045] [Loading process]

[0046] In the loading process, at least norbornene monomer and ethylene are loaded into the polymerization container as monomers. In the polymerization container, monomers other than norbornene monomer and ethylene may be loaded to a extent that does not adversely affect the manufacturing method of this embodiment. The total ratio of structural units derived from norbornene monomer and structural units derived from ethylene in the cyclic olefin copolymer is typically preferably 80% by mass or more, more preferably 95% by mass or more, and even more preferably 98% by mass or more, relative to the total structural units.

[0047] The method of loading ethylene into the polymerization solution is not particularly limited as long as the desired amount of ethylene is loaded into the polymerization vessel. Typically, ethylene is loaded into the polymerization vessel at a loading pressure of 0.5 MPa or higher. The loading pressure is preferably 0.55 MPa or higher, more preferably 0.6 MPa or higher. Increasing the loading pressure reduces the amount of catalyst required per unit of polymer produced. An upper limit for the loading pressure is preferably 10 MPa or lower, more preferably 5 MPa or lower, and even more preferably 3 MPa or lower.

[0048] The solvent, norbornene monomer, and ethylene can also be loaded into the polymerization container together. There are no particular restrictions on the solvent as long as it does not interfere with the polymerization reaction. Examples of solvents include hydrocarbon solvents such as pentane, hexane, heptane, octane, isooctane, isododecane, mineral oil, cyclohexane, methylcyclohexane, decahydronaphthalene, benzene, toluene, and xylene, as well as halogenated hydrocarbon solvents such as chloroform, methylene chloride, dichloromethane, dichloroethane, and chlorobenzene.

[0049] When norbornene monomer is incorporated into a solvent, the lower limit of the concentration of norbornene monomer is preferably 0.5% by mass or more, more preferably 10% by mass or more. The upper limit is preferably 50% by mass or less, more preferably 35% by mass or less.

[0050] The following is a detailed description of norbornene monomer.

[0051] [norbornene monomer]

[0052] Examples of norbornene monomers include norbornene and substituted norbornene, with norbornene being preferred. One norbornene monomer may be used alone or in combination of two or more.

[0053] The aforementioned substituted norbornene is not particularly limited, and the substituents present in the substituted norbornene may include, for example, halogen atoms, monovalent or divalent hydrocarbon groups. Specific examples of substituted norbornene include compounds represented by the following general formula (I).

[0054] [Chemical Formula 4]

[0055]

[0056] In general formula (I), R 1 ~R 12 These can be the same or different and can be selected from hydrogen atoms, halogen atoms, and hydrocarbon groups.

[0057] R 9 and R 10 R 11 and R 12 They can form a divalent hydrocarbon group in one piece.

[0058] R 9 or R 10 With R 11 or R 12 They can form a ring around each other.

[0059] Furthermore, n represents 0 or a positive integer.

[0060] When n is 2 or more, R 5 ~R 8 Within each repeating unit, they can be the same or different.

[0061] However, when n=0, R 1 ~R 4 and R 9 ~R 12 At least one of them is not a hydrogen atom.

[0062] The substituted norbornene represented by general formula (I) will be described. R in general formula (I)1 ~R 12 These can be the same or different and can be selected from hydrogen atoms, halogen atoms, and hydrocarbon groups.

[0063] As R 1 ~R 8 Specific examples include hydrogen atoms; halogen atoms such as fluorine, chlorine, and bromine; alkyl groups with 1 to 20 carbon atoms, which can be different, partially different, or completely the same.

[0064] In addition, as R 9 ~R 12 Specific examples include hydrogen atoms; halogen atoms such as fluorine, chlorine, and bromine; alkyl groups with 1 to 20 carbon atoms; cycloalkyl groups such as cyclohexyl; substituted or unsubstituted aromatic hydrocarbon groups such as phenyl, tolyl, ethylphenyl, isopropylphenyl, naphthyl, and anthracene; benzyl, phenethyl, and other aryl groups with aryl groups substituted in the alkyl group, etc. They can be different individually, partially different, or completely the same.

[0065] As R 9 With R 10 Or R 11 With R 12 Specific examples of alkylene groups that form a divalent hydrocarbon group through integration include alkylene groups such as ethylene, propyleneene, and isopropyleneene.

[0066] In R 9 or R 10 With R 11 or R 12 When rings are formed, the resulting rings can be monocyclic or polycyclic, cross-linked polycyclic rings, rings with double bonds, or combinations of these rings. Furthermore, these rings can also have substituents such as methyl groups.

[0067] Specific examples of substituted norbornene represented by 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-ethylene-bicyclo[2.2.1]hept-2-ene, 5-hexyl-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-methylene-bicyclo[2.2.1]hept-2-ene, 5-vinyl-bicyclo[2.2.1]hept-2-ene, 5-propenyl-bicyclo[2.2.1]hept-2-ene, and other bicyclic olefins.

[0068] Three Rings [4.3.0.1]2,5 ] Dec-3,7-diene (common name: dicyclopentadiene), tricyclo[4.3.0.1 2,5 ] Dec-3-ene; Tricyclic [4.4.0.1 2,5 Undecyl-3,7-diene or tricyclic [4.4.0.1] 2,5 Undecyl-3,8-diene or their partial hydrides (or adducts of cyclopentadiene and cyclohexene), i.e., tricyclic...

[0069] [4.4.0.1 2,5 Undecyl-3-ene; tricyclic cyclic alkenes such as 5-cyclopentyl-bicyclo[2.2.1]hept-2-ene, 5-cyclohexyl-bicyclo[2.2.1]hept-2-ene, 5-cyclohexenylbicyclo[2.2.1]hept-2-ene, and 5-phenyl-bicyclo[2.2.1]hept-2-ene;

[0070] Fourth Ring Road [4.4.0.1] 2,5 .1 7,10 Dodecyl-3-ene (abbreviated as tetracyclododecene), 8-methyltetracyclo[4.4.0.1] 2, 5 .1 7,10 Dodecyl-3-ene, 8-ethyltetracyclo[4.4.0.1] 2,5 .1 7,10 Dodecyl-3-ene, 8-methylenetetracyclo[4.4.0.1] 2,5 .1 7 ,10 Dodecyl-3-ene, 8-ethylidene tetracyclo[4.4.0.1] 2,5 .1 7,10 Dodecyl-3-ene, 8-vinyltetracyclo[4,4.0.1] 2,5 .1 7 ,10 Dodecyl-3-ene, 8-propenyl-tetracyclo[4.4.0.1] 2,5 .1 7,10 Tetracyclic olefins such as dodecyl-3-ene;

[0071] 8-Cyclopentyl-tetracyclo[4.4.0.1] 2,5 .1 7,10 Dodecyl-3-ene, 8-cyclohexyl-tetracyclo[4.4.0.1] 2,5 .1 7,10 Dodecyl-3-ene, 8-cyclohexenyl-tetracyclo[4.4.0.1] 2,5 .1 7,10 Dodecyl-3-ene, 8-phenyl-cyclopentyl-tetracyclo[4.4.0.1] 2 ,5 .1 7,10Dodecyl-3-ene; tetracyclo[7.4.1] 3,6 .0 1,9 .0 2,7 [Tetradecyl-4,9,11,13-tetraene (also known as 1,4-bridged methylene-1,4,4a,9a-tetrahydrofluorene), tetracyclic [8.4.1] 4,7 .0 1,10 .0 3,8 [Pentadecano-5,10,12,14-tetraene (also known as 1,4-bridged methylene-1,4,4a,5,10,10a-hexahydroanthracene); pentacyclic [6.6.1.1] 3,6 .0 2,7 .0 9,14 ]-4-Hexadecene, Pentane [6.5.1.1 3, 6 .0 2,7 .0 9,13 ]-4-Pentadene, Pentane [7.4.0.0] 2,7 .1 3,6 .1 10,13 ]-4-Pentadene; Heptacyclic [8.7.0.1 2,9 .1 4,7 .1 11 ,17 .0 3,8 .0 12,16 ]-5-eicosene, heptacyclic [8.7.0.1 2,9 .0 3,8 .1 4,7 .0 12,17 .1 13,l6 Polycyclic cyclic olefins such as 1,4-eicosene; tetramers of cyclopentadiene.

[0072] Preferably, alkyl-substituted norbornene (e.g., bicyclo[2.2.1]hept-2-ene substituted with one or more alkyl groups) or alkylene-substituted norbornene (e.g., bicyclo[2.2.1]hept-2-ene substituted with one or more alkyl groups), and especially preferably 5-ethylene-bicyclo[2.2.1]hept-2-ene (common name: 5-ethylene-2-norbornene or simply ethylene norbornene).

[0073] There are no particular restrictions on norbornene monomers and other monomers besides ethylene, as long as they can be copolymerized with norbornene monomers and ethylene. Typical examples of other monomers involved include α-olefins. α-olefins can be substituted with at least one substituent such as a halogen atom.

[0074] The preferred α-olefin is a C3 to C12 α-olefin. There are no particular limitations on the C3 to C12 α-olefin, and examples 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. Among these, 1-hexene, 1-octene, and 1-decene are preferred.

[0075] [Polymerization Process]

[0076] In the polymerization process, monomers within a polymerization vessel are polymerized in the presence of a specific catalyst having phosphonium imide groups.

[0077] There are no particular limitations on the polymerization temperature. However, due to the good yield of cyclic olefin copolymers, the polymerization temperature is preferably 20°C or higher, more preferably 30°C or higher, even more preferably 50°C or higher, and still more preferably 60°C or higher, particularly preferably 70°C or higher. The polymerization temperature can also be 80°C or higher, or 85°C or higher.

[0078] There is no particular upper limit to the temperature during polymerization. For example, the upper limit of the temperature during polymerization can be below 200°C, below 140°C, or below 120°C.

[0079] (Catalysts with phosphonium imide groups)

[0080] The catalyst with a phosphonium imide group (hereinafter also referred to as "catalyst A") used in the manufacturing method of this embodiment is represented by the following general formula (A). Furthermore, the group consisting of -(CH2) in the following general formula (A)... n R represents a substituent that satisfies condition A.

[0081] Condition A: In the case of -(CH2) n R represents compounds in which a substituent is bonded to a benzene ring (C6H5-(CH2)). n In R), -(CH2) n The charge of the carbon atom in the substituent represented by R that is directly bonded to the benzene ring is less than -0.46.

[0082] [Chemical Formula 5]

[0083]

[0084] In general formula (A), M represents a transition metal of group 4 in the periodic table, X represents an organic substituent or halogen atom containing 1 to 20 carbon atoms (which may contain heteroatoms), and R...a1 ~R a3 Each can independently represent a hydrogen atom, which may be the same or different, and an organic or inorganic substituent containing 1 to 20 carbon atoms, which may contain heteroatoms. R represents one or more selected from hydrogen atoms, alkyl, cycloalkyl, haloalkyl, aryl, haloaryl, alkylsilyl, and arylsilyl, and n represents an integer from 1 to 5.

[0085] In general formula (A), M represents a group 4 transition metal in the periodic table, specifically Ti, Zr, or Hf. Ti is preferred as M.

[0086] In general formula (A), X is an organic substituent or halogen atom that may contain 1 to 20 carbon atoms and may contain heteroatoms.

[0087] Regarding organic substituents with 1 to 20 carbon atoms that may contain heteroatoms, there are no particular restrictions on the types of heteroatoms. Specific examples of heteroatoms include oxygen atoms, nitrogen atoms, sulfur atoms, phosphorus atoms, silicon atoms, selenium atoms, and halogen atoms.

[0088] There are no particular limitations on the type of organic substituent as long as it does not impede the formation reaction of the compound represented by the above general formula (A). Examples include alkyl groups with 1 to 20 carbon atoms, alkoxy groups with 1 to 20 carbon atoms, cycloalkyl groups with 3 to 20 carbon atoms, aliphatic acyl groups with 2 to 20 carbon atoms, benzoyl groups, α-naphthalenecarbonyl groups, β-naphthalenecarbonyl groups, aromatic hydrocarbon groups with 6 to 20 carbon atoms, aralkyl groups with 7 to 20 carbon atoms, trialkylsilyl groups with 3 to 20 carbon atoms, triarylsilyl groups with 3 to 20 carbon atoms, monosubstituted amino groups substituted with hydrocarbon groups with 1 to 20 carbon atoms, and disubstituted amino groups substituted with hydrocarbon groups with 1 to 20 carbon atoms.

[0089] Among these organic substituents, 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, trialkylsilyl groups having 3 to 10 carbon atoms, and triarylsilyl groups having 3 to 10 carbon atoms are preferred.

[0090] More preferably, the organic substituents are 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, butyryl, phenyl, trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, triphenylsilyl, and tripentafluorophenylsilyl.

[0091] X is preferably a halogen atom, more preferably a chlorine atom or a bromine atom, and especially preferably a chlorine atom.

[0092] In general formula (A), R a1 ~R a3 Each can be an organic or inorganic substituent, consisting of hydrogen atoms (which may be the same or different) and carbon atoms (1 to 20) containing heteroatoms. Additionally, it can be selected from R... a1 ~R a3 The two groups can combine with each other to form a ring.

[0093] Regarding R a1 ~R a3 Organic substituents containing 1 to 20 carbon atoms may be used, and there are no particular restrictions on the types of heteroatoms. Specific examples of heteroatoms include oxygen, nitrogen, sulfur, phosphorus, silicon, selenium, and halogen atoms.

[0094] There are no particular limitations on the type of organic substituent as long as it does not impede the formation reaction of the compound represented by the above general formula (A). Examples include alkyl groups with 1 to 20 carbon atoms, alkoxy groups with 1 to 20 carbon atoms, cycloalkyl groups with 3 to 20 carbon atoms, aliphatic acyl groups with 2 to 20 carbon atoms, benzoyl groups, α-naphthalenecarbonyl groups, β-naphthalenecarbonyl groups, aromatic hydrocarbon groups with 6 to 20 carbon atoms, aralkyl groups with 7 to 20 carbon atoms, trialkylsilyl groups with 3 to 20 carbon atoms, triarylsilyl groups with 3 to 20 carbon atoms, monosubstituted amino groups substituted with hydrocarbon groups with 1 to 20 carbon atoms, and disubstituted amino groups substituted with hydrocarbon groups with 1 to 20 carbon atoms.

[0095] Among these organic substituents, 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, trialkylsilyl groups having 3 to 10 carbon atoms, and triarylsilyl groups having 3 to 10 carbon atoms are preferred.

[0096] More preferably, the organic substituents are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, adamantyl, methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, tert-butyloxy, acetyl, propionyl, butyryl, phenyl, o-tolyl, trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, triphenylsilyl, and tripentafluorophenylsilyl.

[0097] In addition, as R a1 ~R a3The organic substituent may contain 1 to 20 carbon atoms of heteroatom, and is more preferably a group represented by the following general formula (a), namely R a1 ~R a3 Each group consists of a hydrocarbon group having 1 to 20 carbon atoms.

[0098] [Chemical Formula 6]

[0099]

[0100] As R a1 ~R a3 Preferred examples of organic substituents containing 1 to 20 carbon atoms of heteroatoms that are groups represented by general formula (a) include -N=P(Me)3, -N=P(Et)3, -N=P(n-Pr)3, -N=P(iso-Pr)3, -N=P(n-Bu)3, -N=P(iso-Bu)3, -N=P(sec-Bu)3, -N=P(tert-Bu)3, -N=P(-N=P(tert-Bu)3)Ph2, and -N=P(Ph)3. Among these, -N=P(tert-Bu)3 and -N=P(iso-Pr)3 are preferred, and -N=P(tert-Bu)3 is more preferred. In addition, Me represents methyl, Et represents ethyl, n-Pr represents n-propyl, iso-Pr represents isopropyl, n-Bu represents n-butyl, iso-Bu represents isobutyl, sec-Bu represents sec-butyl, tert-Bu represents tert-butyl, and Ph represents phenyl.

[0101] As R a1 ~R a3 There are no particular restrictions on the inorganic substituents, as long as they do not hinder the formation reaction of the compound represented by the above general formula (A).

[0102] Specific examples of inorganic substituents include halogen atoms, nitro groups, unsubstituted amino groups, and cyano groups.

[0103] R in general formula (A) a1 ~R a3 Preferably, it is a cyclic or acyclic tertiary alkyl group or an aromatic cyclic group having at least one alkyl group at the ortho position. Examples of cyclic tertiary alkyl groups include adamantyl, and examples of acyclic tertiary alkyl groups include tert-butyl. Examples of aromatic cyclic groups having at least one alkyl group at the ortho position include o-tolyl and mesitylene. In R a1 ~R a3 When the tertiary alkyl group is cyclic or acyclic, it can be all different tertiary alkyl groups, preferably two out of three are the same tertiary alkyl group, and more preferably all are the same tertiary alkyl group.

[0104] In general formula (A), R represents one or more selected from hydrogen atom, alkyl, cycloalkyl, haloalkyl, aryl, haloaryl, alkylsilyl and arylsilyl.

[0105] Examples of alkyl groups R include alkyl groups having 1 to 5 carbon atoms, with alkyl groups having 1 to 4 carbon atoms being preferred. Specific examples of alkyl groups R include methyl, ethyl, isopropyl, n-butyl, tert-butyl, etc., with tert-butyl being preferred.

[0106] Examples of cycloalkyl groups R include those with 3 to 20 carbon atoms, preferably those with 3 to 10 carbon atoms, and more preferably those with 5 to 8 carbon atoms. Specific examples of cycloalkyl groups R include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc., with cyclohexyl being the most preferred.

[0107] The haloalkyl group R is an alkyl group having at least one halogen element as a substituent. Examples of haloalkyl groups with 1 to 7 carbon atoms include alkyl groups with 1 to 5 carbon atoms, and more preferably haloalkyl groups with 1 to 3 carbon atoms. Furthermore, the halogen element in the haloalkyl group R is preferably fluorine or chlorine. Specific examples of haloalkyl groups R include monofluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, heptafluoropropyl, trichloromethyl, etc., with trifluoromethyl being preferred.

[0108] Aryl groups of R can be 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, and more preferably 7 to 8 carbon atoms.

[0109] Specific examples of aryl groups of R include phenyl, tolyl, xylyl, mesitylelyl, naphthyl, aralkyl, biphenyl, etc., with phenyl being the preferred choice.

[0110] The halogenated aryl group R is an aryl group having at least one halogen element as a substituent on the aryl group R described above. Examples of aryl groups with 6 to 20 carbon atoms include aryl groups with 6 to 10 carbon atoms, and more preferably aryl groups with 7 to 8 carbon atoms. Furthermore, the halogen element in the halogenated aryl group R is preferably fluorine or chlorine. Specific examples of the halogenated aryl group R include 4-fluorophenyl, 2,4-difluorophenyl, 2,4,6-trifluorophenyl, 2,3,6-trifluorophenyl, perfluorophenyl (-C6F5), perfluorobiphenyl, perchlorophenyl (-C6Cl5), etc., among which perfluorophenyl (-C6F5) is preferred.

[0111] Examples of alkylsilyl groups as R include trimethylsilyl, triethylsilyl, etc., with trimethylsilyl being the preferred choice.

[0112] Examples of arylsilyl groups as R include triphenylsilyl, tripentafluorophenylsilyl, and triarylsilyl groups, with triphenylsilyl being the preferred choice.

[0113] Among these R groups, the preferred ones are hydrogen atoms, groups with a large number of carbon atoms in the alkyl group (carbon number: 3 to 12), or groups containing fluorine atoms. For example, hydrogen atoms, tert-butyl, phenyl, perfluorophenyl (-C6F5), and trimethylsilyl are particularly preferred.

[0114] In general formula (A), n represents an integer from 1 to 5, preferably from 1 to 3.

[0115] The following are specific examples of compounds represented by general formula (A), but this embodiment is not limited to the following compounds.

[0116] [Chemical Formula 7]

[0117]

[0118] [Chemical Formula 8]

[0119]

[0120] On the other hand, catalyst A is composed of -(CH2) in general formula (A). n R represents a substituent that satisfies condition A.

[0121] Condition A: When using -(CH2) n R represents compounds in which a substituent is bonded to a benzene ring (C6H5-(CH2)). n In the case of R), under the influence of -(CH2) n The charge of the carbon atom in the substituent represented by R that is directly bonded to the benzene ring is -0.46 or less. When the charge of this carbon atom exceeds -0.46, the activity as a catalyst decreases. This charge is preferably -0.47 or less, more preferably -0.48 or less, even more preferably -0.49 or less, even more preferably -0.50 or less, and particularly preferably -0.60 or less. Furthermore, the lower limit of the charge of the carbon atom is preferably -0.70.

[0122] Furthermore, the charge of the carbon atom can be calculated as follows: using the DFT theory known as M11 (as a natural bond orbital analysis) and the basis function known as cc-pvdz, the charge can be calculated relative to the charge of the -(CH2) atom. n R represents the C6H5-(CH2) compound in which a substituent is attached to a benzene ring. n Quantum chemical calculations of R. Natural bond orbital analysis was performed relative to the obtained molecular orbitals, and the atomic charge (electron charge) of the carbon atom (C) bonded to the benzene ring was calculated.

[0123] The following shows the expression in general formula (A) consisting of -(CH2). n R represents compounds in which a substituent is bonded to a benzene ring (C6H5-(CH2)). n In R), -(CH2) n R represents the charge of the carbon atom in the substituent that is directly bonded to the benzene ring, i.e., the charge of the carbon atom involved in condition A.

[0124] -CH2-C6F5: -0.49

[0125] -CH2CH2-C6F5: -0.46

[0126] -CH2CH2-C6H5: -0.46

[0127] -CH2CH2-C(CH3)3: -0.47

[0128] -CH2CH2-Si(CH3)3: -0.47

[0129] -CH2-C6H5: -0.48

[0130] -CH3: -0.68

[0131] However, in the above, -C6F5 is a perfluorophenyl.

[0132] From the viewpoint of improving activity, the insertion activation energy of ethylene relative to titanium-ethylene-ethylene in catalyst A is preferably 7 kcal / mol or less, more preferably 0.8 to 6.9 kcal / mol. Similarly, the insertion activation energy of norbornene relative to titanium-norbornene-ethylene in catalyst A is preferably 31 kcal / mol or less, more preferably 17 to 30 kcal / mol.

[0133] The activation energies mentioned above were obtained by performing a reactivity analysis using quantum chemical calculations (Gaussian), employing the DFT theory known as M11 and the basis function known as cc-pvdz, and calculating the activation enthalpy in the polymerization reaction.

[0134] When catalyst A (a compound represented by general formula (A)) is in an unactivated state and comes into contact with norbornene, a viscous substance sometimes forms. It is presumed that the formation of this viscous substance is due to the hydrolysis of catalyst A by water to generate HCl, which then facilitates the cationic polymerization of norbornene. Furthermore, even if R in general formula (A) contains only one fluorine molecule, the formation of this viscous substance can be suppressed. That is, the more fluorine molecules in R in general formula (A), the higher the hydrophobicity, the more suppressed the formation of HCl, and the more suppressed the formation of the viscous substance. Therefore, R in general formula (A) preferably contains one or more fluorine molecules. Specifically, the fluorine in R in general formula (A) is preferably... 2 Carbon bonds (e.g., -(CH2)) n -C6F5), or three fluorine atoms bonded to the same carbon atom (e.g., -(CH2)). n -CF3). Among them, from the perspective of ease of synthesis, it is especially preferred to be similar to sp. 2 Carbon bonds (e.g., -(CH2)) n -C6F5). However, when there is too much fluorine, the electron attraction increases, raising concerns about the instability of catalyst A. Therefore, a balance between suppressing viscous substances and ensuring the stability of catalyst A is preferred. Furthermore, sp 2 Carbon refers to the carbon that forms sp. 2 Carbon atoms with mixed orbitals.

[0135] The compound represented by the general formula (A) that serves as catalyst A can be prepared with reference to Douglas W. Stephan et al., Organometallics 1999, 18, 1116-1118.

[0136] The polymerization of the monomer is preferably carried out in the presence of catalyst A and a cocatalyst. The cocatalyst can be any compound commonly used in the polymerization of olefins, without particular limitation. Preferred examples of cocatalysts include aluminoxanes and ionic compounds. For the ease of polymerization, it is particularly preferred to use at least one of an aluminoxane and a borate compound (an ionic compound) as a cocatalyst. Further details regarding cocatalysts will be described later.

[0137] In this embodiment, during the polymerization process, catalyst A (and co-catalysts as described below as needed) is used to copolymerize norbornene monomer with ethylene. Details will be described together with the catalyst composition described below.

[0138] <Catalyst Composition>

[0139] The catalyst composition of this embodiment is a catalyst composition containing a phosphonium imide group for copolymerizing norbornene monomer and ethylene. Furthermore, the catalyst containing the phosphonium imide group is a compound represented by the following general formula (A), wherein the -(CH2) group in general formula (A) is... n R represents a substituent that satisfies condition A.

[0140] Condition A: In the case of -(CH2) n R represents compounds in which a substituent is bonded to a benzene ring (C6H5-(CH2)). n In R), -(CH2) n The charge of the carbon atom in the substituent represented by R that is directly bonded to the benzene ring is less than -0.46.

[0141] [Chemical Formula 9]

[0142]

[0143] In general formula (A), M represents a transition metal of group 4 in the periodic table, X represents an organic substituent or halogen atom containing 1 to 20 carbon atoms (which may contain heteroatoms), and R... a1 ~R a3 Each can independently represent an organic or inorganic substituent, which may be the same or different hydrogen atom and may contain 1 to 20 carbon atoms (including heteroatoms). R represents one or more selected from hydrogen atom, alkyl, cycloalkyl, haloalkyl, aryl, haloaryl, alkylsilyl, and arylsilyl, and n represents an integer from 1 to 5.

[0144] The catalyst in the catalyst composition of this embodiment is the same as catalyst A described in the manufacturing method of this embodiment. That is, the catalyst composition of this embodiment contains catalyst A. Therefore, the description of the catalyst in the catalyst composition of this embodiment is directly applicable to the description of catalyst A, so the description is omitted here, and the following description focuses on the components other than the catalyst.

[0145] The catalyst composition of this embodiment preferably contains a co-catalyst in addition to catalyst A. Aluminoxanes and / or ionic compounds are preferably used as the co-catalyst.

[0146] Here, ionic compounds are compounds that generate cationic transition metal compounds through reaction with a metal-containing catalyst.

[0147] The catalyst composition of this embodiment is preferably prepared using a solution of catalyst A. There are no particular limitations on the solvent contained in the solution of catalyst A. Preferred solvents include hydrocarbon solvents such as pentane, hexane, heptane, octane, isooctane, isododecane, mineral oil, cyclohexane, methylcyclohexane, decahydronaphthalene, benzene, toluene, and xylene, as well as halogenated hydrocarbon solvents such as chloroform, methylene chloride, dichloromethane, dichloroethane, and chlorobenzene.

[0148] The amount of solvent used is not particularly limited as long as it is sufficient to produce a catalyst composition with the desired performance. Typically, the concentration of catalyst A, aluminoxane, and ionic compound is preferably 0.00000001 to 100 mol / L, more preferably 0.00000005 to 50 mol / L, and particularly preferably 0.0000001 to 20 mol / L.

[0149] When mixing a liquid containing a catalyst composition, it is preferable that the molar number of the transition metal M in catalyst A is M. a The number of moles of aluminum in aluminoxane is M. b1 The number of moles of the ionic compound is M. b2 In the case of (M) b1 +M b2 ) / M a The liquid containing the catalyst composition is mixed with a value preferably of 1 to 200,000, more preferably 5 to 100,000, and especially preferably 10 to 80,000.

[0150] The temperature of the liquid containing the catalyst composition is not particularly limited, but is preferably -100 to 100°C, more preferably -50 to 50°C.

[0151] The mixing of the solution of catalyst A used to prepare the catalyst composition with aluminum oxane and / or ionic compounds can be carried out in a separate apparatus, different from the polymerization vessel, before polymerization, or in the polymerization vessel, before or during polymerization.

[0152] The following describes the materials used in the preparation of the catalyst composition and the preparation conditions of the catalyst composition.

[0153] [Aluminoxane]

[0154] As aluminum oxanes, various aluminum oxanes that have been used as co-catalysts in the polymerization of various olefins can be used without particular restriction. Typically, aluminum oxanes are organoalumina oxanes.

[0155] In the manufacture of catalyst compositions, aluminum oxanes can be used alone or in combination of two or more.

[0156] Alkyl aluminum oxanes are preferred as aluminum oxanes. Examples of alkyl aluminum oxanes include compounds represented by formulas (b1-1) or (b1-2) below. The alkyl aluminum oxanes represented by formulas (b1-1) or (b1-2) below are products obtained by the reaction of trialkylaluminum with water.

[0157] [Chemical Formula 10]

[0158]

[0159] [In formulas (b1-1) and (b1-2), R represents an alkyl group with 1 to 4 carbon atoms, and n represents an integer from 0 to 40, preferably from 2 to 30.]

[0160] Examples of alkylaluminoxanes include methylaluminoxane and modified methylaluminoxanes (MMAO) in which a portion of the methyl group of methylaluminoxane is substituted with other alkyl groups. For example, the substituted alkyl group is preferably a modified methylaluminoxane having alkyl groups with 2 to 4 carbon atoms, such as ethyl, propyl, isopropyl, butyl, or isobutyl, and is particularly more preferably a modified methylaluminoxane in which a portion of the methyl group is substituted with isobutyl. Specific examples of alkylaluminoxanes include methylaluminoxane, ethylaluminoxane, propylaluminoxane, butylaluminoxane, isobutylaluminoxane, methylethylaluminoxane, methylbutylaluminoxane, and methylisobutylaluminoxane, among which methylaluminoxane and methylisobutylaluminoxane are preferred.

[0161] Alkyl aluminum oxanes can be prepared by known methods. Furthermore, commercially available products can be used as alkyl aluminum oxanes. Examples of commercially available alkyl aluminum oxanes include MMAO-3A, ​​TMAO-200 series, TMAO-340 series, solid MAO (all manufactured by Tosoh Finechem Co., Ltd.), and methyl aluminum oxane solutions (manufactured by Albemarle Co., Ltd.). From the perspective of easily suppressing the formation of polyethylene-like impurities, the use of alkyl aluminum oxanes other than solid MAO is more preferable.

[0162] [Ionic compounds]

[0163] Ionic compounds are compounds that react with catalyst A to form cationic transition metal compounds.

[0164] The ionic compounds involved can be anions containing tetra(pentafluorophenyl)borate, or dimethylphenylammonium cations ((CH3)2N(C6H5)H + ) amine cations with active protons, (C6H5)3C+ Ionic compounds containing ions such as trisubstituted carbocations, carborane cations, metallic carborane cations, and ferrocene cations containing transition metals.

[0165] Preferred examples of ionic compounds include borates. Specific examples of borates include tetra(pentafluorophenyl)triphenylmethylborate, dimethylphenylammonium tetra(pentafluorophenyl)borate, and N,N-dimethylaniline tetra(pentafluorophenyl)borate, N-methyldidecylammonium tetra(pentafluorophenyl)borate, etc., specifically N-methyldialkylammonium tetra(pentafluorophenyl)borate.

[0166] Next, in the manufacturing method of this embodiment, the process of copolymerizing norbornene monomer with ethylene using catalyst A or the catalyst composition of this embodiment will be described.

[0167] From the perspective of easily producing cyclic olefin copolymers in good yield, it is preferable that one or more of aluminum oxanes and alkyl aluminum compounds are present before adding a metal catalyst or a catalyst composition containing a metal catalyst into the polymerization vessel.

[0168] Regarding aluminum oxanes, as described above.

[0169] Alkyl aluminum compounds can be used without particular limitation, including compounds conventionally used in the polymerization of olefins. Examples of alkyl aluminum compounds include those represented by the following general formula (II).

[0170] (R 10 ) z AlX 3-z (II)

[0171] (In general formula (II), R) 10 It is an alkyl group having 1 to 15 carbon atoms, preferably 1 to 8, where X is a halogen atom or a hydrogen atom, and z is an integer from 1 to 3.

[0172] Examples of alkyl groups having 1 to 15 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and n-octyl.

[0173] Specific examples of alkylaluminum compounds include trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, trisec-butylaluminum, and tri-n-octylaluminum; dialkylaluminum halides such as dimethylaluminum chloride and diisobutylaluminum chloride; dialkylaluminum hydride such as diisobutylaluminum hydride; and dialkylaluminum alcohols such as dimethylmethoxide aluminum.

[0174] The amount of aluminoxane added to the polymerization vessel before adding catalyst A or a catalyst composition containing catalyst A is preferably 1 to 1,000,000 moles of aluminum relative to 1 mole of aluminoxane containing a transition metal compound, and more preferably 10 to 100,000 moles.

[0175] The amount of alkyl aluminum compound added to the polymerization vessel before adding catalyst A or a catalyst composition containing catalyst A is preferably 1 to 500,000 moles of aluminum relative to 1 mole of transition metal compound, more preferably 10 to 50,000 moles.

[0176] The polymerization conditions are not particularly limited as long as they are conditions that yield cyclic olefin copolymers with the desired physical properties; known conditions can be used.

[0177] The amount of catalyst A can be derived from the amount of transition metal compound used in its preparation. The amount of catalyst composition, as the mass of the transition metal compound used in its preparation, is preferably 0.000000001 to 0.005 moles, more preferably 0.00000001 to 0.0005 moles, relative to 1 mole of norbornene monomer.

[0178] There is no particular time limit for polymerization; polymerization continues until the desired yield is achieved or the molecular weight of the polymer increases to the desired level.

[0179] The polymerization time varies depending on the temperature, catalyst composition, and monomer composition, but is typically 0.01 hours to 120 hours, preferably 0.1 hours to 80 hours, and more preferably 0.2 hours to 10 hours.

[0180] Preferably, at least a portion, preferably all, of catalyst A or the catalyst composition is continuously added to the polymerization vessel.

[0181] Cycloolefin copolymers can be continuously manufactured by adding catalyst A or a catalyst composition, thereby reducing the manufacturing cost of cycloolefin copolymers.

[0182] According to the method described above, by copolymerizing monomers containing norbornene monomer and ethylene, the formation of impurities in polyethylene-like products can be suppressed and cyclic olefin copolymers can be manufactured with high efficiency.

[0183] The glass transition temperature of the obtained cyclic olefin copolymer is not particularly limited, but from the viewpoint of processability, it is preferably below 185°C, more preferably below 160°C, further preferably below 130°C, even more preferably below 120°C, and especially preferably below 100°C.

[0184] Furthermore, following the method described in JIS K7121, when a sample of a cyclic olefin copolymer prepared by the above method is measured using a differential scanning calorimeter (DSC) under a nitrogen atmosphere and a heating rate of 20°C / min, the obtained DSC curve preferably shows a melting point (enthalpy of fusion) peak free of impurities originating from polyethylene. This means that polyethylene-like impurities are absent or present in very small amounts in the cyclic olefin copolymer. Furthermore, in the case where the cyclic olefin copolymer contains polyethylene-like impurities, the melting point peak of these impurities on the DSC curve is typically detected in the range of 100°C to 140°C.

[0185] Example

[0186] The following examples will be used to illustrate this embodiment in more detail, but this embodiment is not limited to the following examples.

[0187] [Examples 1-5, Comparative Examples 1-2]

[0188] Add decahydronaphthalene (decahydronaphthalene) and the amount of 2-norbornene (75-185 mmol) listed in Table 1 to a dried 150 mL stainless steel autoclave containing a stirrer.

[0189] Next, 250 μmol of triisobutylaluminum (manufactured by Tosoh Finechem Co., Ltd.) was added, and the autoclave was heated to 90°C. A catalyst solution of the catalyst types listed in Table 1, prepared using toluene, was added at a catalyst amount of 0.5 μmol. Then, a solution of N-methyldialkylammonium tetra(pentafluorophenyl)borate (alkyl group: C14–C18 (average: C17.5) (manufactured by Tosoh Finechem Co., Ltd.), prepared using decahydronaphthalene, was added at a N-methyldialkylammonium tetra(pentafluorophenyl)borate amount of 1.5 μmol. Next, an ethylene pressure of 0.9 MPa was applied, and polymerization began after 30 seconds.

[0190] In addition, the total volume of the monomer solution before applying ethylene pressure is 80 mL.

[0191] Fifteen minutes after the start of polymerization, the ethylene supply was stopped, and the pressure was carefully returned to atmospheric pressure. Isopropyl alcohol was then added to the reaction solution to stop the reaction. Next, the polymerization solution was added to a mixture of 300 mL acetone, methanol, or 200 mL isopropyl alcohol and 5 mL 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 the copolymer of norbornene and ethylene.

[0192] Furthermore, in Table 1, examples 1-5 correspond to the specific examples of compounds represented by general formula (A) shown above. The structures of compounds 1-2 are compared below. Moreover, "charge of the carbon atom" refers to the charge on the catalyst consisting of -(CH2). n R represents compounds in which a substituent is bonded to a benzene ring (C6H5-(CH2)). n The charge of the carbon atom directly bonded to the benzene ring is calculated using R). However, regarding the absence of -(CH2)... n For comparative compounds 1 and 2, where R represents a substituent, similarly, for compounds where the substituent is bonded to the cyclopentadiene ring and the substituent is bonded to the benzene ring, the charges of the carbon or silicon atoms directly bonded to the benzene ring are calculated for C6H5-C(CH3)3 or C6H5-Si(CH3)3. In Table 1, the Ti-EE activation energy represents the insertion activation energy of ethylene relative to titanium-ethylene-ethylene, and the Ti-NE activation energy represents the insertion activation energy of norbornene relative to titanium-norbornene-ethylene.

[0193] [Chemical Formula 11]

[0194]

[0195] [evaluate]

[0196] (1) Yield of cyclic olefin copolymers

[0197] In each embodiment and comparative example, the copolymer yield (kg) per 1g of catalyst was calculated based on the amount of catalyst used and the yield of the copolymer. The calculation results are shown in Table 1.

[0198] (2) Determination of glass transition temperature (Tg)

[0199] The glass transition temperatures of the cyclic olefin copolymers obtained from each example and comparative example were determined using the DSC method (as described in JIS K7121) with a differential scanning calorimeter (DSC-Q1000, manufactured by TA Instruments) under a nitrogen atmosphere and at a heating rate of 20°C / min. The results are shown in Table 1.

[0200] (3) Thermal analysis of impurities

[0201] In the DSC curve obtained by measuring the glass transition temperature, the calorific value (mJ / mg) is calculated based on the peak area of ​​the melting point of impurities derived from polyethylene-like substances observed in the range of 100–140 °C. The higher the calculated calorific value, the greater the content of impurities derived from polyethylene-like substances.

[0202] In addition, the "not detected" in Table 1 indicates that no peak of the melting point of impurities originating from polyethylene was detected on the DSC curve.

[0203] (4) Turbidity test

[0204] After dissolving 0.1 g of the cyclic olefin copolymers obtained in the various examples and comparative examples in 10 g of toluene, the presence or absence of turbidity in the solution was observed. Cases where no turbidity was observed were rated as "good," and cases where turbidity was observed were rated as "poor." The evaluation results are shown in Table 1.

[0205] (5) Formation of viscous substances

[0206] 3 mL of a decahydronaphthalene solution (concentration: 35% by mass) was added relative to 1 μmol of the catalyst used in the examples and comparative examples, and the formation of a gel-like substance (viscous substance) was visually observed. The absence of gel formation was evaluated as "no," and the formation of gel formation was evaluated as "yes." The evaluation results are shown in Table 1.

[0207] [Table 1]

[0208]

[0209] As shown in Table 1, in Examples 1-5, the yield was higher and the catalyst activity was higher compared to Comparative Examples 1-2. Furthermore, in Examples 1-5, no impurities were detected by impurity thermal analysis. Additionally, the polymer solution did not show turbidity in the turbidity test, indicating that the formation of impurities in the polyethylene-like material was suppressed.

[0210] On the other hand, when a decahydronaphthalene solution of norbornene was added to the catalyst used in the various examples, no viscous substances were generated in Examples 1, 2, and 5, but viscous substances were generated in Examples 3 and 4. Based on these comparisons, it can be seen that when R in general formula (A) contains fluorine, the formation of viscous substances can be suppressed.

Claims

1. A method for producing a cyclic olefin copolymer containing a structural unit derived from a norbornene monomer and a structural unit derived from ethylene, characterized by comprising: a step of charging at least a norbornene monomer and ethylene as monomers into a polymerization vessel; and a step of causing the monomers in the polymerization vessel to polymerize in the presence of a catalyst having a phosphinimine group and a borate. [Chemical Formula 1] 2. The method for producing a cyclic olefin copolymer according to claim 1, characterized in that, when M in the general formula (A) is titanium, an activation energy of insertion of ethylene with respect to titanium-ethylene-ethylene of the catalyst is 7 kcal / mol or less.

3. The method for producing a cyclic olefin copolymer according to claim 1 or 2, characterized in that, when M in the general formula (A) is titanium, an activation energy of insertion of norbornene with respect to titanium-norbornene-ethylene of the catalyst is 31 kcal / mol or less. The catalyst having the phosphinimide group is a compound represented by the following general formula (A), and the substituent represented by -(CH2) n R represents a substituent satisfying the following condition A, Condition A: In the case of -(CH2) n R represents compounds in which a substituent is bonded to a benzene ring (C6H5-(CH2)). n In R), the -(CH2) n The charge of the carbon atom in the substituent represented by R that is directly bonded to the benzene ring is less than -0.

46.

4. The method for producing a cyclic olefin copolymer according to claim 1 or 2, characterized in that, when M in the general formula (A) is titanium, an activation energy of insertion of norbornene with respect to titanium-norbornene-ethylene of the catalyst is 31 kcal / mol or less. In General Formula (A), M represents a transition metal of Group 4 of the periodic table, X represents an organic substituent having 1 to 20 carbon atoms which can contain a hetero atom or a halogen atom, R a1 ~R a3 each independently represents a hydrogen atom, an organic substituent having 1 to 20 carbon atoms which can contain a hetero atom or an inorganic substituent, which can be the same or different, R represents one or more selected from a hydrogen atom, an alkyl group, a cycloalkyl group, a halogenated alkyl group, an aryl group, a halogenated aryl group, an alkylsilyl group and an arylsilyl group, and n represents an integer of 1 to 5.

5. The method for producing a cyclic olefin copolymer according to claim 1 or 2, characterized in that, R in the general formula (A) is a perfluorophenyl group.

6. Use of a catalyst composition containing a catalyst having a phosphinimine group and a borate in the production of a copolymer of a norbornene monomer and ethylene, characterized in that, [Chemical Formula 2] 7. The use according to claim 6, characterized in that, when M in the general formula (A) is titanium, an activation energy of insertion of ethylene with respect to titanium-ethylene-ethylene of the catalyst is 7 kcal / mol or less.

8. The use according to claim 6 or 7, characterized in that, R in the general formula (A) is a perfluorophenyl group. ​ R in the general formula (A) is a tertiary alkyl group or an aromatic ring group having at least one or more alkyl groups at the ortho position, which is cyclic or acyclic. a1 R is a tertiary alkyl group or an aromatic ring group having at least one or more alkyl groups at the ortho position, which is cyclic or acyclic. a3 R is a tertiary alkyl group or an aromatic ring group having at least one or more alkyl groups at the ortho position, ​ ​ ​ The catalyst having the phosphinimide group is a compound represented by the following general formula (A), and the substituent represented by -(CH2) n R represents a substituent satisfying the following condition A, Condition A: In the case of -(CH2) n R represents compounds in which a substituent is bonded to a benzene ring (C6H5-(CH2)). n In R), the -(CH2) n The charge of the carbon atom in the substituent represented by R that is directly bonded to the benzene ring is less than -0.

46. ​ In General Formula (A), M represents a transition metal of Group 4 of the periodic table, X represents an organic substituent having 1 to 20 carbon atoms which can contain a hetero atom or a halogen atom, R a1 ~R a3 each independently represents a hydrogen atom, an organic substituent having 1 to 20 carbon atoms which can contain a hetero atom or an inorganic substituent, which can be the same or different, R represents one or more selected from a hydrogen atom, an alkyl group, a cycloalkyl group, a halogenated alkyl group, an aryl group, a halogenated aryl group, an alkylsilyl group and an arylsilyl group, and n represents an integer of 1 to 5. ​ R in the general formula (A) is a tertiary alkyl group or an aromatic ring group having at least one or more alkyl groups at the ortho position, which is cyclic or acyclic. a1 R is a tertiary alkyl group or an aromatic ring group having at least one or more alkyl groups at the ortho position, which is cyclic or acyclic. a3 R is a tertiary alkyl group or an aromatic ring group having at least one or more alkyl groups at the ortho position, ​ ​

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