Method for producing cyclic olefin copolymer

Abstract

To provide a method for efficiently producing a cyclic olefin-based copolymer reduced in an aluminum content of 100 ppm or less.SOLUTION: A method for producing a cyclic olefin-based copolymer includes a polymerization step of copolymerizing α-olefin (X') having 2 to 20 carbon atoms, cyclic olefin (Y') having no aromatic ring, and cyclic olefin (Z') having an aromatic ring, in the presence of a catalyst for olefin polymerization containing a transition metal compound (A) and a compound (B), and a catalyst removal step of removing the catalyst for olefin polymerization, in which the cyclic olefin-based copolymer obtained by the production method has a structural unit (X) derived from the α-olefin (X'), a structural unit (Y) derived from the cyclic olefin (Y') and a structural unit (Z) derived from the cyclic olefin (Z'), an aluminum content of the cyclic olefin-based copolymer is 100 ppm or less, the transition metal compound (A) contains one or two or more selected from the group consisting of a transition metal compound (A-1), a transition metal compound (A-2) and a transition metal compound (A-3), and the compound (B) contains one or two or more selected from the group consisting of an organometal compound (B-1), an organic aluminum oxy compound (B-2), and a compound (B-3) forming an ion pair by reacting with the metal compound (A).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing a cyclic olefin copolymer, and a cyclic olefin copolymer. More specifically, the present invention relates to a method for producing a cyclic olefin copolymer in which metal residues derived from polymerization catalyst components are reduced. [Background technology]

[0002] Cyclic olefin polymers are used in optical lenses such as imaging lenses, Fθ lenses, pickup lenses, etc. Cyclic olefin polymers used in molded articles such as optical lenses are required to have properties such as high transparency, excellent dimensional stability, and excellent heat resistance.

[0003] Examples of techniques relating to such cyclic olefin polymers include those described in Patent Documents 1 and 2. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 10-287713 [Patent Document 2] Japanese Patent Application Laid-Open No. 2010-235719 Summary of the Invention [Problem to be solved by the invention]

[0005] Polymerization of cyclic olefins is generally carried out by solution polymerization. Among these, solution polymerization using a polymerization catalyst is one of the polymerization methods preferably used for producing cyclic olefin copolymers because it has good reaction controllability and can produce highly uniform polymers. However, while solution polymerization has various advantages, it has the problem that when a polymerization catalyst component is dissolved in the polymerization reaction solution, metal components derived from the polymerization catalyst component are likely to remain in the resulting polymer.

[0006] In addition, a co-catalyst such as an organoaluminum compound may be used in combination with the polymerization catalyst to activate it, but in this case, the amount of the co-catalyst such as the organoaluminum compound used is usually larger than that of the polymerization catalyst, which poses a problem of an extremely large content of aluminum components in the cyclic olefin polymer. Such residual metal components such as aluminum have an adverse effect on color tone and physical properties during molding, and therefore need to be thoroughly removed.

[0007] In the polymerization of cyclic olefin polymers using a polymerization catalyst, the polymerization catalyst is deactivated after the polymerization reaction is completed, and then the deactivated polymerization catalyst is removed by generally mixing an aqueous alkaline solution such as sodium hydroxide with the polymerization reaction solution and extracting metal components into the alkaline aqueous layer. During this process, the liquid viscosity of the polymerization solution increases, making it difficult to extract the metal component residues derived from the catalyst into the alkaline aqueous layer, and inhibiting removal of the metal component residues.

[0008] In this regard, it is known that some cyclic olefin polymers, such as copolymers obtained by polymerizing norbornene and ethylene, increase in viscosity and solidify after a certain period of time has elapsed since the preparation of the polymer solution (see, for example, paragraph

[0007] of JP 2013-064114 A). Therefore, in the production of cyclic olefin polymers, the increased viscosity of the polymerization solution hinders the removal of metal component residues, which has been a problem.

[0009] To address the above issues, a method has been disclosed in which the polymerization reaction solution is diluted with a solvent to reduce the viscosity of the polymerization reaction solution and promote the removal of metal component residues (Patent No. 5735367 [Claim 1], etc.). However, this method poses a problem in terms of production efficiency, as it increases the amount of polymerization solution that must be treated in subsequent processes (catalyst removal process and polymer separation process).

[0010] An object of the present invention is to provide a method for efficiently producing a cyclic olefin copolymer having an aluminum content reduced to 100 ppm or less. [Means for solving the problem]

[0011] The present inventors have conducted extensive research to solve the above problems, and as a result have found that by carrying out polymerization in the presence of an olefin polymerization catalyst containing a transition metal compound (A) and a compound (B), it is possible to reduce metal residues derived from the polymerization catalyst components contained in a cyclic olefin copolymer, thereby completing the present invention.

[0012] That is, according to the present invention, there is provided the following method for producing a cyclic olefin copolymer.

[0013] [1] a polymerization step of copolymerizing an α-olefin (X') having 2 to 20 carbon atoms, a cyclic olefin (Y') having no aromatic ring, and a cyclic olefin (Z') having an aromatic ring in the presence of an olefin polymerization catalyst containing a transition metal compound (A) and a compound (B); a catalyst removal step of removing the olefin polymerization catalyst; A method for producing a cyclic olefin copolymer, comprising: The cyclic olefin copolymer obtained by this production method has a structural unit (X) derived from the α-olefin (X'), a structural unit (Y) derived from the cyclic olefin (Y'), and a structural unit (Z) derived from the cyclic olefin (Z'), the cyclic olefin copolymer has an aluminum content of 100 ppm or less; The transition metal compound (A) is A transition metal compound (A-1) represented by the following formula (I): A transition metal compound (A-2) represented by the following formula (II), and The transition metal compound (A-3) contains one or more transition metal compounds selected from the group consisting of transition metal compounds (A-3) represented by the following formula (III): The compound (B) is Organometallic compound (B-1), Organoaluminum oxy compound (B-2), and A method for producing a cyclic olefin copolymer, which contains one or more compounds (B-3) selected from the group consisting of compounds that react with the transition metal compound (A) to form an ion pair. [ka] In the above formula (I), M 1 indicates a transition metal atom in Group 4 of the periodic table, R 0 represents a group selected from the group consisting of an alkylene group, an alkylidene group, an arylene group, and a silylene group, and substituted groups thereof; R 1 and R 2 each independently represents a cycloalkadienyl group or a substituted cycloalkadienyl group, R 3 and R 4 each independently represents an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a silicon-containing group, a boron-containing group, and an aluminum-containing group, and substitution products thereof. [ka] In the above formula (II), M 2 indicates a transition metal atom in Group 4 of the periodic table, n 1 represents an integer from 1 to 3, L each independently represents a monovalent anionic ligand having an atom of Group 15 of the periodic table as a coordinating atom; X 1 each independently represents a group or atom selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a silicon-containing group, a boron-containing group, and an aluminum-containing group, and substitution products thereof; R 5 ~R 9each independently represents a group or atom selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a silicon-containing group, a boron-containing group, and an aluminum-containing group, and a substitution product thereof; R 5 ~R 9 Any two or three of these may be fused to form a ring, and the ring formed may have aromaticity containing a conjugated double bond. [ka] In the above formula (III), M 3 indicates a transition metal atom in Group 4 of the periodic table, n 2 represents an integer from 1 to 4, X 2 each independently represents an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a silicon-containing group, a boron-containing group, and an aluminum-containing group; R 10 ~R 17 each independently represents an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a silicon-containing group, a boron-containing group, and an aluminum-containing group, and the group consisting of substituted groups thereof; R 10 ~R 17 Adjacent ones of these may be bonded to each other to form a ring, and the ring formed may have aromaticity containing a conjugated double bond. [2] A method for producing the cyclic olefin copolymer according to [1], In the above formula (I), R 1 and R 2each independently represent a group selected from the group consisting of a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group, a dimethylcyclopentadienyl group, an indenyl group, a tetrahydroindenyl group, a fluorenyl group, and a substituted group thereof. [3] A method for producing the cyclic olefin copolymer according to [1], In the above formula (II), A method for producing a cyclic olefin copolymer, wherein L is a monovalent anionic ligand represented by the following formula (IV): [ka] In the above formula (IV), Y represents an atom in group 15 of the periodic table, Z represents one type of atom selected from Group 14, 15, or 16 of the periodic table; n 3 represents an integer from 1 to 3, R 18 each independently represents a group or atom selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a silicon-containing group, a boron-containing group, and an aluminum-containing group, and the group consisting of substituted groups thereof, and each may be bonded to each other to form a ring, and the formed ring may have aromaticity including a conjugated double bond, or the formed ring may be bonded to a cyclopentadienyl group. [4] A method for producing the cyclic olefin copolymer according to [1], In the above formula (III), R 10 ~R 14 and R 17 each independently represents an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, and a silicon-containing group, and the group consisting of substituted groups thereof; R 10 ~R 14Adjacent ones of these may be bonded to each other to form a ring, and the ring formed may have aromaticity containing a conjugated double bond. R 15 and R 16 and each independently represent an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, and substitution products thereof.

[0014] Furthermore, according to the present invention, there is provided the following cyclic olefin copolymer.

[0015] [5] A cyclic olefin copolymer having a structural unit (X) derived from an α-olefin (X') having 2 to 20 carbon atoms, a structural unit (Y) derived from a cyclic olefin (Y') having no aromatic ring, and a structural unit (Z) derived from a cyclic olefin (Z') having an aromatic ring, The cyclic olefin copolymer has an aluminum content of 100 ppm or less. [6] [5] The cyclic olefin copolymer according to [5], When the total content of the structural unit (X), the structural unit (Y) and the structural unit (Z) in the cyclic olefin copolymer is taken as 100 mol %, the content of the structural unit (X) in the cyclic olefin copolymer is 10 mol % or more and 80 mol % or less. [7] The cyclic olefin copolymer according to [5] or [6], When the total content of the structural unit (Y) and the structural unit (Z) in the cyclic olefin copolymer is taken as 100 mol %, the content of the structural unit (Z) in the cyclic olefin copolymer is 5 mol % or more and 95 mol % or less. [8] [5] to [7], wherein the cyclic olefin copolymer is The structural unit (Y) comprises a structural unit derived from a compound represented by the following formula (V): [ka] In the above formula (V), n 101 indicates 0 or 1, m 101 indicates 0 or a positive integer, q 101 indicates 0 or 1, R 101 ~R 118 and R a and R b each independently represents a hydrogen atom, a halogen atom, or a hydrocarbon group optionally substituted with a halogen atom; R 115 ~R 118 may be bonded to each other to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring may have a double bond, and R 115 and R 116 and, or R 117 and R 118 and may form an alkylidene group, provided that the alkylidene group does not contain an aromatic ring. [9] [5] to [8], wherein the cyclic olefin copolymer is The structural unit (Z) is a cyclic olefin copolymer containing a structural unit derived from one or more compounds selected from the group consisting of a compound represented by the following formula (VI), a compound represented by the following formula (VII), and a compound represented by the following formula (VIII). [ka] In the above formula (VI), n 201 and q 201 are each independently 0, 1 or 2, R 201 ~R 217each independently represents a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom other than a fluorine atom, R 210 ~R 217 One of them is a bond, q 201 When = 0, R 210 and R 211 , R 211 and R 212 , R 212 and R 213 , R 213 and R 214 , R 214 and R 215 , R 215 and R 210 may be bonded to each other to form a monocyclic or polycyclic ring, q 201 = 1 or 2, R 210 and R 211 , R 211 and R 217 , R 217 and R 217 , R 217 and R 212 , R 212 and R 213 , R 213 and R 214 , R 214 and R 215 , R 215 and R 216 , R 216 and R 216 , R 216 and R 210 may be bonded to each other to form a monocyclic or polycyclic ring, The monocyclic ring or the polycyclic ring may have a double bond, The monocyclic ring or the polycyclic ring may be an aromatic ring. [ka] In the above formula (VII), n 202 and m 201 are each independently 0, 1 or 2, q 202 is 1, 2 or 3, R 218 ~R 231 each independently represents a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom other than a fluorine atom, q 202 When =1, R 228 and R 229 , R 229 and R 230 , R 230 and R 231 may be bonded to each other to form a monocyclic or polycyclic ring, q 202 = 2 or 3, R 228 and R 228 , R 228 and R 229 , R 229 and R 230 , R 230 and R 231 , R 231 and R 231 may be bonded to each other to form a monocyclic or polycyclic ring, The monocyclic ring or the polycyclic ring may have a double bond, The monocyclic ring or the polycyclic ring may be an aromatic ring. [ka] In the above formula (VIII), q 203 is 1, 2 or 3, R 232 ~R 239 each independently represents a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom other than a fluorine atom, q 203 When =1, R 236 and R 237 , R 237 and R 238 , R 238 and R 239 may be bonded to each other to form a monocyclic or polycyclic ring, q 203 = 2 or 3, R 236 and R236 , R 236 and R 237 , R 237 and R 238 , R 238 and R 239 , R 239 and R 239 may be bonded to each other to form a monocyclic or polycyclic ring, The monocyclic ring or the polycyclic ring may have a double bond, The monocyclic ring or the polycyclic ring may be an aromatic ring.

[10] The cyclic olefin copolymer according to any one of [5] to [9], A cyclic olefin copolymer having a glass transition temperature (Tg) of 120°C or higher and 180°C or lower, as measured by a differential scanning calorimeter (DSC). [Effects of the Invention]

[0016] According to the present invention, a method for efficiently producing a cyclic olefin copolymer having an aluminum content reduced to 100 ppm or less can be provided. DETAILED DESCRIPTION OF THE INVENTION

[0017] Hereinafter, the present invention will be described based on the embodiments. In the present embodiments, "A to B" indicating a numerical range means A or more and B or less unless otherwise specified.

[0018] [Method of producing cyclic olefin copolymer] The process for producing the cyclic olefin copolymer of the present invention will be described in detail below.

[0019] The method for producing a cyclic olefin copolymer of the present embodiment includes a polymerization step of copolymerizing an α-olefin (X') having 2 to 20 carbon atoms, a cyclic olefin (Y') having no aromatic ring, and a cyclic olefin (Z') having an aromatic ring in the presence of an olefin polymerization catalyst containing a transition metal compound (A) and a compound (B). By carrying out polymerization in the presence of an olefin polymerization catalyst containing a transition metal compound (A) and a compound (B), a method for producing a cyclic olefin copolymer in which the aluminum content is reduced to 100 ppm or less can be provided.

[0020] <Transition metal compound (A)> The transition metal compound (A) is A transition metal compound (A-1) represented by the following formula (I): A transition metal compound (A-2) represented by the following formula (II), and The transition metal compound (A-3) contains one or more transition metal compounds selected from the group consisting of the transition metal compounds (A-3) represented by the following formula (III).

[0021] (Transition metal compound (A-1)) The transition metal compound (A-1) is represented by the following formula (I).

[0022] [ka]

[0023] In the above formula (I), M 1 indicates a transition metal atom in Group 4 of the periodic table. M 1 Examples of the atom include a titanium atom, a zirconium atom, and a hafnium atom.

[0024] M 1 is preferably a titanium atom or a zirconium atom, and more preferably a zirconium atom.

[0025] R 0 represents a group selected from the group consisting of alkylene groups, alkylidene groups, arylene groups, and silylene groups, and substituted groups thereof.

[0026] R 0 Examples of the alkylene group represented by the formula include a methylene group, an ethylene group, a propylene group, a butylene group, and a diphenylmethylene group. R 0 Examples of the alkylidene group represented by the formula include an isopropylidene group and a cyclohexylidene group. R 0 The arylene group represented by the formula (I) can be exemplified by a phenylene group.

[0027] R 0 Examples of the alkylene, alkylidene, arylene or silylene group substituted with methyl group include a dimethylmethylene group, a diphenylphenylene group and a dimethylsilylene group.

[0028] R 0 is preferably an alkylene group or a substituted alkylene group, more preferably a methylene group or a substituted methylene group, and even more preferably a dimethylmethylene group or a diphenylphenylene group.

[0029] R 0 Preferably, the alkyl group has 1 to 20 carbon atoms, and more preferably has 1 to 10 carbon atoms.

[0030] R 1 and R 2 each independently represents a cycloalkadienyl group or a substituted cycloalkadienyl group.

[0031] R 1 and R 2 are each independently a group selected from the group consisting of a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group, a dimethylcyclopentadienyl group, an indenyl group, a tetrahydroindenyl group, a fluorenyl group, and substituted groups thereof. R 1 and R 2 and are each independently a cyclopentadienyl group, a fluorenyl group, or a substituted derivative thereof.

[0032] R 1 and R 2and each independently preferably have 1 to 20 carbon atoms.

[0033] R 3 and R 4 each independently represents an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a silicon-containing group, a boron-containing group, and an aluminum-containing group, and substitution products thereof.

[0034] R 3 and R 4 Examples of the halogen atom represented by include a fluorine atom, a chlorine atom, and a bromine atom.

[0035] R 3 and R 4 The hydrocarbon group represented by alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, hexyl, octyl, 2-ethylhexyl, or decyl; cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a norbornyl group, a bicyclononyl group, or a tricyclodecane group; aryl groups such as a phenyl group, a tolyl group, a naphthyl group, a biphenyl group, a terphenyl group, a phenanthryl group, or an anthracenyl group; aralkyl groups such as benzyl or phenylethyl; Divalent diene derivative groups such as a 1,3-butadienyl group, an isoprenyl (2-methyl-1,3-butadienyl) group, a piperylenyl (1,3-pentadienyl) group, a 2,4-hexadienyl group, a 1,4-diphenyl-1,3-pentadienyl group, or a cyclopentadienyl group; Examples include:

[0036] R 3 and R 4 The halogen-containing group represented by halogen-containing hydrocarbon groups such as trifluoromethyl, pentafluoroethyl, 1,1,1,3,3,3-hexafluoro-2-propyl, or nonafluoro-t-butyl; Halogen-containing aryl groups such as pentafluorophenyl and pentachlorophenyl; Examples include:

[0037] R 3 and R 4 The oxygen-containing group represented by alkoxy groups such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, or a t-butoxy group; aryloxy groups such as a phenoxy group, a 2,6-dimethylphenoxy group, or a 2,4,6-trimethylphenoxy group; ester groups such as an acetyloxy group, a benzoyloxy group, a methoxycarbonyl group, a phenoxycarbonyl group, or a p-chlorophenoxycarbonyl group; ether groups; acyl groups such as a formyl group, an acetyl group, a benzoyl group, a p-chlorobenzoyl group, or a p-methoxybenzoyl group; carboxyl group; Carbonate group; hydroxy groups; peroxy group; carboxylic acid anhydride group; Furyl group; Examples include:

[0038] R 3 and R 4 The sulfur-containing group represented by mercapto group; thioester groups such as an acetylthio group, a benzoylthio group, a methylthiocarbonyl group, or a phenylthiocarbonyl group; dithioester groups; alkylthio groups such as methylthio or ethylthio groups; arylthio groups such as a phenylthio group, a methylphenylthio group, or a naphthylthio group; thioacyl group; thioether groups; thiocyanate groups; isothiocyanate groups; sulfonate ester groups such as methyl sulfonate, ethyl sulfonate, or phenyl sulfonate; sulfonamide groups such as a phenylsulfonamide group, an N-methylsulfonamide group, or an N-methyl-p-toluenesulfonamide group; Thiocarboxyl group; Dithiocarboxyl group; sulfo group; sulfonyl group; sulfinyl group; sulfenyl group; Examples include:

[0039] R 3 and R 4 The nitrogen-containing group represented by amino group; alkylamino groups such as a dimethylamino group or an ethylmethylamino group; arylamino groups such as diphenylamino groups; imino group; alkylimino groups such as a methylimino group, an ethylimino group, a propylimino group, or a butylimino group; arylimino groups such as phenylimino groups; amide group; an alkylamide group such as an acetamide group or an N-methylacetamide group; arylamide groups such as N-methylbenzamide groups; Imide groups; alkylimide groups such as acetimide groups; arylimido groups such as benzimido groups; Pyrrolidino group; hydrazino group; hydrazono group; nitro group; nitroso group; cyano group; isocyano groups; cyanate ester groups; Amidino group; diazo groups; Amino groups converted to ammonium salts Examples include: R 3 and R 4 Examples of the nitrogen-containing group substituents represented by Examples include a silylamide group and a phosphinoamide group.

[0040] R 3 and R 4 The phosphorus-containing group represented by phosphido groups; phosphoryl group; thiophosphoryl group; phosphato group Examples include:

[0041] R 3 and R 4 The silicon-containing group represented by alkylsilyl groups such as a methylsilyl group, a dimethylsilyl group, a trimethylsilyl group, an ethylsilyl group, a diethylsilyl group, a triethylsilyl group, a diphenylmethylsilyl group, a triphenylsilyl group, a dimethylphenylsilyl group, or a dimethyl-t-butylsilyl group; Examples include:

[0042] R 3 and R 4 The boron-containing group represented by Boranediyl group; Boranetriyl group; Diboranyl group; Examples include: R 3 and R 4 Examples of the boron-containing group substituents represented by an alkyl group-substituted boron group represented by (Et)2B-, (iPr)2B-, (iBu)2B-, (Et)3B, (iPr)3B, or (iBu)3B; Aryl group-substituted boron, such as (C6H5)2B-, (C6H5)3B, (C6F5)3B, or (3,5-(CF3)2C6H3)3B; Boron halides, such as BCl2- or BCl3; Alkyl-substituted boron halides such as (Et)BCl-, (iBu)BCl-, or (C6H5)2BCl; Examples include: Here, Et represents an ethyl group, iPr represents an isopropyl group, and iBu represents an isobutyl group.

[0043] R 3 and R 4 Examples of the aluminum-containing group substituents represented by the formula: Alkyl-substituted aluminum represented by (Et)2Al-, (iPr)2Al-, (iBu)2Al-, (Et)3Al, (iPr)3Al or (iBu)3Al, etc.; Aryl group-substituted aluminum represented by (C6H5)2Al-, etc.; Aluminum halides, such as AlCl2- or AlCl3; Alkyl-substituted aluminum halides represented by (Et)AlCl-, (iBu)AlCl-, etc.; Here, Et represents an ethyl group, iPr represents an isopropyl group, and iBu represents an isobutyl group.

[0044] R 3 and R 4 is a group selected from the group consisting of hydrocarbon groups, halogen-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, phosphorus-containing groups, silicon-containing groups, boron-containing groups, and aluminum-containing groups, and substitution products thereof; 3 and R 4 Each of these independently preferably has 1 to 20 carbon atoms.

[0045] R 3 and R 4 are preferably each independently a halogen atom or a hydrocarbon group.

[0046] R 3 and R 4 is a halogen atom, R 3 and R 4 are each independently a chlorine atom.

[0047] R 3 and R 4 is a hydrocarbon group, R 3 and R 4 are each independently more preferably an alkyl group, and even more preferably a methyl group.

[0048] (Transition metal compound (A-2)) The transition metal compound (A-2) is represented by the following formula (II).

[0049] [ka]

[0050] In the above formula (II), M 2 indicates a transition metal in Group 4 of the periodic table. M 2 Examples of the atom include a titanium atom, a zirconium atom, and a hafnium atom.

[0051] M 2 is preferably a titanium atom or a zirconium atom, and more preferably a titanium atom.

[0052] n 1 represents an integer of 1 to 3. 1 is M 2 Valence and X 1 Depending on the type of the transition metal compound (A-2) represented by formula (II), the transition metal compound (A-2) is selected so that the entire transition metal compound (A-2) represented by formula (II) is electrically neutral. n 1 is preferably 2.

[0053] Each L independently represents a monovalent anionic ligand in which an atom of Group 15 of the periodic table is the coordinating atom.

[0054] L is preferably a monovalent anionic ligand represented by formula (IV).

[0055] [ka]

[0056] In the above formula (IV), Y represents an atom in Group 15 of the periodic table. Examples of Y include a nitrogen atom, a phosphorus atom, and an arsenic atom.

[0057] Y is preferably a nitrogen atom.

[0058] Z represents one type of atom selected from Group 14, Group 15, or Group 16 of the periodic table. Examples of Z include a carbon atom or a silicon atom, etc., which belong to Group 14; a nitrogen atom, a phosphorus atom, or an arsenic atom, etc., which belong to Group 15; and an oxygen atom or a sulfur atom, etc., which belong to Group 16.

[0059] Z is preferably a carbon atom or a nitrogen atom, more preferably a carbon atom.

[0060] n 3 represents an integer of 1 to 3. 3 is the valence of Z and R 18 Depending on the type of the anionic ligand, the anionic group represented by formula (IV) is selected so that the entire anionic group is electrically neutral.

[0061] n 2 is preferably 1 or 2, and more preferably 2.

[0062] R 18 each independently represents a group or atom selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a silicon-containing group, a boron-containing group, and an aluminum-containing group, and the group consisting of substituted groups thereof, and each may be bonded to each other to form a ring, and the formed ring may have aromaticity including a conjugated double bond, or the formed ring may be bonded to a cyclopentadienyl group.

[0063] R 18The halogen atoms, hydrocarbon groups, halogen-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, phosphorus-containing groups, silicon-containing groups, boron-containing groups and aluminum-containing groups represented by R 3 and R 4 Examples of the halogen atom include a halogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a silicon-containing group, a boron-containing group, and an aluminum-containing group, as well as those exemplified as substitution products thereof.

[0064] R 18 Examples of structures in which the groups bond to each other to form a ring and the formed ring is bonded to a cyclopentadienyl group include the following:

[0065] [ka]

[0066] R 18 is a group selected from the group consisting of hydrocarbon groups, halogen-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, phosphorus-containing groups, silicon-containing groups, boron-containing groups, and aluminum-containing groups, and substituted groups thereof; 19 Each of the groups independently has preferably 1 to 20 carbon atoms, and more preferably 1 to 10 carbon atoms.

[0067] R 18 are preferably each independently an atom or a group selected from the group consisting of a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an amide group, an aryl group, an aralkyl group, a silyl group, an alkylamide group, an alkylsilyl group, an arylamide group, a silylamide group, a phosphinoamide group, and a phosphido group, and substitution products thereof; More preferably, it is an alkyl group, a cycloalkyl group, an aryl group, or a substituted group thereof, More preferably, it is a t-butyl group, a tricyclodecane group, a phenyl group, or a substituted group thereof, Even more preferably, it is a t-butyl group.

[0068] X 1 each independently represents a group or atom selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a silicon-containing group, a boron-containing group, and an aluminum-containing group, and substitution products thereof.

[0069] X 1 The halogen atoms, hydrocarbon groups, halogen-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, phosphorus-containing groups, silicon-containing groups, boron-containing groups and aluminum-containing groups represented by R 3 and R 4 Examples of the halogen atom include a halogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a silicon-containing group, a boron-containing group, and an aluminum-containing group, as well as those exemplified as substitution products thereof.

[0070] X 1 is a group selected from the group consisting of hydrocarbon groups, halogen-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, phosphorus-containing groups, silicon-containing groups, boron-containing groups, and aluminum-containing groups, and substituted groups thereof; 1 Each of the groups independently has preferably 1 to 20 carbon atoms, and more preferably 1 to 10 carbon atoms.

[0071] X 1 is preferably a halogen atom, more preferably a chlorine atom.

[0072] R 5 ~R 9 each independently represents a group or atom selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a silicon-containing group, a boron-containing group, and an aluminum-containing group, and a substitution product thereof; R 5 ~R 9Any two or three of these may be fused to form a ring, and the ring formed may have aromaticity containing a conjugated double bond.

[0073] R 5 ~R 9 The halogen atoms, hydrocarbon groups, halogen-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, phosphorus-containing groups, silicon-containing groups, boron-containing groups and aluminum-containing groups represented by R 3 and R 4 Examples of the halogen atom include a halogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a silicon-containing group, a boron-containing group, and an aluminum-containing group, as well as those exemplified as substitution products thereof.

[0074] R 5 ~R 9 is a group selected from the group consisting of hydrocarbon groups, halogen-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, phosphorus-containing groups, silicon-containing groups, boron-containing groups, and aluminum-containing groups, and substituted groups thereof; 5 ~R 9 Each of the groups independently has preferably 1 to 20 carbon atoms, and more preferably 1 to 10 carbon atoms.

[0075] R 5 ~R 9 is preferably a hydrogen atom.

[0076] (Transition metal compound (A-3)) The transition metal compound (A-3) is represented by the following formula (III).

[0077] [ka]

[0078] In the above formula (III), M 3 indicates a transition metal in Group 4 of the periodic table. M 3Examples of the atom include a titanium atom, a zirconium atom, and a hafnium atom.

[0079] M 3 is preferably a titanium atom or a zirconium atom, and more preferably a titanium atom.

[0080] n 2 represents an integer of 1 to 4. n 2 is M 3 Valence and X 2 Depending on the type of the transition metal compound (A-3) represented by formula (III), the transition metal compound (A-3) is selected so that the entire transition metal compound (A-3) represented by formula (III) is electrically neutral.

[0081] n 2 is preferably 2.

[0082] X 2 each independently represents an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a silicon-containing group, and a boron-containing group, and substitution products thereof.

[0083] X 2 The halogen atoms, hydrocarbon groups, halogen-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, phosphorus-containing groups, silicon-containing groups, boron-containing groups and aluminum-containing groups represented by R 3 and R 4 Examples of the halogen atom include a halogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a silicon-containing group, a boron-containing group, and an aluminum-containing group, as well as those exemplified as substitution products thereof.

[0084] X 2 is a group selected from the group consisting of hydrocarbon groups, halogen-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, phosphorus-containing groups, silicon-containing groups, boron-containing groups, and aluminum-containing groups, and substituted groups thereof; 2Each of the groups independently has preferably 1 to 20 carbon atoms, and more preferably 1 to 10 carbon atoms.

[0085] X 2 is preferably a halogen atom, more preferably a chlorine atom.

[0086] R 10 ~R 17 each independently represents an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a silicon-containing group, and a boron-containing group, and the group consisting of substituted groups thereof; R 10 ~R 14 Adjacent ones of these may be bonded to each other to form a ring, and the ring formed may have aromaticity containing a conjugated double bond.

[0087] R 10 ~R 17 The halogen atoms, hydrocarbon groups, halogen-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, phosphorus-containing groups, silicon-containing groups, boron-containing groups and aluminum-containing groups represented by R 3 and R 4 Examples of the halogen atoms, hydrocarbon groups, halogen-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, phosphorus-containing groups, silicon-containing groups, boron-containing groups and aluminum-containing groups shown in the groups indicated by the symbols, as well as substitution products thereof, can be given.

[0088] R 10 ~R 17 is a group selected from the group consisting of hydrocarbon groups, halogen-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups, phosphorus-containing groups, silicon-containing groups, boron-containing groups, and aluminum-containing groups, and substitution products thereof; 10 ~R 17 Each of the groups independently has preferably 1 to 20 carbon atoms, and more preferably 1 to 10 carbon atoms.

[0089] R 10 ~R17 Specific examples of combinations of R 10 ~R 14 and R 17 are each independently an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, and a silicon-containing group, and substitution products thereof, and R 15 and R 16 are preferably each independently an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, and a substitution product thereof. R 10 ~R 14 Adjacent ones of these may be bonded to each other to form a ring, and the ring formed may have aromaticity containing a conjugated double bond.

[0090] R 10 ~R 17 Specific examples of combinations of R 10 ~R 14 and R 17 are each independently a hydrogen atom or a hydrocarbon group, and R 15 and R 16 are each independently a hydrogen atom, a hydrocarbon group, or a halogen-containing hydrocarbon group.

[0091] R 10 ~R 17 Specific examples of combinations of R 10 ~R 14 and R 17 are each independently a hydrogen atom, an alkyl group, or a cyclic hydrocarbon group to which two or more substituents are bonded, and R 15 and R 16 and are each independently a hydrogen atom, a hydrocarbon group, or a halogen-containing alkyl group.

[0092] R 10 ~R 17 Specific examples of combinations of R 10 ~R 14 and R 17are each independently a hydrogen atom or a t-butyl group, and R 15 and R 16 are each independently a hydrogen atom or an isopropyl group.

[0093] R 10 ~R 17 Specific examples of combinations of R 10 ~R 14 are each independently a hydrogen atom, a branched alkyl group, or a cyclic hydrocarbon group to which two or more substituents are bonded, and R 15 and R 16 are each independently hydrogen, a cyclic hydrocarbon group, a branched alkyl group, or a halogen-containing alkyl group, and R 17 is preferably a hydrogen atom, a branched alkyl group or a halogen-containing alkyl group.

[0094] <Compound (B)> Compound (B) is Organometallic compound (B-1), Organoaluminum oxy compound (B-2), and The compound (B-3) contains one or more compounds selected from the group consisting of a transition metal compound represented by the above formula (I), a transition metal compound represented by the above formula (II), or a transition metal compound represented by the above formula (III) that reacts to form an ion pair.

[0095] (Organometallic compound (B-1)) Examples of the organometallic compound (B-1) (hereinafter also referred to as "component (B-1)") include organometallic compounds of Groups 1, 2, 12, and 13, such as organoaluminum compounds (B-1a) represented by general formula (B-1a), complex alkyl compounds of Group 1 metals and aluminum (B-1b) represented by general formula (B-1b), and dialkyl compounds of Group 2 or Group 12 metals (B-1c) represented by general formula (B-1c).

[0096] (B-1a):Ra m Al(ORb) n H pX q In formula (B-1a), Ra and Rb are each independently a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X is a halogen atom, m satisfies 0 < m ≦ 3, n satisfies 0 ≦ n < 3, p satisfies 0 ≦ p < 3, q satisfies 0 ≦ q < 3, and m + n + p + q = 3. Examples of the organoaluminum compound (B-1a) include trialkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, dialkylaluminum hydrides such as diisobutylaluminum hydride, and tricycloalkylaluminum.

[0097] (B-1b): M2AlRa4 In formula (B-1b), M2 is Li, Na or K, and Ra is a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. Examples of the complex alkyl compound (B-1b) include LiAl(C2H5)4, LiAl(C7H 15 )4.

[0098] (B-1c): RaRbM3 In formula (B-1c), Ra and Rb are each independently a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M3 is Mg, Zn or Cd. Examples of the compound (B-1c) include dimethylmagnesium, diethylmagnesium, di-n-butylmagnesium, ethyl-n-butylmagnesium, diphenylmagnesium, dimethylzinc, diethylzinc, di-n-butylzinc, and diphenylzinc.

[0099] Among the organometallic compounds (B-1), the organoaluminum compound (B-1a) is preferred.

[0100] (Organoaluminum oxy compound (B-2)) As the organoaluminum oxy compound (B-2) (hereinafter also referred to as "component (B-2)"), a conventionally known aluminoxane can be used as it is. Specific examples include compounds represented by the following general formula [B2-1] and / or the following general formula [B2-2], benzene-insoluble organoaluminum oxy compounds described in JP-A Nos. 2-78687 and 2-167305, and aluminoxanes having two or more types of alkyl groups described in JP-A No. 3-103407. In the formula, R represents a hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 2 or more.

[0101] [ka]

[0102] [ka]

[0103] Further, examples of the organoaluminum oxy compound (B-2) include modified methylaluminoxanes represented by the following general formula [B2-3]. In the formula, R represents a hydrocarbon group having 1 to 10 carbon atoms, and m and n each independently represent an integer of 2 or greater.

[0104] [ka]

[0105] This modified methylaluminoxane is prepared using trimethylaluminum and alkylaluminums other than trimethylaluminum. Such compounds are commonly referred to as MMAO. Such MMAOs can be prepared by the methods described in U.S. Patent Nos. 4,960,878 and 5,041,584.

[0106] Further examples of the organoaluminum oxy compound (B-2) include boron-containing organoaluminum oxy compounds represented by the following general formula [B2-4]. In the formula, R c R represents a hydrocarbon group having 1 to 10 carbon atoms.d may be the same or different and represent a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 10 carbon atoms.

[0107] [ka]

[0108] As the organoaluminum oxy-compound (B-2), methylaluminoxane, which is commercially available and therefore easily available, and MMAO prepared from trimethylaluminum and triisobutylaluminum are preferred. Among these, MMAO, which has improved solubility in various solvents and storage stability, is particularly preferred.

[0109] (Compound (B-3) that reacts with transition metal compound (A) to form an ion pair)

[0110] Examples of the compound (B-3) (hereinafter also referred to as "ionic compound (B-3)" or "component (B-3)") that reacts with the transition metal compound (A) to form an ion pair include Lewis acids, ionic compounds, borane compounds, and carborane compounds described in JP-A Nos. 1-501950, 1-502036, 3-179005, 3-179006, 3-207703, 3-207704, and US Pat. No. 5,321,106. Heteropoly compounds and isopoly compounds are also included. However, this does not include the aforementioned (B-2) organoaluminum oxy compounds.

[0111] The ionic compound (B-3) is preferably a boron compound represented by the following general formula [B3-1]. In the formula, R e+ As for H + , carbenium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, ferrocenium cation having a transition metal, etc. f From R imay be the same or different and are substituents selected from hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing groups, nitrogen-containing groups, oxygen-containing groups, halogen atoms and halogen-containing groups, and are preferably substituted aryl groups.

[0112] [ka]

[0113] Examples of the boron compound represented by the general formula [B3-1] include triphenylcarbenium tetrakis(pentafluorophenyl)borate and those described in paragraphs

[0133] to

[0144] of WO 2015 / 122414.

[0114] The method for producing a cyclic olefin copolymer according to this embodiment includes a catalyst removal step of removing the olefin polymerization catalyst.

[0115] The polymerization reaction solution obtained in the polymerization step is mixed with an alkaline aqueous solution such as an aqueous sodium hydroxide solution, and after mixing, the mixture is allowed to stand until the liquid-liquid interface separates, thereby extracting the cyclic olefin copolymer into the organic phase side and the catalyst into the alkaline aqueous layer side, and separating the olefin copolymer and the catalyst.

[0116] The aluminum content of the cyclic olefin copolymer obtained by the method for producing a cyclic olefin copolymer of this embodiment is very low, at 100 ppm or less. The mechanism by which the aluminum content of the cyclic olefin copolymer can be reduced by the production method of this embodiment is not clear, but it is thought that the use of an olefin polymerization catalyst containing the transition metal compound (A) and the compound (B) can reduce the liquid viscosity of the polymerization reaction solution or suppress precipitation of the polymer in the polymerization solution, making it easier for the catalyst to be extracted into the alkaline water layer, and efficiently removing aluminum derived from the catalyst from the cyclic olefin copolymer.

[0117] The upper limit of the aluminum content in the cyclic olefin copolymer obtained by the method for producing a cyclic olefin copolymer of this embodiment is preferably 70 ppm or less, more preferably 50 ppm or less. The lower limit of the aluminum content of the cyclic olefin copolymer obtained by the method for producing a cyclic olefin copolymer of the present embodiment is not particularly limited, but is usually 0.0001 ppm or more.

[0118] The method for producing a cyclic olefin copolymer of the present embodiment may include other steps such as a precipitation step of precipitating the obtained polymer.

[0119] [Cyclic olefin copolymer] The cyclic olefin copolymer of the present embodiment is a cyclic olefin copolymer having a structural unit (X) derived from an α-olefin (X') having 2 to 20 carbon atoms, a structural unit (Y) derived from a cyclic olefin (Y') having no aromatic ring, and a structural unit (Z) derived from a cyclic olefin (Z') having an aromatic ring, The cyclic olefin copolymer has an aluminum content of 100 ppm or less.

[0120] The structural unit (X) according to this embodiment may be linear or branched, and examples thereof include linear α-olefins having 2 to 20 carbon atoms, such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene; and branched α-olefins having 4 to 20 carbon atoms, such as 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, and 3-ethyl-1-hexene. Among these, linear α-olefins having 2 to 4 carbon atoms are preferred, and ethylene is particularly preferred. Such linear or branched α-olefins can be used singly or in combination of two or more.

[0121] In the cyclic olefin copolymer of this embodiment, when the total content of the structural units (X), (Y), and (Z) in the cyclic olefin copolymer is taken as 100 mol%, the content of the structural unit (X) in the cyclic olefin copolymer is preferably 10 mol% or more and 80 mol% or less, more preferably 30 mol% or more and 75 mol% or less, and even more preferably 40 mol% or more and 70 mol% or less. By ensuring that the content of the structural unit (X) is at least the above lower limit, the heat resistance and dimensional stability of the molded article obtained from the cyclic olefin copolymer of this embodiment can be improved. Furthermore, by ensuring that the content of the structural unit (X) is at most the above upper limit, the transparency and other properties of the molded article obtained can be improved. In this embodiment, the content of the structural unit (X) is, for example, 1 H-NMR or 13 It can be measured by C-NMR.

[0122] From the viewpoint of further improving the refractive index of a molded article obtained from the cyclic olefin copolymer of this embodiment, the structural unit (Y) of this embodiment preferably contains a structural unit derived from a compound represented by the following formula (V):

[0123] [ka]

[0124] In the above formula (V), n 101 indicates 0 or 1, m 101 indicates 0 or a positive integer, q 101 indicates 0 or 1, R 101 ~R 118 and R a and R b each independently represents a hydrogen atom, a halogen atom, or a hydrocarbon group optionally substituted with a halogen atom; R 115 ~R 118may be bonded to each other to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring may have a double bond, and R 115 and R 116 and, or R 117 and R 118 and may form an alkylidene group, provided that the alkylidene group does not contain an aromatic ring.

[0125] Among these, the structural unit (Y) according to this embodiment preferably comprises at least one structural unit selected from structural units derived from bicyclo[2.2.1]-2-heptene, structural units derived from tetracyclo[4.4.0.12,5.17,10]-3-dodecene, and structural units derived from hexacyclo[6,6,1,13,6,110,13,02,7,09,14]heptadecene-4, and more preferably comprises at least one structural unit selected from structural units derived from bicyclo[2.2.1]-2-heptene and structural units derived from tetracyclo[4.4.0.12,5.17,10]-3-dodecene, and particularly preferably comprises a structural unit derived from tetracyclo[4.4.0.12,5.17,10]-3-dodecene.

[0126] The structural unit according to this embodiment ( Z ) preferably contains a structural unit derived from one or more compounds selected from the group consisting of a compound represented by the following formula (VI), a compound represented by the following formula (VII), and a compound represented by the following formula (VIII).

[0127] [ka]

[0128] In the above formula (VI), n 201 and q 201 are each independently 0, 1 or 2, R 201 ~R 217each independently represents a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom other than a fluorine atom, R 210 ~R 217 One of them is a bond, q 201 When = 0, R 210 and R 211 , R 211 and R 212 , R 212 and R 213 , R 213 and R 214 , R 214 and R 215 , R 215 and R 210 may be bonded to each other to form a monocyclic or polycyclic ring, q 201 = 1 or 2, R 210 and R 211 , R 211 and R 217 , R 217 and R 217 , R 217 and R 212 , R 212 and R 213 , R 213 and R 214 , R 214 and R 215 , R 215 and R 216 , R 216 and R 216 , R 216 and R 210 may be bonded to each other to form a monocyclic or polycyclic ring, The monocyclic ring or the polycyclic ring may have a double bond, The monocyclic ring or the polycyclic ring may be an aromatic ring.

[0129] [ka]

[0130] In the above formula (VII), n 202 and m 201are each independently 0, 1 or 2, q 202 is 1, 2 or 3, R 218 ~R 231 each independently represents a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom other than a fluorine atom, q 202 When =1, R 228 and R 229 , R 229 and R 230 , R 230 and R 231 may be bonded to each other to form a monocyclic or polycyclic ring, q 202 = 2 or 3, R 228 and R 228 , R 228 and R 229 , R 229 and R 230 , R 230 and R 231 , R 231 and R 231 may be bonded to each other to form a monocyclic or polycyclic ring, The monocyclic ring or the polycyclic ring may have a double bond, The monocyclic ring or the polycyclic ring may be an aromatic ring.

[0131] [ka]

[0132] In the above formula (VIII), q 203 is 1, 2 or 3, R 232 ~R 239 each independently represents a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom other than a fluorine atom, q 203 When =1, R 236 and R 237 , R 237 and R238 , R 238 and R 239 may be bonded to each other to form a monocyclic or polycyclic ring, q 203 = 2 or 3, R 236 and R 236 , R 236 and R 237 , R 237 and R 238 , R 238 and R 239 , R 239 and R 239 may be bonded to each other to form a monocyclic or polycyclic ring, The monocyclic ring or the polycyclic ring may have a double bond, The monocyclic ring or the polycyclic ring may be an aromatic ring.

[0133] Examples of hydrocarbon groups having 1 to 20 carbon atoms in the structural unit (Z) of this embodiment are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, and an aromatic hydrocarbon group. More specifically, alkyl groups include methyl, ethyl, propyl, isopropyl, amyl, hexyl, octyl, decyl, dodecyl, and octadecyl groups. Examples of cycloalkyl groups include cyclohexyl groups. Examples of aromatic hydrocarbon groups include aryl groups or aralkyl groups such as phenyl, tolyl, naphthyl, benzyl, and phenylethyl. These hydrocarbon groups may be substituted with halogen atoms other than fluorine atoms.

[0134] Among these, the cyclic olefin having an aromatic ring according to this embodiment is preferably one having one aromatic ring, and for example, at least one selected from benzonorbornadiene, indenenorbornene, and methylphenylnorbornene is preferred.

[0135] Examples of the cyclic olefin having an aromatic ring according to this embodiment include a compound represented by the following formula (VI'), a compound represented by the following formula (VII'), a compound represented by the following formula (VIII'), etc. These cyclic olefins having an aromatic ring may be used alone or in combination of two or more.

[0136] [ka]

[0137] [ka]

[0138] [ka]

[0139] In the above formula (VI'), the above formula (VII'), and the above formula (VIII'), m 301 , n 301 and n 302 is 0, 1, or 2, and R 301 ~R 336 are each independently a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom other than a fluorine atom, and R 310 and R 311 , R 311 and R 312 , R 312 and R 313 , R 313 and R 314 , R 325 and R 326 , R 326 and R 327 , R 327 and R 328 , R 333 and R 334 , R 334 and R 335 , R 335 and R 336may be bonded to each other to form a single ring, and the single ring may have a double bond.

[0140] In addition, in the above formula (VI'), the above formula (VII'), and the above formula (VIII'), m 301 is preferably 0 or 1, and more preferably 1. 301 and n 302 is preferably 0 or 1, and more preferably 0. 301 ~R 336 is preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrogen atom.

[0141] Furthermore, the hydrocarbon groups having 1 to 20 carbon atoms in the above formulas (VI'), (VII'), and (VIII') each independently include, for example, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, and an aromatic hydrocarbon group. More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, and an octadecyl group. Examples of the cycloalkyl group include a cyclohexyl group. Examples of the aromatic hydrocarbon group include an aryl group or an aralkyl group such as a phenyl group, a tolyl group, a naphthyl group, a benzyl group, and a phenylethyl group. These hydrocarbon groups may be substituted with a halogen atom other than a fluorine atom.

[0142] Among these, the cyclic olefin having an aromatic ring according to this embodiment is preferably one having one aromatic ring, and for example, at least one selected from benzonorbornadiene, indenenorbornene, and methylphenylnorbornene is preferred.

[0143] In the cyclic olefin copolymer of this embodiment, when the total content of the structural units (Y) and (Z) in the cyclic olefin copolymer is taken as 100 mol%, the content of the structural unit (Z) in the cyclic olefin copolymer is preferably 5 mol% or more and 95 mol% or less, more preferably 10 mol% or more and 90 mol% or less, even more preferably 20 mol% or more and 80 mol% or less, even more preferably 30 mol% or more and 79 mol% or less, and even more preferably 40 mol% or more and 78 mol% or less. By ensuring that the content of the structural unit (Z) is at least the above lower limit, the molded article obtained from the cyclic olefin copolymer according to this embodiment can have a high refractive index and a lower Abbe number. Furthermore, by ensuring that the content of the structural unit (Z) is at most the above upper limit, the balance between the refractive index and Abbe number of the molded article obtained from the cyclic olefin copolymer according to this embodiment can be made even better. In this embodiment, the content of the structural unit (Y) and the structural unit (Z) is, for example, 1 H-NMR or 13 It can be measured by C-NMR.

[0144] The copolymerization type of the cyclic olefin copolymer according to this embodiment is not particularly limited, and examples thereof include a random copolymer, a block copolymer, etc. A random copolymer is preferred from the viewpoint of being able to obtain a molded article having excellent optical properties such as transparency, Abbe number, refractive index, and birefringence from the cyclic olefin copolymer according to this embodiment.

[0145] The glass transition temperature (Tg) of the cyclic olefin copolymer according to this embodiment, as measured by a differential scanning calorimeter (DSC), is preferably 120°C or higher and 180°C or lower, more preferably 130°C or higher and 170°C or lower, and even more preferably 140°C or higher and 160°C or lower, from the viewpoint of further improving the heat resistance while maintaining good transparency, haze, Abbe number, birefringence, refractive index, etc. of a molded article obtained from the cyclic olefin copolymer of this embodiment.

[0146] The intrinsic viscosity [η] (in decalin at 135°C) of the cyclic olefin copolymer according to this embodiment is, for example, 0.05 to 5.0 dl / g, preferably 0.2 to 4.0 dl / g, more preferably 0.3 to 2.0 dl / g, and particularly preferably 0.4 to 1.0 dl / g.

[0147] The aluminum content of the cyclic olefin copolymer according to this embodiment is 100 ppm or less, preferably 70 ppm or less, and more preferably 50 ppm or less.

[0148] The use of the cyclic olefin copolymer according to this embodiment is not particularly limited, and it can be used for films, sheets, lenses, containers, etc. The aluminum content of the cyclic olefin copolymer according to this embodiment is very low, at 100 ppm or less, and adverse effects on color tone and physical properties during molding of the cyclic olefin copolymer are suppressed, so the copolymer can be suitably used in applications requiring transparency, such as optical lenses and medical containers.

[0149] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various other configurations can also be adopted. Furthermore, the present invention is not limited to the above-described embodiment, and modifications and improvements within the scope of achieving the object of the present invention are included in the present invention. [Example]

[0150] Hereinafter, embodiments of the present invention will be specifically described based on examples, but the embodiments of the present invention are not limited to these examples.

[0151] [Example 1] Nitrogen as an inert gas was passed through a 2000 ml glass reaction vessel equipped with a stirrer at a flow rate of 100 Nl / hr for 30 minutes, and then the following reagent (i-1) was supplied in the following amount, and the solvent temperature was raised to 50°C while stirring the polymerization solvent at 600 rpm.

[0152] (i-1) Cyclohexane / hexane (3 / 1) mixed solvent: 845 ml Triisobutylaluminum (hereinafter referred to as TiBAL) in a cyclohexane / hexane (3 / 1) mixture (concentration 97.6 g / L): 88 ml Tetracyclododecene (hereinafter referred to as TD): 30 ml Benzonorbornadiene (hereinafter referred to as BNBD): 37ml

[0153] After the temperature of the solvent reached a predetermined temperature, the flow gas was switched from nitrogen to ethylene / hydrogen, and ethylene and hydrogen were flowed at flow rates of 150 Nl / hr and 5.0 Nl / hr, respectively (flow rate ratio 30 / 1), and the following reagent (ii-1) was continuously fed at the following feed rate, and polymerization was carried out while occasionally removing the solution so as to maintain the liquid level of the polymerization solution constant.

[0154] (ii-1) Cyclohexane / hexane (3 / 1) mixed solvent: 1280 ml / hr TiBAL cyclohexane / hexane (3 / 1) mixed solution (concentration 97.6g / L): 176ml / hr Triphenylcarbenium tetrakis(pentafluorophenyl)borate (hereinafter referred to as borate (1)) in a cyclohexane / hexane (3 / 1) mixture (concentration 18.4 g / L): 173 ml / hr Isopropylidenecyclopentadienyl-9-fluorenylzirconium dimethyl (hereinafter referred to as transition metal compound (1)) in toluene solution (concentration 3.04 g / L): 111 ml / hr TD: 134 ml / hr BNBD: 126 ml / hr

[0155] The transition metal compound (1) corresponds to the transition metal compound (A-1).

[0156] One hour and 30 minutes after the start of charging the reagent (ii-1) above, the solution in the reaction vessel was sampled over 30 minutes, and the sampled solution was brought into contact with 6.9 g of methanol to obtain a cyclic olefin copolymer solution.

[0157] 500 mL of the obtained cyclic olefin copolymer solution was placed in a glass container equipped with a stirrer. The same volume of aqueous sodium hydroxide solution (1.0 mass%) was added and stirred. After waiting for the liquid-liquid interface to separate, the aqueous layer was removed. The same procedure was carried out with ion-exchanged water to obtain a catalyst-removed solution.

[0158] 50 g of the resulting catalyst-removed solution was diluted with 270 g of cyclohexane. The diluted catalyst-removed solution was then gradually added to 1700 mL of stirred acetone to precipitate a cyclic olefin copolymer. The precipitated cyclic olefin copolymer was collected by suction filtration and dried in a vacuum dryer at 130°C for 10 hours, yielding 4.75 g of cyclic olefin copolymer.

[0159] [Example 2] A cyclic olefin copolymer solution was obtained in the same manner as in Example 1 except for the following points. The above reagent (i-1) was replaced with the following reagent (i-2): The above reagent (ii-1) was replaced with the following reagent (ii-2): After 3 hours had passed since the start of adding the reagents (ii-2) below, the solution in the reaction vessel was sampled over 1 hour. The solution taken from the reaction vessel was brought into contact with 13.8 g of methanol.

[0160] (i-2) Cyclohexane / hexane (3 / 1) mixed solvent: 771 ml TiBAL cyclohexane / hexane (3 / 1) mixed solution (concentration 97.6g / L): 176ml TD: 23ml BNBD: 31ml

[0161] (ii-2) Cyclohexane / hexane (3 / 1) mixed solvent: 544 ml / hr TiBAL cyclohexane / hexane (3 / 1) mixed solution (concentration 97.6g / L): 176ml / hr Borate (1) in a cyclohexane / hexane (3 / 1) mixture (concentration 8.2 g / L): 79 ml / hr Transition metal compound (1) in toluene solution (concentration 1.93 g / L): 72 ml / hr TD: 67ml / hr BNBD: 63ml / hr

[0162] A catalyst-removed solution was obtained in the same manner as in Example 1 from 500 mL of the resulting cyclic olefin copolymer solution.

[0163] 50 g of the resulting catalyst-removed solution was diluted with 393 g of cyclohexane. The diluted catalyst-removed solution was then gradually added to 2350 mL of stirred acetone to precipitate a cyclic olefin copolymer. The precipitated cyclic olefin copolymer was collected by suction filtration and dried in a vacuum dryer at 130°C for 10 hours, yielding 6.65 g of cyclic olefin copolymer.

[0164] [Example 3] A cyclic olefin copolymer solution was obtained in the same manner as in Example 1 except for the following points. The above reagent (i-1) was replaced with the following reagent (i-3): The above reagent (ii-1) was replaced with the following reagent (ii-3)

[0165] (i-3) Cyclohexane / hexane (3 / 1) mixed solvent: 842 ml TiBAL cyclohexane / hexane (3 / 1) mixed solution (concentration 97.6g / L): 88ml TD: 43ml BNBD: 28ml

[0166] (ii-3) Cyclohexane / hexane (3 / 1) mixed solvent: 1275 ml / hr TiBAL cyclohexane / hexane (3 / 1) mixed solution (concentration 97.6g / L): 176ml / hr Borate (1) in a cyclohexane / hexane (3 / 1) mixture (concentration 20.3 g / L): 157 ml / hr Transition metal compound (1) in toluene (concentration 2.94 g / L): 115 ml / hr TD: 184 ml / hr BNBD: 93 ml / hr

[0167] A catalyst-removed solution was obtained in the same manner as in Example 1 from 500 mL of the resulting cyclic olefin copolymer solution.

[0168] 50 g of the resulting catalyst-removed solution was diluted with 328 g of cyclohexane. The diluted catalyst-removed solution was then gradually added to 2000 mL of stirred acetone to precipitate a cyclic olefin copolymer. The precipitated cyclic olefin copolymer was collected by suction filtration and dried in a vacuum dryer at 130°C for 10 hours, yielding 5.67 g of cyclic olefin copolymer.

[0169] [Example 4] A cyclic olefin copolymer solution was obtained in the same manner as in Example 1 except for the following points. The above reagent (i-1) was replaced with the following reagent (i-4): The above reagent (ii-1) was replaced with the following reagent (ii-4)

[0170] (i-4) Cyclohexane / hexane (3 / 1) mixed solvent: 850 ml TiBAL cyclohexane / hexane (3 / 1) mixed solution (concentration 97.6g / L): 88ml Tetracyclododecene (hereinafter referred to as TD): 27 ml Benzonorbornadiene (hereinafter referred to as BNBD): 36 ml

[0171] (ii-4) Cyclohexane / hexane (3 / 1) mixed solvent: 1511 ml / hr TiBAL cyclohexane / hexane (3 / 1) mixed solution (concentration 97.6g / L): 176ml / hr Borate (1) in a cyclohexane / hexane (3 / 1) mixture (concentration 20.3 g / L): 74 ml / hr Transition metal compound (1) in toluene (concentration 2.94 g / L): 40 ml / hr TD: 98ml / hr BNBD: 101 ml / hr

[0172] A catalyst-removed solution was obtained in the same manner as in Example 1 from 500 mL of the resulting cyclic olefin copolymer solution.

[0173] 50 g of the resulting catalyst-removed solution was diluted with 164 g of cyclohexane. The diluted catalyst-removed solution was then gradually added to 1250 mL of stirred acetonitrile to precipitate a cyclic olefin copolymer. The precipitated cyclic olefin copolymer was collected by suction filtration and dried in a vacuum dryer at 130°C for 10 hours, yielding 3.21 g of cyclic olefin copolymer.

[0174] [Example 5] A cyclic olefin copolymer solution was obtained in the same manner as in Example 1 except for the following points. The above reagent (i-1) was replaced with the following reagent (i-5): Ethylene was supplied at a flow rate of 156 Nl / hr and hydrogen at a flow rate of 1.44 L / hr (flow rate ratio 108 / 1). The above reagent (ii-1) was replaced with the following reagent (ii-5) The solution taken from the reaction vessel was brought into contact with 0.7 g of methanol.

[0175] (i-5) Cyclohexane / hexane (3 / 1) mixed solvent: 907 ml TiBAL cyclohexane / hexane (3 / 1) mixed solution (concentration 97.6g / L): 9ml TD: 28ml BNBD: 56ml

[0176] (ii-5) Cyclohexane / hexane (3 / 1) mixed solvent: 1564 ml / hr TiBAL cyclohexane / hexane (3 / 1) mixed solution (concentration 97.6g / L): 18ml / hr Borate (1) in a cyclohexane / hexane (3 / 1) mixture (concentration 18.4 g / L): 90 ml / hr Diphenylmethylenecyclopentadienyl-9-fluorenylzirconium dichloride (hereinafter referred to as transition metal compound (2)) in toluene solution (concentration 2.51 g / L): 99 ml / hr TD: 88ml / hr BNBD: 142 ml / hr

[0177] The transition metal compound (2) corresponds to the transition metal compound (A-1).

[0178] A catalyst-removed solution was obtained in the same manner as in Example 1 from 500 mL of the resulting cyclic olefin copolymer solution.

[0179] 50 g of the resulting catalyst-removed solution was diluted with 123 g of cyclohexane. The diluted catalyst-removed solution was then gradually added to 920 mL of stirred acetone to precipitate a cyclic olefin copolymer. The precipitated cyclic olefin copolymer was collected by suction filtration and dried in a vacuum dryer at 130°C for 10 hours, yielding 2.60 g of cyclic olefin copolymer.

[0180] [Example 6] A cyclic olefin copolymer solution was obtained in the same manner as in Example 1 except for the following points. The above reagent (i-1) was replaced with the following reagent (i-6) The above reagent (ii-1) was replaced with the following reagent (ii-6) The solution taken from the reaction vessel was brought into contact with 1.4 g of methanol.

[0181] (i-6) Cyclohexane / hexane (3 / 1) mixed solvent: 884 ml TiBAL cyclohexane / hexane (3 / 1) mixed solution (concentration 97.6g / L): 18ml TD: 56ml BNBD: 42ml

[0182] (ii-6) Cyclohexane / hexane (3 / 1) mixed solvent: 1494 ml / hr TiBAL cyclohexane / hexane (3 / 1) mixed solution (concentration 97.6g / L): 37ml / hr Borate (1) in cyclohexane / hexane (3 / 1) solution (concentration 32.2 g / L): 103 ml / hr Isopropylidenecyclopentadienyl-3,6-di-t-butyl-9-fluorenylzirconium dichloride (hereinafter referred to as transition metal compound (3)) in toluene (concentration 4.66 g / L): 105 ml / hr TD: 148ml / hr BNBD: 112 ml / hr

[0183] The transition metal compound (3) corresponds to the transition metal compound (A-1).

[0184] A catalyst-removed solution was obtained in the same manner as in Example 1 from 500 mL of the resulting cyclic olefin copolymer solution.

[0185] 50 g of the resulting catalyst-removed solution was diluted with 133 g of cyclohexane. The diluted catalyst-removed solution was then gradually added to 970 mL of stirred acetone to precipitate a cyclic olefin copolymer. The precipitated cyclic olefin copolymer was collected by suction filtration and dried in a vacuum dryer at 130°C for 10 hours, yielding 2.75 g of cyclic olefin copolymer.

[0186] [Example 7] A cyclic olefin copolymer solution was obtained in the same manner as in Example 1 except for the following points. The above reagent (i-1) was replaced with the following reagent (i-7) Ethylene was circulated at a flow rate of 156 Nl / hr and hydrogen at a flow rate of 0.96 Nl / hr (flow rate ratio 163 / 1). The above reagent (ii-1) was replaced with the following reagent (ii-7) The solution taken from the reaction vessel was brought into contact with 0.6 g of methanol.

[0187] (i-7) Cyclohexane / hexane (3 / 1) mixed solvent: 942 ml TiBAL cyclohexane / hexane (3 / 1) mixed solution (concentration 97.6 g / L): 7 ml TD: 21ml BNBD: 31ml

[0188] (ii-7) Cyclohexane / hexane (3 / 1) mixed solvent: 1631 ml / hr TiBAL cyclohexane / hexane (3 / 1) mixed solution (concentration 97.6g / L): 14ml / hr Borate (1) in cyclohexane / hexane (3 / 1) solution (concentration 18.4 g / L): 55 ml / hr Diphenylmethylenecyclopentadienyl indenyl zirconium dichloride (hereinafter referred to as transition metal compound (4)) in toluene solution (concentration 1.53 g / L): 91 ml / hr TD: 102 ml / hr BNBD: 107 ml / hr

[0189] The transition metal compound (4) corresponds to the transition metal compound (A-1).

[0190] A catalyst-removed solution was obtained in the same manner as in Example 1 from 500 mL of the resulting cyclic olefin copolymer solution.

[0191] 50 g of the resulting catalyst-removed solution was diluted with 239 g of cyclohexane. The diluted catalyst-removed solution was then gradually added to 1550 mL of stirred acetone to precipitate a cyclic olefin copolymer. The precipitated cyclic olefin copolymer was collected by suction filtration and dried in a vacuum dryer at 130°C for 10 hours, yielding 4.34 g of cyclic olefin copolymer.

[0192] [Example 8] A cyclic olefin copolymer solution was obtained in the same manner as in Example 1 except for the following points. The above reagent (i-1) was replaced with the following reagent (i-8) Ethylene was circulated at a flow rate of 156 Nl / hr and hydrogen at a flow rate of 1.44 Nl / hr (flow rate ratio 108 / 1). The above reagent (ii-1) was replaced with the following reagent (ii-8) The solution taken from the reaction vessel was brought into contact with 0.7 g of methanol.

[0193] (i-8) Cyclohexane / hexane (3 / 1) mixed solvent: 964 ml TiBAL cyclohexane / hexane (3 / 1) mixed solution (concentration 97.6g / L): 9ml TD: 10ml BNBD: 17ml

[0194] (ii-8) Cyclohexane / hexane (3 / 1) mixed solvent: 1651 ml / hr TiBAL cyclohexane / hexane (3 / 1) mixed solution (concentration 97.6g / L): 17ml / hr Borate (1) in cyclohexane / hexane (3 / 1) solution (concentration 18.6 g / L): 84 ml / hr Bis-t-butylketimide cyclopentadienyltitanium dichloride (hereinafter referred to as transition metal compound (5)) in toluene (concentration 1.58 g / L): 87 ml / hr TD: 86ml / hr BNBD: 75ml / hr

[0195] The transition metal compound (5) corresponds to the transition metal compound (A-2).

[0196] A catalyst-removed solution was obtained in the same manner as in Example 1 from 500 mL of the resulting cyclic olefin copolymer solution.

[0197] 50 g of the resulting catalyst-removed solution was diluted with 257 g of cyclohexane. The diluted catalyst-removed solution was then gradually added to 1650 mL of stirred acetone to precipitate a cyclic olefin copolymer. The precipitated cyclic olefin copolymer was collected by suction filtration and dried in a vacuum dryer at 130°C for 10 hours, yielding 4.61 g of cyclic olefin copolymer.

[0198] [Example 9] A cyclic olefin copolymer solution was obtained in the same manner as in Example 1 except for the following points. The above reagent (i-1) was replaced with the following reagent (i-8) Ethylene was circulated at a flow rate of 156 Nl / hr and hydrogen at a flow rate of 0.24 Nl / hr (flow rate ratio 650 / 1). The above reagent (ii-1) was replaced with the following reagent (ii-8) The solution taken from the reaction vessel was brought into contact with 0.6 g of methanol.

[0199] (i-9) Cyclohexane / hexane (3 / 1) mixed solvent: 655 ml TiBAL cyclohexane / hexane (3 / 1) mixed solution (concentration 97.6 g / L): 7 ml TD: 5ml BNBD: 23ml

[0200] (ii-9) Cyclohexane / hexane (3 / 1) mixed solvent: 1329 ml / hr TiBAL cyclohexane / hexane (3 / 1) mixed solution (concentration 97.6g / L): 14ml / hr Borate (1) in cyclohexane / hexane (3 / 1) solution (concentration 16.1 g / L): 223 ml / hr 3,5-bismethylethyl-1-pyrazolate-t-butylcyclopentadienyltitanium dichloride (hereinafter referred to as transition metal compound (6)) in toluene solution (concentration 1.83 g / L): 278 ml / hr TD: 68ml / hr BNBD: 88ml / hr

[0201] The transition metal compound (6) corresponds to the transition metal compound (A-3).

[0202] A catalyst-removed solution was obtained in the same manner as in Example 1 from 500 mL of the resulting cyclic olefin copolymer solution.

[0203] 50 g of the resulting catalyst-removed solution was diluted with 210 g of cyclohexane. The diluted catalyst-removed solution was then gradually added to 1,370 mL of stirred acetone to precipitate a cyclic olefin copolymer. The precipitated cyclic olefin copolymer was collected by suction filtration and dried in a vacuum dryer at 130°C for 10 hours, yielding 3.90 g of cyclic olefin copolymer.

[0204] [Comparative Example 1] A cyclic olefin copolymer solution was obtained in the same manner as in Example 1 except for the following points. The above reagent (i-1) was replaced with the following reagent (i-1') Ethylene was circulated at a flow rate of 150 Nl / hr and hydrogen at a flow rate of 3.2 Nl / hr (flow rate ratio 47 / 1). The above reagent (ii-1) was replaced with the following reagent (ii-1') The solution taken from the reaction vessel was brought into contact with 2.0 g of methanol.

[0205] (i-1´) Cyclohexane / hexane (3 / 1) mixed solvent: 932 ml Methylaluminoxane toluene solution (concentration of organoaluminum oxy compound: 6.5% by mass): 6 ml TD: 20ml BNBD: 24ml

[0206] (ii-1´) Cyclohexane / hexane (3 / 1) mixed solvent: 1865 ml / hr Methylaluminoxane toluene solution (concentration of organoaluminum oxy compound: 6.5% by mass): 12 ml / hr TD: 40ml / hr BNBD: 47ml / hr Bis-[N-(3-phenylsalicylidene)-4-t-butylanilinato]titanium dichloride (hereinafter referred to as transition metal compound (7)) in toluene (concentration 1.78 g / L): 36 ml / hr

[0207] A catalyst-removed solution was obtained in the same manner as in Example 1 from 500 mL of the resulting cyclic olefin copolymer solution.

[0208] 50 g of the resulting catalyst-removed solution was diluted with 83 g of cyclohexane. The diluted catalyst-removed solution was then gradually added to 700 mL of stirred acetone to precipitate a cyclic olefin copolymer. The precipitated cyclic olefin copolymer was collected by suction filtration and dried in a vacuum dryer at 130°C for 10 hours, yielding 2.00 g of cyclic olefin copolymer.

[0209] Comparative Example 2 A cyclic olefin copolymer solution was obtained in the same manner as in Example 1 except for the following points. The above reagent (i-1) was replaced with the following reagent (i-2') Ethylene was circulated at a flow rate of 150 Nl / hr and hydrogen at a flow rate of 3.2 Nl / hr (flow rate ratio 47 / 1). The above reagent (ii-1) was replaced with the following reagent (ii-2') The solution taken from the reaction vessel was brought into contact with 2.0 g of methanol.

[0210] (i-2´) Cyclohexane / hexane (3 / 1) mixed solvent: 930 ml Methylaluminoxane toluene solution (concentration of organoaluminum oxy compound: 6.5% by mass): 6 ml TD: 21ml BNBD: 28ml

[0211] (ii-2´) Cyclohexane / hexane (3 / 1) mixed solvent: 1860 ml / hr Methylaluminoxane toluene solution (concentration of organoaluminum oxy compound: 6.5% by mass): 12 ml / hr TD: 43ml / hr BNBD: 55ml / hr Transition metal compound (7) in toluene (concentration 2.14 g / L): 30 ml / hr

[0212] A catalyst-removed solution was obtained in the same manner as in Example 1 from 500 mL of the resulting cyclic olefin copolymer solution.

[0213] 50 g of the resulting catalyst-removed solution was diluted with 103 g of cyclohexane. The diluted catalyst-removed solution was then gradually added to 800 mL of stirred acetone to precipitate a cyclic olefin copolymer. The precipitated cyclic olefin copolymer was collected by suction filtration and dried in a vacuum dryer at 130°C for 10 hours, yielding 2.30 g of cyclic olefin copolymer.

[0214] Comparative Example 3 A cyclic olefin copolymer solution was obtained in the same manner as in Example 1 except for the following points. The above reagent (i-1) was replaced with the following reagent (i-3') The above reagent (ii-1) was replaced with the following reagent (ii-3') The solution taken from the reaction vessel was brought into contact with 2.1 g of methanol.

[0215] (i-3´) Cyclohexane / hexane (3 / 1) mixed solvent: 900 ml Methylaluminoxane toluene solution (concentration of organoaluminum oxy compound: 6.5% by mass): 8 ml, TD: 6ml, BNBD: 14ml

[0216] (ii-3´) Cyclohexane / hexane (3 / 1) mixed solvent: 1838 ml / hr Methylaluminoxane toluene solution (concentration of organoaluminum oxy compound: 6.5% by mass): 13 ml / hr TD: 49ml / hr BNBD: 65ml / hr Transition metal compound (7) in toluene (concentration 1.93 g / L): 35 ml / hr

[0217] A catalyst-removed solution was obtained in the same manner as in Example 1 from 500 mL of the resulting cyclic olefin copolymer solution.

[0218] 50 g of the resulting catalyst-removed solution was diluted with 33 g of cyclohexane. The diluted catalyst-removed solution was then gradually added to 450 mL of stirred acetone to precipitate a cyclic olefin copolymer. The precipitated cyclic olefin copolymer was collected by suction filtration and dried in a vacuum dryer at 130°C for 10 hours, yielding 1.25 g of cyclic olefin copolymer.

[0219] Comparative Example 4 In the same manner as in Comparative Example 3, a cyclic olefin copolymer solution was obtained.

[0220] A catalyst-removed solution was obtained in the same manner as in Example 1 from 500 mL of the resulting cyclic olefin copolymer solution.

[0221] 50 g of the resulting catalyst-removed solution was gradually added to 270 mL of stirred acetone to precipitate a cyclic olefin copolymer. The precipitated cyclic olefin copolymer was collected by suction filtration and dried in a vacuum dryer at 130°C for 10 hours, yielding 0.75 g of the cyclic olefin copolymer.

[0222] Comparative Example 5 A cyclic olefin copolymer solution was obtained in the same manner as in Example 1 except for the following points. The above reagent (i-1) was replaced with the following reagent (i-5') The above reagent (ii-1) was replaced with the following reagent (ii-5') The solution taken from the reaction vessel was brought into contact with 2.0 g of methanol.

[0223] (i-5´) Cyclohexane / hexane (3 / 1) mixed solvent: 926 ml Methylaluminoxane toluene solution (concentration of organoaluminum oxy compound: 6.5% by mass): 6 ml TD: 22ml BNBD: 29ml

[0224] (ii-5´) Cyclohexane / hexane (3 / 1) mixed solvent: 1853 ml / hr Methylaluminoxane toluene solution (concentration of organoaluminum oxy compound: 6.5% by mass): 12 ml / hr TD: 45ml / hr BNBD: 57ml / hr Transition metal compound (7) in toluene (concentration 1.90 g / L): 33 ml / hr

[0225] A catalyst-removed solution was obtained in the same manner as in Example 1 from 500 mL of the resulting cyclic olefin copolymer solution.

[0226] 50 g of the resulting catalyst-removed solution was diluted with 100 g of cyclohexane. The diluted catalyst-removed solution was then gradually added to 800 mL of stirred acetone to precipitate a cyclic olefin copolymer. The precipitated cyclic olefin copolymer was collected by suction filtration and dried in a vacuum dryer at 130°C for 10 hours, yielding 2.25 g of cyclic olefin copolymer.

[0227] Various physical properties were evaluated by the following methods for Examples 1 to 9 and Comparative Examples 1 to 5. The results are shown in Table 1.

[0228] (Comonomer (cyclic olefin) content of cyclic olefin copolymer) According to the description in paragraph

[0132] of WO2019 / 107363, the comonomer (cyclic olefin) content of the polymer was determined by 13C-NMR spectrum.

[0229] (glass transition temperature Tg (℃)) The glass transition temperature (Tg) of the cyclic olefin copolymer was measured under an N2 (nitrogen) atmosphere using a DSC-6220 manufactured by Shimadzu Science Co., Ltd. The cyclic olefin copolymer was heated from room temperature to 250°C at a heating rate of 10°C / min, held at that temperature for 5 minutes, and then cooled to -20°C at a heating rate of 10°C / min, held at that temperature for 5 minutes. The glass transition temperature (Tg) of the cyclic olefin copolymer was determined from the endothermic curve obtained when the temperature was raised to 250°C at a heating rate of 10°C / min.

[0230] (Intrinsic viscosity η) Using a moving viscometer (Rigo Co., Ltd., Type VNR053U), 0.25 to 0.30 g of cyclic olefin copolymer was dissolved in 25 ml of decalin to prepare a sample. The specific viscosity of the cyclic olefin copolymer was measured at 135°C in accordance with ASTM J1601, and the ratio of this to the concentration was extrapolated to a concentration of 0 to determine the intrinsic viscosity η of the cyclic olefin copolymer.

[0231] (Concentration of cyclic olefin copolymer in the solution after catalyst removal treatment) The concentration of the cyclic olefin copolymer in the solution after the catalyst removal treatment was calculated from the weight of the cyclic olefin copolymer relative to the weight of the solution after the catalyst removal treatment.

[0232] (Solidification behavior of solution after catalyst removal treatment) The catalyst-removed solution was placed in a glass container and left to stand for one day. The container was then tilted 90 degrees and the fluidity of the solution was visually confirmed to evaluate the solidification behavior of the polymerization solution. 〇: Fluidity is good; the solution moves in the tilted direction and the liquid surface spreads evenly △: Poor fluidity; the solution moves in the tilted direction, but the liquid surface is not uniform ×: No fluidity; the solution does not move when tilted

[0233] (Solubility of Cyclic Olefin Copolymers) 0.12 g of the cyclic olefin copolymer and 1.5 ml of a cyclohexane / hexane (3 / 1) mixed solvent were added to a vial, and the mixture was shaken at room temperature to evaluate the solubility of the cyclic olefin copolymer. ○: Soluble; cyclic olefin copolymer is dissolved ×: Insoluble; cyclic olefin copolymer is not soluble

[0234] (Solidification behavior of redissolved solution) The solution prepared to evaluate the solubility of the cyclic olefin copolymer was left to stand for 24 hours, and then the container was tilted 90 degrees to visually check the fluidity of the solution, thereby evaluating the solidification behavior of the polymerization solution. Note that samples that were evaluated as × in the evaluation of the solubility of the cyclic olefin copolymer were not included in the evaluation of solidification behavior, and are marked with a diagonal line in the table. 〇: Fluidity is good; the solution moves in the tilted direction and the liquid surface spreads evenly △: Poor fluidity; the solution moves in the tilted direction, but the liquid surface is not uniform ×: No fluidity; the solution does not move when tilted

[0235] (Elemental analysis) Measurements were performed using an Agilent Technologies ICP-MS (Agilent 7500cs). For quantitative analysis of aluminum, the sample was wet decomposed with sulfuric acid, then diluted with dilute acid containing the internal standard element and analyzed. The aluminum content was evaluated according to the following criteria. ○: Less than 50 ppm △: 50 ppm or more to 100 ppm or less ×: More than 100ppm

[0236] [Table 1]

[0237] As shown in Table 1, in the methods for producing cyclic olefin copolymers of Examples 1 to 9 according to the embodiments of the present invention, the aluminum content of the obtained cyclic olefin copolymers was reduced to 100 ppm or less.

[0238] As shown in Table 1, in the methods for producing a cyclic olefin copolymer according to Examples 1 to 9 of the embodiment of the present invention, solidification of the cyclic olefin copolymer was suppressed. Furthermore, the cyclic olefin copolymers obtained by the methods for producing a cyclic olefin copolymer according to Examples 1 to 9 of the embodiment of the present invention had excellent solubility. Therefore, it is believed that in the method for producing a cyclic olefin copolymer according to the embodiment of the present invention, the catalyst could be efficiently removed even when the cyclic olefin copolymer had a high concentration, and the aluminum content could be reduced to 100 ppm or less.

Claims

1. a polymerization step of copolymerizing an α-olefin (X') having 2 to 20 carbon atoms, a cyclic olefin (Y') having no aromatic ring, and a cyclic olefin (Z') having an aromatic ring in the presence of an olefin polymerization catalyst containing a transition metal compound (A) and a compound (B); a catalyst removal step of removing the olefin polymerization catalyst; A method for producing a cyclic olefin copolymer, comprising: The cyclic olefin copolymer obtained by this production method has a structural unit (X) derived from the α-olefin (X'), a structural unit (Y) derived from the cyclic olefin (Y'), and a structural unit (Z) derived from the cyclic olefin (Z'), the cyclic olefin copolymer has an aluminum content of 100 ppm or less; The transition metal compound (A) is A transition metal compound (A-1) represented by the following formula (I): A transition metal compound (A-2) represented by the following formula (II), and The present invention comprises one or more transition metal compounds (A-3) selected from the group consisting of transition metal compounds represented by the following formula (III): The compound (B) is an organoaluminum compound (B-1a) represented by the following general formula (B-1a): An alkyl complex compound (B-1b) of a Group 1 metal and aluminum represented by the following general formula (B-1b), and Contains one or more organic aluminum oxy compounds (B-2) selected from the group consisting of The cyclic olefin (Z') having an aromatic ring contains one or more compounds selected from the group consisting of a compound represented by the following formula (VI'), a compound represented by the following formula (VII'), and a compound represented by the following formula (VIII'): 【Chemical 1】 In the formula (I), M １ represents a transition metal atom of Group 4 of the periodic table, R ０ represents a group selected from the group consisting of an alkylene group, an alkylidene group, an arylene group, and a silylene group, and substituted groups thereof; R １ and R ２ each independently represents a cycloalkadienyl group or a substituted cycloalkadienyl group, R ３ and R ４ each independently represents an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a silicon-containing group, a boron-containing group, and an aluminum-containing group, and substitution products thereof. 【Chemistry 2】 In the formula (II), M ２ represents a transition metal atom of Group 4 of the periodic table, n １ represents an integer of 1 to 3, L each independently represents a monovalent anionic ligand having an atom of Group 15 of the periodic table as a coordinating atom; X １ each independently represents a group or atom selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a silicon-containing group, a boron-containing group, and an aluminum-containing group, and substitution products thereof; R ５ ~R ９ each independently represents a group or atom selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a silicon-containing group, a boron-containing group, and an aluminum-containing group, and a substitution product thereof; R ５ Any two or three of R to R9 may be fused to form a ring, and the ring formed may have aromaticity containing a conjugated double bond. 【Chemistry 3】 In the formula (III), M ３ represents a transition metal atom of Group 4 of the periodic table, n ２ represents an integer from 1 to 4, X ２ each independently represents an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a silicon-containing group, a boron-containing group, and an aluminum-containing group, and substitution products thereof; R １０ ~R １７ each independently represents an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a silicon-containing group, a boron-containing group, and an aluminum-containing group, and the group consisting of substituted groups thereof; R １０ ~R １７ Adjacent ones of these may be bonded to each other to form a ring, and the ring formed may have aromaticity containing a conjugated double bond. (B-1a):Ra ｍ Al(ORb) ｎ H ｐ X ｑ In formula (B-1a), Ra and Rb each independently represent a hydrocarbon group having 1 to 15 carbon atoms, X represents a halogen atom, m represents a number satisfying 0<m≦3, n represents a number satisfying 0≦n<3, p represents a number satisfying 0≦p<3, and q represents a number satisfying 0≦q<3, and m+n+p+q=3. (B-1b):M2AlRa ４ In formula (B-1b), M2 is Li, Na or K, and Ra is a hydrocarbon group having 1 to 15 carbon atoms. 【Chemistry 4】 【Chemistry 5】 【Chemistry 6】 In the above formula (VI'), formula (VII') and formula (VIII'), m 301 , n 301 and n 302 are 0, 1 or 2, R 301 to R 336 are each independently a hydrogen atom, a halogen atom other than a fluorine atom or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom other than a fluorine atom, R 310 and R 311 , R 311 and R 312 , R 312 and R 313 , R 313 and R 314 , R 325 and R 326 , R 326 and R 327 , R 327 and R 328 , R 333 and R 334 , R 334 and R 335 , R 335 and R 336 may be bonded to each other to form a single ring, and the single ring may have a double bond.

2. A method for producing the cyclic olefin copolymer according to claim 1, comprising: In the formula (I), R １ and R ２ each independently represent a group selected from the group consisting of a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group, a dimethylcyclopentadienyl group, an indenyl group, a tetrahydroindenyl group, a fluorenyl group, and a substituted group thereof.

3. A method for producing the cyclic olefin copolymer according to claim 1, comprising: In the formula (II), A method for producing a cyclic olefin copolymer, wherein L is a monovalent anionic ligand represented by the following formula (IV): 【Chemistry 7】 In the formula (IV), Y represents an atom of Group 15 of the periodic table; Z represents one kind of atom selected from Group 14, 15, or 16 of the periodic table; n ３ represents an integer of 1 to 3, R １８ each independently represents a group or atom selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a phosphorus-containing group, a silicon-containing group, a boron-containing group, and an aluminum-containing group, and the group consisting of substituted groups thereof, and each may be bonded to each other to form a ring, and the formed ring may have aromaticity including a conjugated double bond, or the formed ring may be bonded to a cyclopentadienyl group.

4. A method for producing the cyclic olefin copolymer according to claim 1, comprising: In the formula (III), R １０ ~R １４ and R １７ each independently represents an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, and a silicon-containing group, and a substitution product thereof; R １０ ~R １４ adjacent ones of these may be bonded to each other to form a ring, and the ring formed may have aromaticity containing a conjugated double bond, R １５ and R １６ and each independently represent an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group, a halogen-containing group, and substitution products thereof.

5. A method for producing the cyclic olefin copolymer according to claim 1, comprising: The compound (B) further contains a compound (B-3) that reacts with the transition metal compound (A) to form an ion pair.

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