Method for producing olefin and cyclic olefin copolymers

Abstract

To provide a suitable method for producing olefin-cyclic olefin copolymer.SOLUTION: The present invention is related to a method for producing olefin-cyclic olefin copolymer that is characterized in that an olefin (X) and a cyclic olefin (Y) are copolymerized in the presence of an olefin polymerization catalyst comprising (A) a transition metal compound represented by the following formula [A-1], and (B) at least one compound (B) selected from the group consisting of (B-1) an organometallic compound, (B-2) an organoaluminumoxy compound, and (B-3) a compound that reacts with transition metal compound (A) to form an ion pair. (A) Transition metal compound represented by the following formula [A-1] (PI)-M-Ln --- [A-1] (In the formula, M is a Group 3 to 11 metal; each PI is independently a ligand represented by the following formula [A-2].).SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to a method for producing olefin-cyclic olefin copolymers. [Background technology]

[0002] Olefin-cyclic olefin copolymers, obtained by copolymerizing olefins with specific cyclic olefins, possess high glass transition temperatures, excellent optical, mechanical, and thermal properties, and a good balance of these properties. Therefore, they are known to be suitable for applications in optical systems, such as DVD pickup lenses, smartphone imaging lenses, memory discs, and optical fibers. Furthermore, their high heat resistance suggests potential as base polymers for various molded articles. (See, for example, Patent Document 1)

[0003] Such olefin-cyclic olefin copolymers have conventionally been produced by copolymerizing an olefin with a specific cyclic olefin in a hydrocarbon solvent such as toluene, cyclohexane, hexane, or heptane, or using the cyclic olefin itself as the solvent, in the presence of a vanadium-based catalyst formed from a soluble vanadium compound and an organoaluminum compound. However, such vanadium-based catalysts tend to have low polymerization activity.

[0004] On the other hand, catalysts consisting of metallocene compounds and organoaluminum compounds have been shown to be superior in terms of polymerization activity for cyclic olefins (for example, Patent Document 2), and transition metal compounds with various structures are being actively developed.

[0005] In particular, metallocene compounds consisting of cyclopentadienyl ligands and heteroatom ligands from groups 15 and 16 of the periodic table have been shown to exhibit high polymerization activity and high copolymerizability of cyclic olefins in copolymerization of ethylene with cyclic olefins such as norbornene. (For example, Patent Document 3 and Non-Patent Document 1) [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2004-107486 [Patent Document 2] Japanese Patent Application Publication No. 61-221206 [Patent Document 3] International Publication No. 2007 / 026743 [Non-patent literature]

[0007] [Non-Patent Document 1] Macromolecules 2011,44,1986-1998 [Overview of the initiative] [Problems that the invention aims to solve]

[0008] However, with conventional transition metal compounds, there was room for further improvement in terms of polymerization activity, molecular weight of the resulting copolymer, and copolymerizability of cyclic olefins in the production of olefin-cyclic olefin copolymers. In view of the above prior art, the present invention aims to provide a suitable method for producing olefin-cyclic olefin copolymers. [Means for solving the problem]

[0009] The inventors discovered that by using a non-metallocene compound having a specific heteroatom ligand, they could produce olefin-cyclic olefin copolymers with a high cyclic olefin content and high molecular weight with high polymerization activity, thus completing the present invention.

[0010] In other words, the present invention is (A) A transition metal compound (A) represented by the following formula [A-1], (B)(B-1) Organometallic compounds, (B-2) Organoaluminum oxy compounds, and (B-3) At least one compound (B) selected from the group consisting of compounds that react with transition metal compounds (A) to form ion pairs. The present invention relates to a method for producing an olefin-cyclic olefin copolymer, characterized by copolymerizing an olefin (X) and a cyclic olefin (Y) in the presence of an olefin polymerization catalyst containing the above.

[0011] (A) Transition metal compounds represented by the following formula [A-1] (PI)-M-Ln···[A-1] [In the formula, M is a metal of Groups 3 to 11.] ;P I is an independent ligand represented by the following equation [A-2]:

[0012] [ka] In formula [A-2], R 1 ~R 3 These may be the same or different from each other, and are a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms, a halogen atom, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, or a phosphorus-containing group, R 1 ~R 3 Two or more of these groups may be bonded to each other to form a ring; L is selected from hydrogen atoms, halogen atoms, hydrocarbon groups having 1 to 40 carbon atoms, silicon-containing groups, oxygen-containing groups, nitrogen-containing groups, and conjugated diene derivative groups, and is a ligand other than a cyclopentadienyl type ligand and the PI ligand; n is an integer between 1 and 6 that satisfies the valence of M, and if n is 2 or greater, multiple Ls may be identical or different from each other. [Effects of the Invention]

[0013] According to the present invention, it is possible to produce olefin-cyclic olefin copolymers with high polymerization activity, high cyclic olefin content, and high molecular weight. [Modes for carrying out the invention]

[0014] The present invention will be described in more detail below. <Transition metal compound (A)> The transition metal compound (A) used in the method for producing olefin-cyclic olefin copolymers of the present invention is characterized by being represented by the following general formula [A-1]. (A) Transition metal compounds represented by the following formula [A-1] (PI)-M-Ln···[A-1] [In the formula, M is an atom selected from transition metal atoms of groups 3 to 11 of the periodic table; (PI) is a ligand represented by the following formula [A-2],

[0015] [ka] In formula [A-2], R 1 ~R 3 These may be the same or different from each other, and are a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms, a halogen atom, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, or a phosphorus-containing group, R 1 ~R 3 Two or more of these groups may be bonded to each other to form a ring; L is selected from hydrogen atoms, halogen atoms, hydrocarbon groups having 1 to 40 carbon atoms, silicon-containing groups, oxygen-containing groups, nitrogen-containing groups, and conjugated diene derivative groups, and is a ligand other than a cyclopentadienyl type ligand and the PI ligand; n is an integer between 1 and 6 that satisfies the valence of M, and if n is 2 or greater, multiple Ls may be identical or different from each other.

[0016] In the general formula [A-1] above, M represents a transition metal atom from groups 3 to 11 of the periodic table (group 3 also includes lanthanides), preferably a metal atom from groups 4 to 5, more preferably a transition metal atom from group 4, and particularly preferably titanium. Specifically, these include scandium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, cobalt, rhodium, yttrium, chromium, molybdenum, tungsten, manganese, rhenium, iron, ruthenium, etc., preferably titanium, zirconium, hafnium, vanadium, niobium, tantalum, etc., more preferably titanium, zirconium, hafnium, and particularly preferably titanium.

[0017] Examples of the hydrocarbon groups having 1 to 40 carbon atoms include linear or branched alkyl groups such as methyl group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group, 1-hexyl group, 1-heptyl group, 1-octyl group, iso-propyl group, sec-butyl group (butane-2-yl group), tert-butyl group (2-methylpropane-2-yl group), iso-butyl group (2-methylpropyl group), pentane-2-yl group, 2-methylbutyl group, iso-pentyl group (3-methylbutyl group), neopentyl group (2,2-dimethylpropyl group), siamyl group (1,2-dimethylpropyl group), iso-hexyl group (4-methylpentyl group), 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, texyl group (2,3-dimethylbuta-2-yl group), and 4,4-dimethylpentyl group; Vinyl group, allyl group, propenyl group (propa-1-en-1-yl group), iso-propenyl group (propa-1-en-2-yl group), allenyl group (propa-1,2-dien-1-yl group), buta-3-en-1-yl group, clotyl group (buta-2-en-1-yl group), buta-3-en-2-yl group, metharyl group (2-methylallyl group), buta-1,3-dienyl group, pen Linear or branched alkenyl groups or unsaturated double bond-containing groups such as ta-4-en-1-yl group, penta-3-en-1-yl group, penta-2-en-1-yl group, iso-pentenyl group (3-methylbuta-3-en-1-yl group), 2-methylbuta-3-en-1-yl group, penta-4-en-2-yl group, and prenyl group (3-methylbuta-2-en-1-yl group); Linear or branched alkynyl groups or unsaturated triple bond-containing groups such as ethynyl group, propa-2-in-1-yl group, and propargyl group (propa-1-in-1-yl group); aromatic linear or branched alkyl groups and unsaturated double bond-containing groups such as benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2,4,6-trimethylbenzyl group, 3,5-dimethylbenzyl group, cuminyl group (4-iso-propylbenzyl group), 2,4,6-tri-iso-propylbenzyl group, 4-tert-butylbenzyl group, 3,5-di-tert-butylbenzyl group, 1-phenylethyl group, benzhydryl group (diphenylmethyl group), and cumyl group; Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cycloheptatrienyl group, norbornyl group, norborneyl group, 1-adamantyl group, 2-adamantyl group, and other cyclic saturated hydrocarbon groups; Aromatic substituents (aryl groups) such as phenyl group, tolyl group (methylphenyl group), xylyl group (dimethylphenyl group), mesityl group (2,4,6-trimethylphenyl group), cumenyl group (iso-propylphenyl group), juryl group (2,3,5,6-tetramethylphenyl group), 2,6-di-iso-propylphenyl group, 2,4,6-tri-iso-propylphenyl group, 4-tert-butylphenyl group, 3,5-di-tert-butylphenyl group, naphthyl group, biphenyl group, terphenyl group, binaphthyl group, acenaphthalenyl group, phenanthryl group, anthracenyl group, pyrenyl group, and ferrocenyl group are examples.

[0018] The aforementioned hydrocarbon groups having 1 to 40 carbon atoms include: heterocyclic compound residues; oxygen-containing groups such as alkoxy groups, allyloxy groups, ester groups, ether groups, acyl groups, carboxyl groups, carbonate groups, hydroxyl groups, peroxy groups, and carboxylic acid anhydride groups; nitrogen-containing groups such as amino groups, imino groups, amide groups, imide groups, hydrazino groups, hydrazono groups, nitro groups, nitroso groups, cyano groups, isocyano groups, cyanate ester groups, amidino groups, diazo groups, and amino groups that have been converted to ammonium salts; boranediyl groups, borantriyl groups, and diboranyl groups. It may also contain boron-containing groups such as mercapto groups, thioester groups, dithioester groups, alkylthio groups, arylthio groups, thioacyl groups, thioether groups, thiocyanate groups, isothianeate groups, sulfone ester groups, sulfonamide groups, thiocarboxyl groups, dithiocarboxyl groups, sulfo groups, sulfonyl groups, sulfinyl groups, sulfenyl groups, sulfenyl groups, etc.; phosphorus-containing groups such as phosphine groups, phosphoryl groups, thiophosphoryl groups, phosphat groups, etc.; silicon-containing groups; germanium-containing groups; or tin-containing groups.

[0019] Examples of the halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. The halogen-containing group includes a hydrocarbon group in which a hydrogen atom is substituted with a halogen. Examples of such hydrocarbon groups in which a hydrogen atom is substituted with a halogen include halogenated hydrocarbon groups having 1 to 20 carbon atoms, such as trifluoromethyl, pentafluorophenyl, and chlorophenyl groups.

[0020] Examples of silicon-containing groups include silyl groups, siloxy groups, hydrocarbon-substituted silyl groups, and hydrocarbon-substituted siloxy groups. More specifically, examples include hydrocarbon-substituted silyl groups such as phenylsilyl group, diphenylsilyl group, trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tricyclohexylsilyl group, triphenylsilyl group, methyldiphenylsilyl group, tritlylsilyl group, and trinaphthylsilyl group; hydrocarbon-substituted silyl ether groups such as trimethylsilyl ether group; silicon-substituted alkyl groups such as trimethylsilylmethyl group; and silicon-substituted aryl groups such as trimethylsilylphenyl group.

[0021] Examples of the oxygen-containing groups include hydroxyl groups; alkoxy groups such as methoxy, ethoxy, propoxy, and butoxy groups; aryloxy groups such as phenoxy, methylphenoxy, dimethylphenoxy, and naphthoxy groups; arylalkoxy groups such as phenylmethoxy and phenylethoxy groups; acetoxy groups; and carbonyl groups.

[0022] Specific examples of the nitrogen-containing group include amino groups; alkylamino groups such as methylamino group, dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, and dicyclohexylamino group; arylamino groups or alkylarylamino groups such as phenylamino group, diphenylamino group, ditolylamino group, dinaphthylamino group, and methylphenylamino group.

[0023] Specific examples of the sulfur-containing groups include: sulfonate groups such as a methyl sulfonate group, a trifluoromethane sulfonate group, a phenyl sulfonate group, a benzyl sulfonate group, a p-toluene sulfonate group, a trimethylbenzene sulfonate group, a triisobutylbenzene sulfonate group, a p-chlorobenzene sulfonate group, and a pentafluorobenzene sulfonate group; sulfinate groups such as a methyl sulfinate group, a phenyl sulfinate group, a benzyl sulfinate group, a p-toluene sulfinate group, a trimethylbenzene sulfinate group, and a pentafluorobenzene sulfinate group; an alkylthio group; and an arylthio group.

[0024] Specific examples of the phosphorus-containing groups include: trialkylphosphine groups such as a trimethylphosphine group, a tributylphosphine group, and a tricyclohexylphosphine group; triarylphosphine groups such as a triphenylphosphine group and a tritolylphosphine group; phosphite groups (phosphide groups) such as a methyl phosphite group, an ethyl phosphite group, and a phenyl phosphite group; a phosphonic acid group; and a phosphinic acid group.

[0025] R 1 ~R 3 is preferably a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. Specific examples thereof include a t-butyl group, an adamantyl group, a cyclohexyl group, a phenyl group, a biphenyl-2-yl group, and an o-tolyl group. Among these, a t-butyl group, an adamantyl group, a cyclohexyl group, a phenyl group, and a biphenyl-2-yl group are preferred.

[0026] L is selected from a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 40 carbon atoms, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, and a conjugated diene derivative group, and is a ligand that is neither a cyclopentadienyl-type ligand nor the aforementioned PI ligand; as the hydrocarbon group, the silicon-containing group, the oxygen-containing group, and the nitrogen-containing group, R in the aforementioned formula [A-2] 1 ~R 3Examples similar to those given as illustrations can be cited.

[0027] The diene derivative group is a hydrocarbon compound that can coordinate to M in the general formula [A-1] with a lone pair of electrons, and examples include 1,3-butadienyl group, isoprenyl group (2-methyl-1,3-butadienyl group), piperilenyl group (1,3-pentadienyl group), 2,4-hexadienyl group, 1,4-diphenyl-1,3-pentadienyl group, cyclopentadienyl group, metallocyclopentenyl group, and 1,5-cyclooctadienyl group.

[0028] The cyclopentadienyl ligand is a substituted ligand having a five-membered carbocyclic ring bonded to a metal by a π-type bond, and includes substituted cyclopentadienyl ligands, substituted tetrahydroindenyl ligands, substituted octahydrofluorenyl ligands, substituted hydroazlenyl ligands, substituted pentahydroazlenyl ligands, substituted dihydrocyclopentenoannulene ligands, substituted cyclopentenopyrrole ligands, substituted cyclopentenothiophene ligands, and substituted cyclopentenodithiophene ligands, as well as substituted indenyl ligands, substituted tetrahydroindenyl ligands, substituted benzoindenyl ligands, substituted dihydroindacenyl ligands, substituted indenopyrrole ligands, substituted indenindole ligands, and substituted indenothiophene ligands, and substituted fluorenyl ligands, etc. Preferred cyclopentadienyl ligands include substituted cyclopentadienyl ligands and substituted indenyl ligands, and more preferably substituted cyclopentadienyl ligands, substituted dihydrocyclopentenoannulene ligands, substituted cyclopentenothiophene ligands, substituted cyclopentenodithiophene ligands, and substituted indenyl ligands.

[0029] Preferred specific examples of L include hydrogen atoms, chlorine atoms, bromine atoms, methyl groups, dimethylamino groups, diethylamino groups, benzyl groups, phenoxy groups, and 1,3-butadienyl groups. n is an integer between 1 and 6 that satisfies the valence of M, and if n is 2 or greater, multiple Ls may be the same or different from each other.

[0030] Below, we show specific examples of transition metal compounds (A) represented by the general formula [A-1] above, as shown by the compounds represented by formulas (a1) to (a12), but transition metal compounds (A) are not limited to these.

[0031] [ka]

[0032] [ka]

[0033] [ka]

[0034] [ka]

[0035] [ka]

[0036] [ka]

[0037] [ka]

[0038] [ka]

[0039] [ka]

[0040] [ka]

[0041] [ka]

[0042] [ka]

[0043] <Compound (B)> Compound (B) used in the method for producing olefin-cyclic olefin copolymers of the present invention is (B-1) organometallic compound, (B-2) Organic aluminum oxy compounds, and (B-3) Compounds that react with transition metal compounds (A) to form ion pairs It is at least one compound (B) selected from the group consisting of the following.

[0044] 《Organometallic compound (B-1)》 Examples of organometallic compounds (B-1) (hereinafter also referred to as "component (B-1)") include organoaluminum compounds represented by general formula (B-1a) (B-1a), complex alkylates of group 1 metals and aluminum represented by general formula (B-1b) (B-1b), and dialkyl compounds of group 2 or group 12 metals represented by general formula (B-1c) (B-1c), which are organometallic compounds of groups 1, 2 and 12 and 13.

[0045] (B-1a):R a m Al(OR b ) n H p X q In formula (B-1a), R a and R beach is independently a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X is a halogen atom, m is a number satisfying 0<m≦3, n is a number satisfying 0≦n<3, p is a number satisfying 0≦p<3, q is a number satisfying 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.

[0046] (B-1b):M 2 AlR a 4 In formula (B-1b), M 2 is Li, Na or K, and R a is a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. Examples of the complex alkylated product (B-1b) include LiAl(C2H5)4 and LiAl(C7H 15 )4.

[0047] (B-1c):R a R b M 3 In formula (B-1c), R a and R b each is independently a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M 3 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.

[0048] Among the organometallic compounds (B-1), the organoaluminum compound (B-1a) is preferable. The organometallic compound (B-1) may be used alone, or two or more kinds thereof may be used in combination.

[0049] <<Organoaluminum Oxy Compound (B-2)>> As the organoaluminum oxy compound (B-2) (hereinafter also referred to as "component (B-2)"), conventionally known aluminoxanes can be used as is. Specifically, the following general formula [B2-1]

[0050] [ka]

[0051] and / or the following general formula [B2-2]

[0052] [ka] Examples include compounds represented by the formula (wherein R represents a hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 2 or more), benzene-insoluble organoaluminum oxy compounds described in Japanese Patent Publication No. 2-78687 and Japanese Patent Publication No. 2-167305, and aluminoxanes having two or more alkyl groups described in Japanese Patent Publication No. 3-103407.

[0053] Furthermore, examples of organoaluminum oxy compounds (B-2) include modified methylaluminoxanes represented by the following general formula [B2-3].

[0054] [ka] (In the formula, R represents a hydrocarbon group having 1 to 10 carbon atoms, and m and n each independently represent an integer greater than or equal to 2.)

[0055] These modified methylaluminoxanes are prepared using trimethylaluminum and alkylaluminum other than trimethylaluminum. Such compounds are commonly referred to as MMAOs. Such MMAOs can be prepared by the methods described in U.S. Patent No. 4,960,878 and U.S. Patent No. 5,041,584.

[0056] Furthermore, as organoaluminum oxy compounds (B-2), organoaluminum oxy compounds containing boron, represented by the following general formula [B2-4], can also be mentioned.

[0057] [ka] (In the formula, R c R represents a hydrocarbon group having 1 to 10 carbon atoms. d These may be identical or different from each other, and represent a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms.

[0058] As the organoaluminum oxy compound (B-2), methylaluminoxane, which is readily available as a commercially available product, and MMAO prepared using trimethylaluminum and triisobutylaluminum are preferred. Of these, MMAO with improved solubility in various solvents and storage stability is particularly preferred.

[0059] Compounds (B-3) that react with transition metal compounds (A) to form ion pairs. Compounds (B-3) that react with transition metal compounds (A) to form ion pairs (hereinafter also referred to as "ionic compounds (B-3)" or "component (B-3)") include Lewis acids, ionic compounds, borane compounds, and carborane compounds described in Japanese Patent Publication No. 1-501950, Japanese Patent Publication No. 1-502036, Japanese Patent Application Publication No. 3-179005, Japanese Patent Application Publication No. 3-179006, Japanese Patent Application Publication No. 3-207703, Japanese Patent Application Publication No. 3-207704, and U.S. Patent No. 5321106, etc. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.

[0060] The ionic compound (B-3) is preferably a boron compound represented by the following general formula [B3-1].

[0061] [ka] (In the formula, R e+ H+ Examples include carbenium cations, oxonium cations, ammonium cations, phosphonium cations, cycloheptyltrienyl cations, and ferrocenium cations containing transition metals.

[0062] R f From R i These substituents may be the same or different from each other and are 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.

[0063] Examples of boron compounds represented by the general formula [B3-1] include those described in paragraphs

[0196] to

[0217] of Japanese Patent Publication No. 2012-72365, among which triphenylcarbenium tetrakis(pentafluorophenyl)borate and N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate are preferred. The ionic compound (B-3) may be used alone or as a mixture of two or more types.

[0064] (Carrier (C)) The carrier (C) is an inorganic or organic compound, in the form of a granular or particulate solid, and can be one that has been conventionally used in olefin polymerization using a transition metal compound and a carrier as a catalyst component, for example, one described in paragraphs

[0220] to

[0235] of Japanese Patent Application Publication No. 2012-72365.

[0065] (Organic compound component (D)) An organic compound component (D) may be used as a component of the olefin polymerization catalyst as needed. The organic compound component (D) is used to improve polymerization performance and the physical properties of the resulting polymer. Examples of organic compound components (D) include alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, amides, polyethers, and sulfonates.

[0066] [Method for producing olefin-cyclic olefin copolymers] The present invention provides a method for producing olefin-cyclic olefin copolymers, characterized by copolymerizing an olefin (X) and a cyclic olefin (Y) in the presence of an olefin polymerization catalyst containing the transition metal compound (A) of the present invention described above. In the method for producing olefin-cyclic olefin copolymers of the present invention, copolymers may be produced by copolymerizing two or more olefins with a cyclic olefin.

[0067] In polymerization, the method of using each component constituting the olefin polymerization catalyst according to the present invention, and the order of addition to the polymerizer, can be arbitrarily selected, but the following methods are examples. Hereinafter, the transition metal compound (A), compound (B), support (C), and organic compound component (D) will also be referred to as "components (A) to (D)," respectively. (1) A method of adding component (A) alone to the polymerizer. (2) A method of adding component (A) and component (B) to a polymerizer in any order. (3) A method of adding a catalyst component in which component (A) is supported on component (C) and component (B) to a polymerizer in any order. (4) A method of adding a catalyst component in which component (B) is supported on component (C) and component (A) to a polymerizer in any order. (5) A method of adding a catalyst component, in which components (A) and (B) are supported on component (C), to a polymerizer.

[0068] In each of the above methods, component (D) may be added at any stage. In each of the above methods, at least two of the catalyst components may be in contact with each other beforehand. In the methods described in (4) and (5) above, in which component (B) is supported, unsupported component (B) may be added in any order as needed. In this case, component (B) may be the same or different. Furthermore, the solid catalyst component in which component (A) is supported on component (C), and the solid catalyst component in which component (A) and component (B) are supported on component (C), may have the olefin prepolymerized, and further catalyst components may be supported on the prepolymerized solid catalyst component.

[0069] Copolymerization of olefins and cyclic olefins can be carried out using either liquid-phase polymerization methods such as solution polymerization or suspension polymerization, or gas-phase polymerization methods. Examples of inert hydrocarbon media used in liquid-phase polymerization include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; and halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane. The inert hydrocarbon media may be used alone or in mixtures of two or more.

[0070] When polymerizing olefins using the above-described catalyst for olefin polymerization, the transition metal compound (A) is typically present in a concentration of 10 per liter of reaction volume. -12 ~10 -2 moles, preferably 10 -10 ~10 -3 It is used in quantities that equal moles.

[0071] The organometallic compound (B-1) is used in an amount such that the molar ratio [(B-1) / M] of the organometallic compound (B-1) to the total transition metal atoms (M) in the transition metal compound (A) is typically 0.01 to 50,000, preferably 0.05 to 10,000.

[0072] The organoaluminum oxy compound (B-2) is used in an amount such that the molar ratio [(B-2) / M] of aluminum atoms in the organoaluminum oxy compound (B-2) to the total transition metal (M) in the transition metal compound (A) is usually 10 to 5,000, preferably 20 to 2,000.

[0073] The ionized ionic compound (B-3) is used in an amount such that the molar ratio [(B-3) / M] of the ionized ionic compound (B-3) to the transition metal atoms (M) in the transition metal compound (A) is usually between 1 and 10,000, preferably between 1 and 5,000.

[0074] When a support (C) is used, it is used in an amount such that the weight ratio of the transition metal compound (A) to the support (C) [(A) / (C)] is preferably 0.0001 to 1, more preferably 0.0005 to 0.5, and even more preferably 0.001 to 0.1.

[0075] In the manufacturing method of the present invention, the polymerization temperature in the polymerization step is usually -50 to +200°C, preferably 0 to 180°C; the polymerization pressure is usually atmospheric pressure to 10 MPa gauge pressure, preferably atmospheric pressure to 5 MPa gauge pressure. The polymerization reaction can be carried out in batch, semi-continuous, or continuous manner. Furthermore, polymerization can be carried out in two or more stages with different reaction conditions.

[0076] The molecular weight of the resulting olefin-cyclic olefin copolymer can be adjusted by the presence of hydrogen in the polymerization system, by changing the polymerization temperature, or by the amount of compound (B) used. When hydrogen is added, the appropriate amount is approximately 0.001 to 5,000 NL per 1 kg of copolymer produced.

[0077] Examples of olefins (X) subjected to the polymerization reaction in the method for producing olefin-cyclic olefin copolymers of the present invention include linear or branched α-olefins. The present invention is characterized by producing an olefin-cyclic olefin copolymer by copolymerizing a linear or branched olefin with a cyclic olefin (Y) in the presence of the catalyst. Preferably, the present invention is characterized by producing an olefin-cyclic olefin copolymer by copolymerizing an olefin defined in (Z-1) below with a cyclic olefin defined in (Z-2).

[0078] (Z-1) Linear or branched α-olefins with 2 to 30 carbon atoms. Examples of the linear or branched α-olefin include linear or branched α-olefins (Z-1) having 2 to 30 carbon atoms.

[0079] The number of carbon atoms in α-olefin (Z-1) is preferably 2 to 20. Specific examples of α-olefins (Z-1) include ethylene, propylene, 1-butene, 2-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. More preferably, linear olefins are used, and particularly preferably ethylene.

[0080] (Z-2) At least one cyclic olefin selected from the group consisting of compounds represented by general formula [ZI], general formula [Z-II], general formula [Z-III], general formula [Z-IV], or general formula [ZV]. The cyclic olefin mentioned above includes at least one cyclic olefin (Z-2) selected from the group consisting of compounds represented by the following general formulas [ZI], [Z-II], [Z-III], [Z-IV], or [ZV].

[0081] [ka] [In equation [ZI], u is either 0 or 1, v is 0 or a positive integer, w is either 0 or 1. R 61 ~R 78 Furthermore, R a1 and R b1 Each is independently selected from a hydrogen atom, a halogen atom, and a hydrocarbon group, R 75 ~R 78 These may be bonded to each other to form a monocycle or polycycle, and the monocycle or polycycle may have a double bond, and R 75 and R 76 And, or R 77 and R 78 They may form alkylidene groups.

[0082] [ka] [In equation [Z-II], x and d are integers of 0 or greater than or equal to 1, y and z are 0, 1, or 2. R 81 ~R 99 Each is independently selected from a hydrogen atom, a halogen atom, and a hydrocarbon group, R 89 and R 90 The carbon atom to which it is bonded, and R 93 The carbon atom or R to which it is bonded 91 The carbon atom to which it is bonded may be directly bonded or bonded via an alkylene group having 1 to 3 carbon atoms, and when y=z=0, R 95 and R 92 or R 95 and R 99 These elements may be bonded to each other to form a monocyclic or polycyclic aromatic ring.

[0083] [ka] [In formula [Z-III], R 100 and R 101 Each of these is independently a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and f is 1 ≤ f ≤ 18.

[0084] [ka] [In the general formula [Z-IV], x is an integer greater than or equal to 0 or 1, R 111 ~R 118 Each is independently selected from a hydrogen atom, a halogen atom, and a hydrocarbon group. R 121 ~R 124 Each of these groups is independently selected from a hydrogen atom, a halogen atom, and a hydrocarbon group, and two adjacent groups may be bonded to each other to form a monocyclic or bicyclic aromatic ring.

[0085] [ka] [In the general formula [ZV], n and m are independently 0, 1, or 2, q is 1, 2, or 3, R 18 ~R 31 Each of these is 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 when q=1, R 28 and R 29 , R 29 and R 30 , R 30 and R 31 They may be bonded to each other to form a monocycle or polycycle, and when q=2 or 3, R 28 and R 29 , R 29 and R 30 , R 30 and R 31 , R 31 and R 31 , R 28 and R 28 These elements may be bonded to each other to form a monocycle or polycycle, and the monocycle or polycycle may have a double bond, and the monocycle or polycycle may be an aromatic ring.

[0086] The general formulas [ZI], [Z-II], [Z-III], [Z-IV], and [ZV] will be explained in detail below.

[0087] 《General formula [ZI]》 In equation [ZI], u is either 0 or 1, v is either 0 or a positive integer, and w is either 0 or 1. When w is 1, the ring expressed using w is a 6-membered ring, and when w is 0, the ring is a 5-membered ring.

[0088] R 61 ~R 78 Furthermore, R a1 and R b1 These elements may be the same or different from each other, and are hydrogen atoms, halogen atoms, or hydrocarbon groups. Here, the halogen atom is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

[0089] The hydrocarbon groups include linear or branched alkyl groups having 1 to 30 carbon atoms, preferably 1 to 20, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, and n-hexyl; linear or branched alkenyl groups having 2 to 30 carbon atoms, preferably 2 to 20, such as vinyl, allyl, and isopropenyl; linear or branched alkynyl groups having 2 to 30 carbon atoms, preferably 2 to 20, such as ethynyl and propargyl; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, Examples include cycloalkyl groups having 3 to 30 carbon atoms, preferably 3 to 20, such as cyclooctyl, adamantyl, norbonyl, and tetracyclododecyl; cyclic unsaturated hydrocarbon groups having 5 to 30 carbon atoms, such as cyclopentadienyl, indenyl, and fluorenyl; aryl groups having 6 to 30 carbon atoms, preferably 6 to 20, such as phenyl, benzyl, naphthyl, biphenyl, terphenyl, phenanthryl, and anthracenyl; and alkyl-substituted aryl groups such as tolyl, iso-propylphenyl, t-butylphenyl, dimethylphenyl, and di-t-butylphenyl.

[0090] The hydrocarbon group described above may have hydrogen atoms substituted with halogens. Examples include alkyl or aryl halogen groups having 1 to 30 carbon atoms, preferably 1 to 20, such as monotrifluoromethyl, ditrifluoromethyl, monofluorophenyl, difluorophenyl, trifluorophenyl, pentafluorophenyl, and chlorophenyl.

[0091] Furthermore, the above hydrocarbon group may be substituted with other hydrocarbon groups, such as benzyl and cumyl aryl-substituted alkyl groups. Further, the aforementioned hydrocarbon group may optionally have: a heterocyclic compound residue; an oxygen-containing group such as an alkoxy group, an aryloxy group, an ester group, an ether group, an acyl group, a carboxyl group, a carbonate group, a hydroxy group, a peroxy group, and a carboxylic acid anhydride group; a nitrogen-containing group such as an amino group, an imino group, an amide group, an imide group, a hydrazino group, a hydrazono group, a nitro group, a nitroso group, a cyano group, an isocyano group, a cyanate ester group, an amidino group, a diazo group, and an amino group formed into an ammonium salt; a boron-containing group such as a boranediyl group, a boranetriyl group, and a diboranyl group; a sulfur-containing group such as a mercapto group, a thioester group, a dithioester group, an alkylthio group, an arylthio group, a thioacyl group, a thioether group, a thiocyanate ester group, an isothiocyanate ester group, a sulfonic ester group, a sulfonamide group, a thiocarboxyl group, a dithiocarboxyl group, a sulfo group, a sulfonyl group, a sulfinyl group, and a sulfenyl group; a phosphorus-containing group such as a phosphide group, a phosphoryl group, a thiophosphoryl group, and a phosphato group; a silicon-containing group; a germanium-containing group; or a tin-containing group.

[0092] Preferred examples of the aforementioned hydrocarbon group include: linear or branched alkyl groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, neopentyl, and n-hexyl; cycloalkyl groups having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, such as cyclopropyl, cyclobutyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl, norbornyl, and tetracyclododecyl; aryl groups having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, such as phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, and anthracenyl; and substituted aryl groups obtained by substituting 1 to 5 substituents selected from a halogen atom, an alkyl or alkoxy group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, and an aryl or aryloxy group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, onto these aryl groups.

[0093] Further, in the aforementioned general formula [Z-I], R 75 and R 76 and are R77 and R 78 and, R 75 and R 77 and, R 76 and R 78 and, R 75 and R 78 and, or R 76 and R 77 may each be bonded (together with each other) to form a monocyclic or polycyclic group, and the thus-formed monocyclic or polycyclic group may have a double bond. Specific examples of the monocyclic or polycyclic group formed herein include the following.

[0094]

Chem.

[0095] In the above examples, the carbon atoms numbered 1 or 2 correspond to R in the above general formula (I), respectively 75 (R 76 ) or R 77 (R 78 ) represents the carbon atom to which is bonded. Further, R 75 and R 76 , or R 77 and R 78 may together form an alkylidene group. Such an alkylidene group is usually an alkylidene group having 2 to 20 carbon atoms, and specific examples of such an alkylidene group include ethylidene, propylidene, isopropylidene and the like.

[0096] <<General Formula [Z-II]>> In formula [Z-II], x and d are 0 or a positive integer, and y and z are 0, 1 or 2.

[0097] Further, R 81 to R 99 may be the same or different from each other, and are each a hydrogen atom, a halogen atom, or a hydrocarbon group. Examples of halogen atoms and hydrocarbon groups include those identical to the halogen atoms and hydrocarbon groups in formula [ZI] above.

[0098] Here, R 89 and R 90 The carbon atom to which it is bonded, and R 93 The carbon atom or R to which it is bonded 91 The carbon atom to which is bonded may be directly bonded or via an alkylene group having 1 to 3 carbon atoms. That is, if the two carbon atoms mentioned above are bonded via an alkylene group, R 89 and R 93 or R 90 and R 91 These groups work together to form an alkylene group consisting of a methylene group (-CH2-), an ethylene group (-CH2CH2-), or a propylene group (-CH2CH2CH2-).

[0099] Furthermore, when y=z=0, R 95 and R 92 or R 95 and R 99 These may be bonded to each other to form a monocyclic or polycyclic aromatic ring. Specifically, when y=z=0, R 95 and R 92 The following aromatic rings are formed by the above.

[0100] [ka] Here, l is the same as d in the general formula [Z-II] above.

[0101] 《General formula [Z-III]》 In formula [Z-III], R 100 and R 101 These elements may be the same or different from each other, and are hydrogen atoms or hydrocarbon groups having 1 to 5 carbon atoms, and f is 1 ≤ f ≤ 18.

[0102] Hydrocarbon groups having 1 to 5 carbon atoms can preferably include alkyl groups, halogenated alkyl groups, or cycloalkyl groups. Specific examples of these are R in the above formula [ZI]. 61 ~R 78 This is similar to the example given earlier.

[0103] 《General formula [Z-IV]》 In the general formula [Z-IV], x is an integer greater than or equal to 0 or 1. R 111 ~R 118 and R 121 ~R 124 These are selected from hydrogen atoms, halogen atoms, and hydrocarbon groups, and may be the same or different from each other.

[0104] Examples of halogen atoms and hydrocarbon groups include those identical to the halogen atoms and hydrocarbon groups in formula [ZI] above. Also, R 121 ~R 124 Two adjacent groups may be bonded to each other to form a monocyclic or bicyclic aromatic ring. Of these, R 121 and R 122 Specific examples of cyclic olefins in which an aromatic ring is formed by the bonding of these molecules include the following structures.

[0105] [ka]

[0106] [ka]

[0107] Also, R 122 and R 123 Specific examples of cyclic olefins in which an aromatic ring is formed by bonding include the following structures.

[0108] [ka]

[0109] [ka]

[0110] Also, R 121 and R 122 , R 123 and R 124 Specific examples of cyclic olefins in which an aromatic ring is formed by bonding include the following structures.

[0111] [ka]

[0112] Examples include cyclic olefins in which substituents selected from halogen atoms, alkyl groups, and aryl groups are substituted on these aromatic rings.

[0113] 《General formula [ZV]》 In the general formula [ZV], m and n are 0, 1, or 2, and R 18 ~R 31 Each of these is 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 28 and R 29 , R 29 and R 30 , R 30 and R 31 These elements may be bonded to each other to form a monoring, and this monoring may have a double bond.

[0114] Furthermore, in the general formula [ZV], m is preferably 0 or 1, and more preferably 1. n is preferably 0 or 1, and more preferably 0. 18 ~R 31 It is preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrogen atom.

[0115] Furthermore, examples of hydrocarbon groups having 1 to 20 carbon atoms include, independently, alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 15 carbon atoms, and aromatic hydrocarbon groups. More specifically, alkyl groups include methyl, ethyl, propyl, isopropyl, amyl, hexyl, octyl, decyl, dodecyl, and octadecyl groups; cycloalkyl groups include cyclohexyl groups; and aromatic hydrocarbon groups include aryl or aralkyl groups such as phenyl, tolyl, naphthyl, benzyl, and phenylethyl groups. These hydrocarbon groups may be substituted with halogen atoms other than fluorine atoms.

[0116] 《General formula [Z-VI]》

[0117] [ka]

[0118] In the above general formula (Z-VI), n and q are independently 0, 1, or 2. 1 ~ R 17 Each of these is 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 10 ~R 17 One of them is a bonding. Also, when q=0, R 10 and R 11 , R 11 and R 12 , R 12 and R 13 , R 13 and R 14 , R 14 and R 15 , R 15 and R 10 These elements may be bonded to each other to form a monocycle or polycycle. Also, when q=1 or 2, R 10 and R 11 , R 11 and R 17 , R 17 and R 12, R 12 and R 13 , R 13 and R 14 , R 14 and R 15 , R 15 and R 16 , R 16 and R 16 , R 17 and R 17 , R 16 and R 10 These elements may be bonded to each other to form a monocycle or polycycle, and the monocycle or polycycle may have a double bond, and the monocycle or polycycle may be an aromatic ring.

[0119] Preferred specific examples of cyclic olefins represented by the above general formulas [ZI], [Z-II], [Z-III], [Z-IV], [ZV], or [Z-VI] include tetracyclo[4.4.0.1 2,5 .1 7,10 Examples include compounds exemplified in paragraphs

[0176] to

[0207] of Japanese Patent Publication No. 2011-122146, such as ]-3-dodecene. Also preferred cyclic olefins are 1,4-dihydro-1,4-methanonaphthalene and 1,4-methano-1,4,4a,9a-tetrahydrofluorene.

[0120] These cyclic olefins (Z-2) represented by general formulas [ZI], [Z-II], [Z-III], [Z-IV], or [ZV] may be used individually or in combination of two or more. In the method for producing olefin polymers of the present invention, other olefins besides (Z-1) and (Z-2) described above may be subjected to polymerization and reaction. Examples of such olefins include conjugated / unconjugated polyenes and vinylcyclohexane.

[0121] Examples of the conjugated / unconjugated polyenes include cyclic or chain-like hydrocarbons having 4 to 30 carbon atoms, preferably 4 to 20, and possessing two or more double bonds. Specific examples include butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 1,3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidene norbornene, vinylone Examples of compounds exemplified in section

[0211] of Japanese Patent Publication No. 2011-122146 include rubornene, dicyclopentadiene, 7-methyl-1,6-octadiene, 4-ethlylidene-8-methyl-1,7-nonadienene, 5,9-dimethyl-1,4,8-decatrienebutadiene, isoprene, ethlylidenenorbornene, vinylnorbornene, and dicyclopentadiene.

[0122] In the method for producing olefin-cyclic olefin copolymers of the present invention, polymerizable compounds other than olefins may be polymerized together with the olefins described above. Examples of such polymerizable compounds include compounds having polar groups and polymerizable unsaturated bonds, aromatic vinyl compounds, and functional group-containing styrene derivatives.

[0123] Specific examples of compounds having polar groups and polymerizable unsaturated bonds include the compounds exemplified as unsaturated hydrocarbons having polar groups in sections

[0208] to

[0211] of Japanese Patent Publication No. 2011-122146.

[0124] Specific examples of aromatic vinyl compounds and functional group-containing styrene derivatives include the compounds exemplified in

[0211] of Japanese Patent Publication No. 2011-122146. A preferred embodiment of the manufacturing method of the present invention is a copolymerization of the α-olefin (Z-1) and the cyclic olefin (Z-2). In this embodiment, ethylene is preferred as the α-olefin (Z-1), and tetracyclo[4.4.0.1 2,5 .1 7,10]-3-dodecene, 1,4-dihydro-1,4-methanonaphthalene, 1,4-methano-1,4,4a,9a-tetrahydrofluorene, bicyclo[2,2,1]hepta-2-ene, and methylphenylnorbornene are preferred.

[0125] In copolymerizing the α-olefin (Z-1) and the cyclic olefin (Z-2), the pressure of the α-olefin (Z-1) and the concentration of the cyclic olefin (Z-2) can be set arbitrarily and are not particularly limited. The pressure of the α-olefin (Z-1) is preferably the polymerization pressure, and the concentration of the cyclic olefin (Z-2) is 0.001 to 100 mol / L, preferably 0.01 to 10 mol / L, and more preferably 0.1 to 1 mol / L.

[0126] The present invention's method for producing olefin-cyclic olefin copolymers exhibits superior polymerization activity and copolymerizability in copolymerization with linear long-chain olefins such as 1-hexene, compared to conventional techniques using metallocene compounds with cyclopentadienyl ligands. However, in copolymerization with the aforementioned cyclic olefins, it shows excellent polymerization activity and copolymerizability. This is a remarkable result and represents a technique that even those skilled in the art would not easily discover.

[0127] [Olefin-cyclic olefin copolymer] The following olefin-cyclic olefin copolymers can be obtained by the production method of the present invention. (molecular weight) The molecular weight of the olefin-cyclic olefin copolymer according to the present invention is a value determined from the intrinsic viscosity measured at 135°C in decalin, and is preferably 0.1 or more and 10.0 or less. The lower limit is more preferably 0.2, and even more preferably 0.4. On the other hand, the upper limit is more preferably 8.0, and even more preferably 7.0.

[0128] The olefin-cyclic olefin copolymer according to the present invention, provided its intrinsic viscosity is within the above range, offers a good balance of moldability, strength, and transparency, and can be suitably used even when strength (toughness) is required as a mechanical property.

[0129] <Glass transition temperature> As described above, the olefin-cyclic olefin copolymer according to the present invention exhibits a high glass transition temperature, for example, 100°C to 250°C. The lower limit is preferably 110°C. On the other hand, from the viewpoint of the heat resistance stability of the polymer during melt molding, the upper limit is more preferably 230°C, and even more preferably 220°C.

[0130] The glass transition temperature values ​​mentioned above were obtained under the following conditions or equivalent conditions. Measurement conditions: Using a differential scanning calorimeter (SII Nanotechnology DSC6220), approximately 5.0 mg of the sample (olefin-cyclic olefin copolymer) is heated from 30°C to 300°C at a heating rate of 10°C / min under a nitrogen atmosphere, and held at that temperature for 5 minutes. (However, for copolymers that decompose in the temperature range of 250°C to 320°C, the holding temperature may be adjusted to a lower temperature as per conventional methods.) The sample is then cooled to 0°C at a cooling rate of 10°C / min, held at that temperature for 5 minutes, and then heated to 300°C at a heating rate of 20°C / min. During this second heating, the DSC curve bends due to the change in specific heat, and the baseline is perceived as having shifted in parallel. The temperature at the intersection of the tangent to the baseline at a temperature lower than this bend and the tangent to the point where the slope is maximum in the bent portion is defined as the glass transition temperature (Tg).

[0131] (Composition of copolymer) The olefin-cyclic olefin copolymer according to the present invention comprises an olefin structural unit derived from (Z-1) and an olefin structural unit derived from (Z-2), and has a structure in which these are linked together.

[0132] Assuming the total olefin structural units are 100 mol%, the preferred lower limit for the content of structural units derived from (Z-1) is 40 mol%, more preferably 50 mol%, and even more preferably 60 mol%. The preferred upper limit is 90 mol%, and even more preferably 80 mol%. On the other hand, the preferred lower limit for the content of structural units derived from (Z-2) is 10 mol%, more preferably 20 mol%. On the other hand, the preferred upper limit is 60 mol%, more preferably 50 mol%, and even more preferably 40 mol%.

[0133] The higher the content of structural units derived from (Z-2), the higher the glass transition temperature tends to be. The olefin-cyclic olefin copolymer may contain other structural units as needed. Examples include conjugated diene compounds such as butadiene and isoprene, unconjugated diene compounds such as 1,5-hexadiene, 4-methyl-1,5-hexadiene, and 7-methyl-1,6-octadiene, and aromatic vinyl compounds such as styrene. The content of structural units derived from such compounds is preferably 10 mol% or less, more preferably 5 mol% or less, and even more preferably 3 mol% or less, when the total olefin structural units are considered to be 100 mol%.

[0134] The olefin-cyclic olefin copolymer according to the present invention can be used without limitation in the applications of conventional cyclic olefin copolymers, such as optical products like plastic lenses and packaging materials like films. [Examples]

[0135] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.

[0136] [Measurement method] [Structure of transition metal compounds] The structure of transition metal compounds is, 1 The determination was made using 1H-NMR spectroscopy (400 MHz, JEOL ECZ400S).

[0137] [Intrinsic viscosity of olefin-cyclic olefin copolymers] Measurements were taken at 135°C in decalin.

[0138] [Cyclic olefin content in olefin-cyclic olefin copolymers] A correlation equation was previously established between the cyclic olefin content of olefin-cyclic olefin copolymers and the glass transition temperature (Tg) measured by DSC (Differential Scanning Calorimeter). The cyclic olefin content was then calculated from the Tg measured by DSC using this correlation equation.

[0139] The cyclic olefin content of the standard olefin-cyclic olefin copolymer is as described in sections

[0216] to

[0219] of Japanese Patent Publication No. 2011-122146. 13 This was determined by 13C-NMR spectroscopy.

[0140] [Glass transition temperature (Tg) of olefin-cyclic olefin copolymers] The Tg of the copolymer was determined by DSC measurement under the following conditions or equivalent conditions. Equipment: SII Nanotechnology Co., Ltd. DSC6220 Measurement conditions: Approximately 5.0 mg of the sample (olefin-cyclic olefin copolymer) is heated from 30°C to 300°C at a heating rate of 10°C / min under a nitrogen atmosphere and held at that temperature for 5 minutes. It is then cooled to 0°C at a cooling rate of 10°C / min and held at that temperature for 5 minutes, after which it is heated again to 300°C at a heating rate of 20°C / min. During this second heating, the DSC curve bends due to the change in specific heat, and the baseline is perceived as having shifted in parallel. The temperature at the intersection of the tangent to the baseline at a temperature lower than this bend and the tangent to the point where the slope is maximum in the bent portion is defined as the glass transition temperature (Tg).

[0141] [Production of transition metal compounds (a1)] The transition metal compound (a1) was synthesized according to the method described in Organometallics, 2000, 19, 2994-3000. Its structure is shown below.

[0142] [ka]

[0143] The transition metal compound (a2)(A-2) was synthesized by the method shown below. (Synthesis of ligand (a2-L)) A 100 mL three-necked flask equipped with a three-way stopcock and a magnetic stirrer was thoroughly purged with nitrogen. Then, 2055 mg (4.71 mmol) of Tris(1-adamantyl)phosphine, 50 mL of toluene, and 800 mg (6.94 mmol) of trimethylsilyl azide were added to the flask, and the mixture was heated under reflux for 16 hours. After returning to room temperature and removing the solvent under reduced pressure, the mixture was washed with hexane. The resulting solid was dried under reduced pressure to obtain 2353 mg (white powder, 95% yield) of the target product represented by the following formula [hereinafter referred to as ligand (a2-L)]. Identification was performed as follows: 1 The results were obtained from 1H-NMR (CDCl3) measurements. 1 H-NMR(400MHz,CDCl3)δ 2.21-1.67(45H,m)ppm, 0.05(9H,s)ppm

[0144] [ka]

[0145] (Synthesis of transition metal compound (a2)) After sufficiently replacing the atmosphere in a 100 mL three-necked flask equipped with a three-way stopcock and a magnetic stirrer with nitrogen, 2353 mg (4.49 mmol) of the ligand (a2-L) obtained in the previous reaction and 45 mL of toluene were added to the three-necked flask. Subsequently, 4.5 mL of a 1.0 mol / L TiCl₄ (4.5 mmol) / toluene solution was gradually added, followed by heating under reflux for 17 hours. After cooling to room temperature, 4.5 mL of a 1.0 mol / L TiCl₄ (4.5 mmol) / toluene solution was added to the solution, followed by heating under reflux for 22 hours. After cooling to room temperature, the solvent was distilled off under reduced pressure, and the residue was washed with hexane. The obtained solid was added to a 100 mL three-necked flask equipped with a three-way stopcock and a magnetic stirrer, and 40 mL of toluene was added thereto. After adding a solution obtained by dissolving 380 mg (2.00 mmol) of TiCl₄ in 2 mL of toluene, the mixture was heated under reflux for 18 hours. After cooling to room temperature, the solvent was distilled off under reduced pressure, and the residue was washed twice with hexane. The obtained solid was dried under reduced pressure to obtain 2502 mg (yellow powder, yield 92%) of the target product represented by the following formula (hereinafter also referred to as "transition metal compound A-2"). Identification was carried out 1 based on the measurement results of ¹H-NMR (CDCl₃). 1 ¹H-NMR (400 MHz, CDCl₃) δ 2.67-1.76 (45H, m) ppm

[0146]

Chemical Formula

[0147] As the transition metal compound (d-1), "titanium(IV) chloride tetrahydrofuran complex" purchased from Sigma-Aldrich Co. LLC was used as it was. The structure thereof is described below.

[0148]

Chemical Formula

[0149] As the transition metal compound (d-2), "cyclopentadienyltitanium(IV) trichloride" purchased from Strem Chemicals, Inc. was used as it was. The structure thereof is described below.

[0150] [ka]

[0151] The transition metal compound (d-3) was synthesized according to the method described in Organometallics, 2003, 22, 1937-1947. Its structure is shown below.

[0152] [ka]

[0153] [Manufacturing of olefin and cyclic olefin copolymers] [Example 1] In a 500 mL glass reactor with a volume of 100 ml, which had been thoroughly purged with nitrogen, 250 mL of cyclohexane / hexane (9 / 1) mixed solution and 60 mmol of tetracyclododecene (hereinafter also referred to as "TD") were charged, and the liquid and gas phases were saturated with ethylene at 50 L / hr. Then, 0.50 mmol of triisobutylaluminum (calculated in terms of aluminum atoms) was added, followed by 0.002 mmol of the above transition metal compound (a1) and 0.008 mmol of triphenylcarbenium tetrakis(pentafluorophenyl) borate, and polymerization was started. Ethylene was continuously supplied at 50 L / hr, and polymerization was carried out at atmospheric pressure and 50°C for 10 minutes, after which polymerization was stopped by adding a small amount of methanol. After polymerization was complete, the reaction product was added to 1 L of acetone / methanol (3 / 1) mixed solvent containing a small amount of hydrochloric acid, and the polymer was precipitated. After washing with the same solvent, it was dried under reduced pressure at 130°C for 10 hours to obtain ethylene-tetracyclododecene copolymer, which is an olefin-cyclic olefin copolymer.

[0154] Table 1 shows the polymerization activity (kg-polymer / mmol-Ti) and physical properties of the ethylene-tetracyclododecene copolymer calculated from the weight (g) of the obtained ethylene-tetracyclododecene copolymer and the amount of transition metal compound (a1) added (mmol-Ti).

[0155] [Example 2] Except for changing the transition metal compound (a1) used in Example 1 to the above-mentioned transition metal compound (a2), the same procedure as in Example 1 was performed to obtain an ethylene-tetracyclododecene copolymer, which is an olefin-cyclic olefin copolymer. Table 1 shows the polymerization activity and the physical properties of the resulting ethylene-tetracyclododecene copolymer.

[0156] [Comparative Example 1] Except for changing the transition metal compound (a1) used in Example 1 to the above-mentioned transition metal compound (d-1), the same procedure as in Example 1 was performed to obtain an ethylene-tetracyclododecene copolymer, which is an olefin-cyclic olefin copolymer. Table 1 shows the polymerization activity and the physical properties of the resulting ethylene-tetracyclododecene copolymer.

[0157] [Comparative Example 2] Except for changing the transition metal compound (a1) used in Example 1 to the above-mentioned transition metal compound (d-2), the same procedure as in Example 1 was performed to obtain an ethylene-tetracyclododecene copolymer, which is an olefin-cyclic olefin copolymer. Table 1 shows the polymerization activity and the physical properties of the resulting ethylene-tetracyclododecene copolymer.

[0158] [Comparative Example 3] Except for changing the transition metal compound (a1) used in Example 1 to the above-mentioned transition metal compound (d-3), the same procedure as in Example 1 was performed to obtain an ethylene-tetracyclododecene copolymer, which is an olefin-cyclic olefin copolymer. Table 1 shows the polymerization activity and the physical properties of the resulting ethylene-tetracyclododecene copolymer.

[0159] [Reference example 1] Into a glass reactor with an internal volume of 500 mL that had been sufficiently purged with nitrogen, 250 mL of toluene was charged, and the liquid phase and gas phase were saturated with ethylene at 100 L / hr. Thereafter, 0.20 mmol of triisobutylaluminum calculated in terms of aluminum atoms, then 0.005 mmol of the above transition metal compound (a1), and 0.0065 mmol of triphenylcarbenium tetrakis(pentafluorophenyl)borate were added to initiate polymerization. Ethylene was continuously supplied at 100 L / hr, polymerization was carried out at 50°C under normal pressure for 5 minutes, and then the polymerization was terminated by adding a small amount of methanol. After completion of the polymerization, the reaction product was added into 750 mL of methanol containing a small amount of hydrochloric acid to precipitate the polymer. After washing with the same solvent, the product was dried under reduced pressure at 80°C for 10 hours to obtain an ethylene polymer. The polymerization activity and physical property values of the obtained ethylene polymer are shown in Table 1.

[0160] [Reference Example 2] An ethylene polymer was obtained by performing the same procedure as in Example 1, except that the transition metal compound (a1) used in Reference Example 1 was changed to the above transition metal compound (d-3). The polymerization activity and physical property values of the obtained ethylene polymer are shown in Table 1.

[0161] [Reference Example 3] Into a glass reactor with an internal volume of 500 mL that had been sufficiently purged with nitrogen, 250 mL of toluene was charged, and the liquid phase and gas phase were saturated with ethylene at 100 L / hr. Thereafter, 10 mL of 1-octene, 0.50 mmol of triisobutylaluminum calculated in terms of aluminum atoms, then 0.01 mmol of the above transition metal compound (a2), and 0.012 mmol of triphenylcarbenium tetrakis(pentafluorophenyl)borate were added to initiate polymerization. Ethylene was continuously supplied at 100 L / hr, polymerization was carried out at 60°C under normal pressure for 10 minutes, and then the polymerization was terminated by adding a small amount of methanol. After completion of the polymerization, the reaction product containing a small amount of hydrochloric acid was added into 1 L of a mixed solvent of acetone / methanol (3 / 1) containing a small amount of hydrochloric acid to precipitate the polymer. After washing with the same solvent, the product was dried under reduced pressure at 120°C for 10 hours to obtain an ethylene·1-octene copolymer. Table 1 shows the polymerization activity and the physical properties of the resulting ethylene-1-octene copolymer.

[0162] [Reference example 4] An ethylene-1-octene copolymer was obtained by performing the same procedure as in Example 1, except that the transition metal compound (a2) used in Reference Example 3 was replaced with the above-mentioned transition metal compound (d-3). Table 1 shows the polymerization activity and the physical properties of the resulting ethylene-1-octene copolymer.

[0163] [Table 1] TD: Tetracyclo[6.2.1.1 3,6 .0 2,7 ] Dodeka-4-en

Claims

1. (A) A transition metal compound represented by the following formula [A-1], (B) At least one compound (B) selected from the group consisting of (B-1) organometallic compounds, (B-2) organoaluminum oxy compounds, and (B-3) transition metal compounds that react with (A) to form an ion pair. The method is characterized by copolymerizing an olefin (X) and a cyclic olefin (Y) in the presence of an olefin polymerization catalyst containing the following: The olefin (X) is a linear or branched α-olefin having 2 to 30 carbon atoms. A method for producing an olefin-cyclic olefin copolymer, wherein the cyclic olefin (Y) is a cyclic olefin represented by the following formulas: [ZI], [Z-II], [Z-III], [Z-IV], [ZV], or [Z-VI]: (A) Transition metal compounds represented by the following formula [A-1] (PI)-M-Ln... [A-1] [In the formula, M is a titanium atom; PI is a ligand independently represented by the following formula [A-2]: 【Chemistry 1】 In formula [A-2], R 1 ~R 3 These may be the same or different from each other, and are a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms, a halogen atom, a halogen-containing group, a silicon-containing group, an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, or a phosphorus-containing group, R 1 ~R 3 Two or more of these groups may be bonded to each other to form a ring; L is selected from hydrogen atoms, halogen atoms, hydrocarbon groups having 1 to 40 carbon atoms, silicon-containing groups, oxygen-containing groups, nitrogen-containing groups, and conjugated diene derivative groups, and is a ligand other than a cyclopentadienyl type ligand and the aforementioned PI ligand; n is an integer between 1 and 6 that satisfies the valence of M, and if n is 2 or greater, multiple Ls may be the same or different from each other. 【Chemistry 2】 [In formula [ZI], u is either 0 or 1, v is 0 or a positive integer, and w is 0 or 1. R 61 to R 78 and R a1 and R R1 are each independently selected from a hydrogen atom, a halogen atom, and a hydrocarbon group. R 75 to R 78 may be bonded to each other to form a monocycle or polycycle, and such monocycle or polycycle may have a double bond. R 75 and R 76, or R 77 and R 78, may form an alkylidene group. 【Transformation 3】 [In equation [Z-II], x and d are integers of 0 or greater than or equal to 1, y and z are 0, 1, or 2. R81 to R99 are each independently selected from a hydrogen atom, a halogen atom, and a hydrocarbon group. The carbon atoms to which R89 and R90 are bonded may be directly bonded to the carbon atoms to which R93 is bonded or to the carbon atoms to which R91 is bonded, or via an alkylene group having 1 to 3 carbon atoms. Furthermore, when y=z=0, R95 and R92 or R95 and R99 may be bonded to each other to form a monocyclic or polycyclic aromatic ring. 【Chemistry 4】 [In formula [Z-III], R 100 and R 101 are each independently a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and f is 1 ≤ f ≤ 18.] 【Transformation 5】 [In equation [Z-IV], x is an integer greater than or equal to 0 or 1, R 111 to R 118 are each independently selected from a hydrogen atom, a halogen atom, and a hydrocarbon group, and R 121 to R 124 are each independently selected from a hydrogen atom, a halogen atom, and a hydrocarbon group, and two adjacent groups may be bonded to each other to form a monocyclic or polycyclic aromatic ring. 【Transformation 6】 [In formula [ZV], n and m are each independently 0, 1, or 2, q is 1, 2, or 3, and R18 to R31 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. When q = 1, R28 and R29, R29 and R30, and R30 and R31 may be bonded to each other to form a monocycle or polycycle. When q = 2 or 3, R28 and R28, R28 and R29, R29 and R30, R30 and R31, and R31 and R31 may be bonded to each other to form a monocycle or polycycle. The monocycle or polycycle may have a double bond, and the monocycle or polycycle may be an aromatic ring.] 【Transformation 7】 [In the above general formula (Z-VI), n and q are each independently 0, 1, or 2. R1 to R17 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 one of R10 to R17 is a bond. Also, when q = 0, R10 and R11, R11 and R12, R12 and R13, R13 and R14, R14 and R15, and R15 and R10 may bond to each other to form a monocycle or polycycle. Furthermore, when q = 1 or 2, R 10 and R 11, R 11 and R 17, R 17 and R 12, R 12 and R 13, R 13 and R 14, R 14 and R 15, R 15 and R 16, R 16 and R 16, R 17 and R 17, and R 16 and R 10 may be bonded to each other to form a monocycle or polycycle, and the monocycle or polycycle may have a double bond, and the monocycle or polycycle may be an aromatic ring.

2. In the above general formula [A-1], R in formula [A-2] 1 ~R 3 The method for producing an olefin / cyclic olefin copolymer according to claim 1, wherein the alkyl group is linear, branched, or cyclic with 1 to 20 carbon atoms, or an aryl group with 6 to 20 carbon atoms.

3. The olefin (X) is ethylene, and the cyclic olefin (Y) is tetracyclo[4.4.0.1 2,5 1. 7,10 A method for producing an olefin / cyclic olefin copolymer according to claim 1 or 2, wherein the copolymer is a cyclic olefin selected from ]-3-dodecene, 1,4-dihydro-1,4-methanonaphthalene, 1,4-methano-1,4,4a,9a-tetrahydrofluorene, bicyclo[2,2,1]hepta-2-ene, and methylphenylnorbornene.

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